Technical Field

The present disclosure relates to a wallpaper laminate, an article using the same, and an intermediate member and a roll body for a wallpaper laminate.

Background

In recent years, adhesive articles, which are pasted to wall surfaces for use, have been developed.

Patent Document 1 (JP 2020-531641 A) includes an adhesive article for attaching an object to a wall surface, including: a first adhesive layer; a nonwoven layer adjacent to the first adhesive layer and defining a periphery, the nonwoven layer containing a nonwoven layer material and including a first major surface and a second major surface; a first arrangement pattern of recessed portions on at least the first major surface of the nonwoven layer, each of the recessed portions terminating at a film containing the nonwoven layer material; and an adhesive interface on a bottom wall surface, the adhesive interface including a contact between the first adhesive layer and the film.

Patent Document 2 (JP 2016-002403 A) discloses a self-adhesive hook in which a back surface of a hook main body integrally provided with a hook piece at a lower end of a surface thereof is detachably stuck to a target wall surface by self-adhesion, wherein the back surface of the hook main body is provided with an adhesive sheet having: an acrylic foam adhesive layer having a surface adhered to the back surface; and a polyurethane self-adhesive layer having a surface adhered to the back surface of the acrylic foam adhesive layer, and wherein the adhesive sheet is stuck in a state where a non-sticky site exists which is non-sticky to upper, lower, left, and right peripheral edges of the back surface of the hook main body, and is provided, at a lower end thereof, with a glue inhibiting portion that is non-sticky to the target wall surface.

Summary

For example, a wallpaper is hung to a wall surface in a house in some cases. Typically, the wallpaper has an uneven pattern formed on its surface to impart a design, or is formed using a variety of materials such as a polyvinyl chloride resin containing a plasticizer that can have a negative impact on adhesiveness, or a polyolefin resin that is resistant to adhesion. Therefore, pasting an adhesive article to a wallpaper while maintaining a good retention force was difficult as compared with pasting the adhesive article to concrete wall surfaces, painted wall surfaces, or the like. In some cases, the wallpaper is composed of a foam, for example. Therefore, the wallpaper is a material that is brittle as compared with concrete wall surfaces, painted wall surfaces, or the like, and is susceptible to damage such as tearing. Therefore, even if an adhesive article could be pasted to the wallpaper while maintaining a good retention force, it was difficult to peel the adhesive article from the wallpaper without pressure-sensitive adhesive residue and without damaging the wallpaper.

The present disclosure provides a wallpaper laminate that can maintain a good retention force when applied to a wallpaper and that can be peeled while reducing or suppressing pressure- sensitive adhesive residue and damage to the wallpaper when peeled from the wallpaper, an article using the same, and an intermediate member and a roll body for a wallpaper laminate.

An embodiment of the present disclosure provides a wallpaper laminate including, in order: a first release liner having a fluorine-based release layer or a non-fluorine-based and non- silicone-based release layer; a first pressure-sensitive adhesive layer containing a modified silicone; a nonwoven layer having a basis weight of 12 g/m ² or greater; a second pressure-sensitive adhesive layer containing a modified silicone; and a second release liner having a fluorine-based release layer or a non-fluorine-based and non-silicone-based release layer, the wallpaper laminate having an embossed pattern, the first pressure-sensitive adhesive layer being applicable to and peelable from a wallpaper.

Another embodiment of the present disclosure provides an article including a base, wherein the wallpaper laminate is pasted to a base surface on a back side of the article via the second pressure-sensitive adhesive layer, and wherein the base surface has at least one recessed portion.

Another embodiment of the present disclosure provides a wallpaper laminate including, in order: a first release liner having a fluorine-based release layer or a non-fluorine-based and non- silicone-based release layer; a first pressure-sensitive adhesive layer containing a modified silicone; a foamed layer; a second pressure-sensitive adhesive layer containing a modified silicone; and a second release liner having a fluorine-based release layer or a non-fluorine-based and non- silicone-based release layer, the first pressure-sensitive adhesive layer being applicable to and peelable from a wallpaper.

Another embodiment of the present disclosure provides an intermediate member for use in the wallpaper laminate, including, in order: a release liner having a release layer; a pressure- sensitive adhesive layer containing a modified silicone; and a release liner having a release layer, wherein either one of the two release liners constitutes the first release liner or the second release liner, and wherein the pressure-sensitive adhesive layer constitutes the first pressure-sensitive adhesive layer or the second pressure-sensitive adhesive layer. Another embodiment of the present disclosure provides a roll body for use in the wallpaper laminate, including, in order: a release liner having a release layer on both sides; and a pressure-sensitive adhesive layer containing a modified silicone, wherein the release liner constitutes the first release liner or the second release liner, and wherein the pressure-sensitive adhesive layer constitutes the first pressure-sensitive adhesive layer or the second pressure- sensitive adhesive layer.

The present disclosure can provide a wallpaper laminate that can maintain a good retention force when applied to a wallpaper and that can be peeled while reducing or suppressing pressure- sensitive adhesive residue and damage to the wallpaper when peeled from the wallpaper, an article using the same, and an intermediate member and a roll body for a wallpaper laminate.

The above description will not be construed to mean that all embodiments of the present invention and all advantages of the present invention are disclosed.

Brief Description of the Drawings

FIG. 1 is a schematic cross sectional view of a wallpaper laminate according to an embodiment of the present disclosure.

FIG. 2 is a schematic cross sectional view of a wallpaper laminate having an embossed pattern according to an embodiment of the present disclosure in a state where a release liner is removed.

FIG. 3 is a schematic illustration of an embossed pattern according to an embodiment of the present disclosure.

FIG. 4 is a schematic illustration of an embossed pattern according to another embodiment of the present disclosure.

FIG. 5 is a schematic diagram of an article according to an embodiment of the present disclosure when peeled from a wallpaper.

FIG. 6 is (a) a rear view, (b) a plan view, (c) a front view, (d) a side view, and (e) a bottom view of the article prior to pasting the wallpaper laminate according to an embodiment of the present disclosure.

FIG. 7 is (a) a side view and (b) a bottom view of the article prior to pasting the wallpaper laminate according to another embodiment of the present disclosure.

FIG. 8 is a schematic diagram of an article according to an embodiment of the present disclosure applied to a wallpaper when detached from the wallpaper.

FIG. 9 is a schematic cross sectional view of an intermediate member according to an embodiment of the present disclosure. FIG. 10 is a schematic cross sectional view of a roll body according to an embodiment of the present disclosure.

Detailed Description

Representative embodiments of the present invention will now be described in greater detail with reference to the drawings as necessary to illustrate the embodiments, but the present invention is not limited to these embodiments.

In the present disclosure, “applicable to and peelable from a wallpaper” means that, when a wallpaper laminate is pasted to a wallpaper via a first pressure-sensitive adhesive layer, the wallpaper laminate is retained without being peeled from the wallpaper while exhibiting the desired retention force, and, on the other hand, that, when the wallpaper laminate is peeled from the wallpaper, it can be peeled without pressure-sensitive adhesive residue on a wallpaper surface after peeling while reducing or suppressing damage to the wallpaper. In an embodiment, “peelable” can mean that the wallpaper laminate can be peeled without using any special jig, with a moderate force (e.g., force of an adult female), without tearing a wallpaper.

In the present disclosure, “islands-in-the-sea structure” means a structure in which non- continuous non-embossed portions, which serve as island portions, are disposed in continuous embossed portions that serve as sea portions, as illustrated in FIG. 3, and, additionally, a structure having at least two straight or non-straight continuous embossed portions (sea portions) in at least one direction, in which a non-embossed portion (island portion) is disposed between the embossed portions, as illustrated in FIG. 4.

In the present disclosure, “(meth)acrylic” means acrylic or methacrylic, and “(meth)acrylate” means acrylate or methacrylate.

In the present disclosure, “non-fluorine-based and non-silicone-based” means that a material is non-fluorine-based and non-silicone-based. That is, the material to be used is neither a fluorine-based material nor a silicone-based material.

As used herein, “curing” may also encompass concepts commonly referred to as “crosslinking”.

As used herein, a “film” also encompasses an article referred to as a “sheet”.

In the present disclosure, “substantially” means including a variation due to, for example, a manufacturing error and is intended to permit a variation of approximately ±20%.

In the present disclosure, for example, “on” in the phrase “a release layer disposed on a substrate” means that the release layer is disposed directly on the substrate, or a release layer is indirectly disposed above the substrate via another layer.

In the present disclosure, for example, “in ordef ’ in “a laminate comprising (including), in order, a first release liner, a first pressure-sensitive adhesive layer, and a nonwoven layer” means that, when focusing on three components, i.e., a first release liner, a first pressure-sensitive adhesive layer, and a nonwoven layer, the laminate includes these components in this order. Any other layer, such as a print layer, may be interposed between these components, e.g., between the first release liner and the first pressure-sensitive adhesive layer.

FIG. 1 is a schematic cross sectional view of a wallpaper laminate (sometimes referred to simply as a “laminate”) according to an embodiment of the present disclosure. A wallpaper laminate 100 in FIG. 1 includes, in order, a first release liner 101, a first pressure-sensitive adhesive layer 103, a core layer 105 as a nonwoven layer or a foamed layer, a second pressure- sensitive adhesive layer 107, and a second release liner 109. In a case where the core layer is a nonwoven layer, the wallpaper laminate of the present disclosure has an embossed pattern as illustrated in FIGS. 2 to 4.

In an embodiment, both the first release liner and the second release liner of the present disclosure have a fluorine-based release layer or a non-fluorine-based and non-silicone-based release layer disposed on a substrate, and are applied to the first pressure-sensitive adhesive layer or the second pressure-sensitive adhesive layer via the release layer. Such release layers can exhibit good peelability performance with respect to the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer of the present disclosure containing a modified silicone, as compared with typical silicone-based release layers. Especially, from the perspective of lifting or peeling of the release liners in the embossed laminate, manufacturing cost, or the like, the release layers are preferably non-fluorine-based and non-silicone-based release layers (also referred to as “NSNF release layers”).

The release layers in the first release liner and the second release liner may be the same or different. Here, examples of a configuration in which the release layer is different includes a configuration in which the release layers are different in type of material, for example, the release layer of the first release liner is a fluorine-based release layer, and the release layer of the second release liner is a non-fluorine-based and non-silicone-based release layer, or the release layer of the first release liner is a non-fluorine-based and non-silicone-based release layer, and the release layer of the second release liner is a fluorine-based release layer. The release layers of the first release liner and the second release liner are both fluorine-based release layers (or non-fluorine- based and non-silicone-based release layers), but also encompass a configuration in which a peel strength of the first pressure-sensitive adhesive layer with respect to the release layer of the first release liner and a peel strength of the second pressure-sensitive adhesive layer with respect to the release layer of the second release liner differ.

From the perspective of usability of the wallpaper laminate, the peel strength of the first pressure-sensitive adhesive layer with respect to the release layer of the first release liner and the peel strength of the second pressure-sensitive adhesive layer with respect to the release layer of the second release liner preferably differ by approximately 2.0 times or greater, approximately 2.5 times or greater, or approximately 3.0 times or greater, and approximately 20 times or less, approximately 10 times or less, approximately 5.0 times or less, approximately 4.5 times or less, or approximately 4.0 times or less. As regards the peel strengths of both the pressure-sensitive adhesive layers, the peel strength of the first pressure-sensitive adhesive layer with respect to the release layer of the first release liner may be higher, or the peel strength of the second pressure- sensitive adhesive layer with respect to the release layer of the second release liner may be higher.

The fluorine-based release layer is not particularly limited, and can be formed by using at least one type of fluorine-based release agent such as a coating agent in which a fluorine resin such as a fluorocarbon-containing material such as a perfluoroalkyl group-containing vinyl ether polymer, a fluorosilicone-containing material, tetrafluoroethylene, or trifluoroethylene is dispersed in a binder resin. As such a fluorine-based release layer, fluorine-based release layers as described in US 4,472,480, US 4,980,443, and US 4,736,048 can be suitably used.

For example, the type and amount of the fluorine-based release agent used in each release layer can be appropriately adjusted to differentiate the peel strengths described above using the fluorine-based release agent.

The non-fluorine-based and non-silicone-based release layers are not particularly limited, and, for example, can be formed using at least one type of (methjacrylic release agent.

In an embodiment, as the (methjacrylic release agent, there can be used a (methjacrylic release agent containing a poly (methjacrylic ester and having a storage modulus from approximately 1.0 ^c 10 ² to approximately 3.0 x 10 ⁶ Pa at 20°C and 1 Hz frequency, the (methjacrylic release agent being used to form a release layer exhibiting a contact angle of approximately 15° or greater with respect to a mixed solution of methanol and water (volume ratio: 90/10) with a wet tension of 25.4 mN/m. This contact angle is advantageous because it effectively suppresses wet spreading of the pressure-sensitive adhesive over a surface of the release layer of the acrylic release agent and tends to be able to reduce affinity with the pressure- sensitive adhesive.

The storage modulus can be approximately 5.0 ^c 10 ² Pa or greater, approximately 1.0 ^c 10 ³ Pa or greater, or approximately 1.5 ^c 10 ³ Pa or greater, and approximately 3.0 ^c 10 ⁶ Pa or less, approximately 1.0 ^c 10 ⁵ Pa or less, or approximately 1.0 ^c 10 ⁴ Pa or less.

Here, in the present disclosure, the storage modulus (G') of the (methjacrylic release agent is a value measured in a shear mode at 20°C and a frequency of 1 Hz using a viscoelastic apparatus (e.g., TA Instruments Japan Inc., rotational rheometer ARES-G2). For example, the contact angle can be approximately 20° or greater, approximately 25° or greater, or approximately 30° or greater, and can be approximately 55° or less, approximately 50° or less, or approximately 45° or less.

Here, in the present disclosure, “contact angle” is defined as a value of a contact angle measured by a mixed solution of methanol and water (volume ratio: 90/10) having a wet tension of 25.4 mN/m, as described in JIS K 6768: 1999. This measurement is performed at a temperature of 23 ± 1°C and a relative humidity of 50 ± 5%.

The (meth)acrylic release agent is a polymer composition containing a polymer such as a poly (meth)acrylic ester.

Examples of poly (meth)acrylic acid esters are copolymers formed from (meth)acrylic monomer components including a (meth)acrylate having an alkyl group with 12 or greater carbon atoms (also referred to as “first alkyl (meth)acrylate”) and a (meth)acrylate having an alkyl group with 12 or less carbon atoms (also referred to as “second alkyl (meth)acrylate”). The first alkyl (meth)acrylate and the second alkyl (meth)acrylate may both have an alkyl group with 12 carbon atoms.

The alkyl group of the first alkyl (meth)acrylate is typically such that it can constitute a relatively long side chain in such a copolymer. Such a long alkyl side chain is effective to lower surface energy of the release layer. Here, this surface energy is estimated by the contact angle as described above. The number of carbon atoms in the alkyl group of the first alkyl (meth)acrylate can be 14 or greater, 18 or greater, 20 or greater, or 24 or greater. An upper limit value of the number of carbon atoms may be, for example, 36 or less, 34 or less, 32 or less, or 30 or less.

From the perspective of peeling force and the like, the long alkyl side chain is preferably free of a polar functional group such as a carboxyl group, a hydroxyl group, or a nitrogen-or phosphorus-containing group. Examples of preferred first alkyl (meth)acrylates include lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, and behenyl (meth)acrylate. The first alkyl (meth)acrylate can be used alone, or two or more thereof can be used in combination.

The alkyl group of the second alkyl (meth)acrylate is typically such that it can constitute a relatively short side chain in the copolymer. Such a short alkyl side chain can reduce a glass transition temperature of the release agent to approximately 30°C or lower. According to this, the storage modulus can also be reduced to from approximately 1 ^c 10 ² to approximately 3 ^c 10 ⁶ Pa, thus providing a non-jerky peel between the release layer formed by the (methjacrylic release agent and the pressure-sensitive adhesive layer. The number of carbon atoms in the alkyl group of the second alkyl (methjacrylate can be 10 or less, 8 or less, or 6 or less. A lower limit value of the number of carbon atoms can be, for example, one or greater, two or greater, or three or greater. From the perspective of peeling force and the like, the short alkyl side chain is preferably free of the polar functional group described above, similarly to the alkyl side chain of the first alkyl (meth)acrylate.

A proportion of the two (meth)acrylic monomer components described above in the copolymer is not particularly limited. For example, the first alkyl (meth)acrylate or the second alkyl (meth)acrylate preferably is contained in an amount from approximately 10 to approximately 90 mass% based on the total mass of the first alkyl (meth)acrylate and the second alkyl (meth)acrylate, from the perspective of non-jerky peelability. For example, by adjusting the proportions of the first alkyl (methjacrylate and the second alkyl (methjacrylate, the above- described peel strengths can be differentiated. For example, the peel strengths can be controlled by appropriately adjusting the proportion of each of the first alkyl (methjacrylate and the second alkyl (methjacrylate within a range selected from: approximately 10 mass% or greater, approximately 20 mass% or greater, approximately 30 mass% or greater, or approximately 40 mass% or greater, and approximately 90 mass% or less, approximately 80 mass% or less, approximately 70 mass% or less, or approximately 60 mass% or less.

In an embodiment, the poly (methjacrylic acid ester is derived from a monomer component that includes an alkyl (methjacrylate having a branched alkyl group with 8 or greater carbon atoms. The number of carbon atoms in the branched alkyl group can be 10 or greater, 14 or greater, 18 or greater, 20 or greater, or 24 or greater. An upper limit value of the number of carbon atoms may be, for example, 36 or less, 34 or less, 32 or less, or 30 or less.

Examples of the alkyl (methjacrylate having a branched alkyl group with 8 or greater carbon atoms include 2-ethylhexyl (methjacrylate, 2-hexyldodecyl (methjacrylate, 2- heptylundecyl (methjacrylate, 2-octyldecyl (methjacrylate, 2-decyltetradecyl (methjacrylate, 2- dodecylhexadecyl (methjacrylate, 2-tetradecyloctadecyl (methjacrylate, and isononyl (methjacrylate. Such a (methjacrylate having a branched side chain can reduce storage modulus and surface energy due to its own reduced crystallinity. Therefore, when an alkyl (methjacrylate having a branched alkyl group with 8 or greater carbon atoms is used, two components of the first alkyl (methjacrylate and the second alkyl (methjacrylate as described above may not be used. Among them, 2-hexyldodecyl (methjacrylate, 2-octyldecyl (methjacrylate, 2-dodecylhexadecyl (methjacrylate, 2-decyltetradecyl (methjacrylate, 2-tetradecyloctadecyl (methjacrylate, and isostearyl (methjacrylate are preferred. The poly (methjacrylic acid ester prepared using these (methjacrylates can easily reduce the surface energy of the release layer.

The polymer contained in the (methjacrylic release agent preferably has a weight average molecular weight of approximately 100000 or greater, approximately 300000 or greater, or approximately 500000 or greater, and approximately 2000000 or less, approximately 1500000 or less, or approximately 1000000 or less, from the perspective of peeling force, handleability of the polymerization reaction, and the like. Here, in the present disclosure, the “weight average molecular weight” refers to a weight average molecular weight in terms of polystyrene as measured by gel permeation chromatography (GPC).

A polymerizable precursor composition containing the monomer components described above is generally polymerized in the presence of a polymerization initiator. A polymerization mode may vary, but a polymer having a high molecular weight that is advantageous for coating formation is obtained, and thus solution polymerization is preferred in which a polymerizable component is dissolved in a solvent. When solution polymerization is used, a solution of a polymerization product can be used, as it is, as a (meth)acrylic polymer release agent after the end of the polymerization.

As the polymerization solvent, an aliphatic hydrocarbon such as n-hexane or n-heptane, an ester such as ethyl acetate or butyl acetate, a ketone such as methyl ethyl ketone or methyl isobutyl ketone, or a mixture thereof can be used. A chain transfer agent or a chain extender can also be used from the perspective of molecular weight control.

Examples of the chain transfer agent include thiol compounds such as 2-mercaptoethanol, 3-mercapto-2-butanol, 3 -mercapto-2 -propanol, 3 -mercapto-1 -propanol, dodecanethiol, isooctyl thioglycolate, and 2-mercapto-ethylamine.

Examples of the chain extender include divalent (meth)acrylic monomers such as 1,6- hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate.

In addition, the (meth)acrylic release agent may additionally contain a (meth)acrylic monomer having, in the side chain, an ionizing radiation-active group such as a (meth)acrylic monomer having a benzophenone structure or an acetophenone structure in the side chain. Such monomers may be blended in the polymerizable precursor composition together with the monomer components to constitute a part of the polymer. The ionizing radiation-active group (e.g., benzophenone structure, acetophenone structure) generates radicals by irradiation of ionizing radiation such as electron beam or ultraviolet light. The generated radicals promote crosslinking of the polymerized product of the polymerizable precursor composition and bonding of a cured product resulting from the crosslinking to the substrate. The use of a (meth)acrylic monomer having an ionizing radiation-active group in the side chain can improve, for example, production efficiency of the release layer. The (meth)acrylic monomer having an ionizing radiation-active group in the side chain can be used alone, or two or more thereof can be used in combination.

The solution polymerization of the polymerizable precursor composition can be typically carried out in an inert gas atmosphere, such as nitrogen gas, for approximately 2 hours to approximately 100 hours at a reaction temperature from approximately 50°C to approximately 100°C.

As the polymerization initiator, a common polymerization initiator can be used. Examples of the polymerization initiator include azo-based compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(2- methylpropionic acid) dimethyl (dimethyl 2,2'-azobis(2-methylpropionate)), and peroxides such as benzoyl peroxide and lauroyl peroxide.

An amount of the polymerization initiator to be used is preferably approximately 0.005 parts by mass or greater and approximately 0.5 parts by mass or less, based on 100 parts by mass of the alkyl (meth)acrylate monomer component. By setting the amount of the polymerization initiator to be used to approximately 0.005 parts by mass or greater, a practical polymerization rate can be ensured. By setting the amount of the polymerization initiator to be used to approximately 0.5 parts by mass or less, the molecular weight of the polymerization product can be increased to an extent sufficient for coating formation.

In an embodiment, the release liner is formed by coating the substrate with the release agent described above, and, as necessary, performing drying, curing by heating, curing by ionizing radiation (e.g. electron beam or ultraviolet light), or the like.

The substrate is not particularly limited, and a plastic film such as a polyester (e.g., polyethylene terephthalate, polyethylene naphthalate, or polybutylene terephthalate) or a polyolefin (e.g., polyethylene), or paper (e.g., kraft paper) or a paper substrate coated with such plastic materials can be used.

A thickness of the substrate is not particularly limited, and can be, for example, approximately 10 micrometers or greater, approximately 15 micrometers or greater, or approximately 20 micrometers or greater, and can be approximately 300 micrometers or less, approximately 200 micrometers or less, or approximately 150 micrometers or less.

The amount of the above-described release agent to be applied can be varied depending on the substrate. For example, the release agent is generally applied to a dry thickness of approximately 0.01 micrometers or greater and approximately 10 micrometers or less. For paper substrates where the substrate is coated with a plastic film such as a polyester or a polyolefin, or a paper substrate coated with a plastic material, the dry thickness is generally approximately 0.05 micrometers or greater and approximately 1 micrometer or less. For substrates having absorbency or low smoothness like paper, the dry thickness is generally approximately 0.1 micrometers or greater and approximately 5 micrometers or less.

In an embodiment, the peel strength (without embossing) of the pressure-sensitive adhesive layer with respect to the release layer of the release liner is approximately 10 N/25 m or less, approximately 7.5 N/25 m or less, approximately 5.0 N/25 m or less, approximately 3.0 N/25 m or less or approximately 1.5 N/25 m or less, and approximately 0.01 N/25 m or greater, approximately 0.02 N/25 m or greater, approximately 0.05 N/25 m or greater, approximately 0.10 N/25 m or greater or approximately 0.20 N/25 m or greater. Here, the peel strength is a peel strength when the release liner is peeled in a 180-degree direction at 300 mm/minute based on JIS Z0237. For example, a release liner exhibiting a peel strength of less than approximately 0.3 N/25 mm prior to embossing can be used as a light release liner, and a release liner exhibiting a peel strength of approximately 0.3 N/25 mm or greater can be used as a heavy release liner. Furthermore, in an embodiment, the peel strength (with embossing) of the pressure-sensitive adhesive layer with respect to the release layer of the release liner is approximately 5.0 N/25 m or less, approximately 4.0 N/25 m or less, approximately 3.0 N/25 m or less, approximately 2.5 N/25 m or less or approximately 1.5 N/25 m or less, and approximately 0.01 N/25 m or greater, approximately 0.02 N/25 m or greater, approximately 0.05 N/25 m or greater, approximately 0.10 N/25 m or greater or approximately 0.20 N/25 m or greater.

In the wallpaper laminate of the present disclosure, the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer containing a modified silicone are disposed on both sides of the nonwoven layer or the foamed layer. The surface of the wallpaper to which the wallpaper laminate is applied is formed of various materials (for example, polyvinyl chloride resin and polyolefin resin generally containing a plasticizer). Because the pressure-sensitive adhesive layer of the present disclosure contains a modified silicone, it enables application of the wallpaper laminate to wallpapers made of various materials as described above, and is effective to peel the wallpaper laminate from wallpapers without pressure-sensitive adhesive residue on the wallpapers and without causing any damage such as tearing. Here, in the present disclosure, the “modified silicone” means a silicone in which a functional group (for example, a functional group having a urethane structure) is imparted to the main chain of the silicone. The modified silicone can be used alone, or two or more thereof can be used in combination. Note that the adhesive layer and the nonwoven layer or the foamed layer may be in direct contact, and another layer may be independently present between the adhesive layer and the nonwoven layer or the foamed layer. In an embodiment, there is a resin layer (e.g., a thermoplastic film) between the adhesive layer and the foamed layer.

The first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer may be the same or different. The first pressure-sensitive adhesive layer is applicable to and peelable from the wallpaper. The configuration in which “the pressure-sensitive adhesive layers are different” encompasses a configuration in which the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer both contain a silicone polyurea block copolymer, but are different in pressure-sensitive adhesive force, in addition to a configuration in which the types of materials of the pressure-sensitive adhesive layer are different so that the first pressure-sensitive adhesive layer contains a silicone polyurea block copolymer and that the second pressure-sensitive adhesive layer contains a silicone polyoxamide block copolymer.

In an embodiment, the first pressure-sensitive adhesive layer and the second pressure- sensitive adhesive layer are made of the same material in order to prevent the risk of product failure due to mistaking the pressure-sensitive adhesive surface. In addition, when different pressure-sensitive adhesives are used in the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer, for example, the second pressure-sensitive adhesive layer that appears by first peeling the second release liner and peeling the second release liner can be used as a pressure-sensitive adhesive surface that contacts a hook, a poster, or the like, in consideration of actual use of the obtained laminate. In this case, the peel strength or adhesive force of the second pressure-sensitive adhesive layer can be designed to be lower than the peel strength or adhesive force of the first pressure-sensitive adhesive layer (pressure-sensitive adhesive surface that contacts the wallpaper).

In an embodiment, the elastic moduli of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer at -20°C are each independently approximately 2 ^c 10 ⁵ Pa or greater, approximately 5 ^c 10 ⁵ Pa or greater, or approximately 1 * 10 ⁶ Pa or greater, and approximately 7 ^c 10 ⁷ Pa or less, approximately 3 ^c 10 ⁷ Pa or less, or approximately 2 ^c 10 ⁷ Pa or less. Here, the measurement of the elastic modulus is a value measured using a viscoelasticity measurement apparatus Discovery HR2 (TA Instruments, Delaware, USA) under the following conditions: a parallel plate: f8 mm, a temperature increase rate: 3°C/minute, a measuring temperature range: from -65°C to 150°C, and a frequency: 1 Hz (6.28 radians/second).

In an embodiment, the weight average molecular weights of soft segments (silicone portions) of the modified silicones contained in the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer are each independently approximately 5000 or greater, approximately 10000 or greater, or approximately 15000 or greater and approximately 70000 or less, approximately 60000 or less, or approximately 50000 or less.

The modified silicone is a silicone in which a functional group (for example, a functional group having a urethane structure) is imparted to the main chain of the silicone, and, typically, the silicone portion constituting this main chain constitutes a soft segment, and a functional group portion constitutes a hard segment. In an embodiment, a mass ratio of the soft segment to the hard segment in the modified silicone contained in each of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer is independently soft segment: hard segment = from approximately 1000: approximately 1 to approximately 50: approximately 1, from approximately 900: approximately 1 to approximately 100: approximately 1, or from approximately 600: approximately 1 to approximately 200: approximately 1.

An amount of the modified silicone to be blended in each of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer can be independently, for example, approximately 30 mass% or greater, approximately 35 mass% or greater, approximately 40 mass% or greater, approximately 45 mass% or greater, or approximately 50 mass% or greater, and can be approximately 80 mass% or less, approximately 75 mass% or less, approximately 70 mass% or less, approximately 65 mass% or less, approximately 60 mass% or less, or approximately 55 mass% or less, relative to the total amount of the pressure-sensitive adhesive layers.

In an embodiment, the first pressure-sensitive adhesive layer and/or the second pressure- sensitive adhesive layer contain(s) an MQ resin (sometimes referred to as an “MQ tackilying resin”).

Useful MQ resins include at least one type selected from the group consisting of MQ silicone resins, MQD silicone resins, and MQT silicone resins. These MQ resins may have a number average molecular weight of approximately 100 or greater or approximately 500 or greater and approximately 50000 or less or approximately 20000 or less, and may have a methyl substituent. Here, in the present disclosure, the “number average molecular weight” refers to a number average molecular weight in terms of polystyrene as measured by gel permeation chromatography (GPC).

The MQ silicone resin can include both a non-functional resin and a functional resin. The functional silicone resin has one or more functionalities including, for example, silicon-bonded hydrogen, silicon-bonded alkenyl, or silanol groups.

The MQ silicone resin is a copolymerizable silicone resin having an R' ₃ SiOi/2 unit (M units) and an S1O4/2 unit (Q unit). Such resins are described in, for example, Encyclopedia of Polymer Science and Engineering, vol. 15, John Wiley Sons, New York, (1989), pp. 265 to 270 as well as US 2,676,182 (Daudt et al.), US 3,627,851 (Brady), US 3,772,247 (Flannigan), and US 5,248,739 (Schmidt et ah). MQ silicone resins having functional groups are disclosed, for example, in US 4,774,310 (Butler) which discloses a silyl-hydride group, US 5,262,558 (Kobayashi et ah) which discloses a vinyl group and a trifluoropropyl group, and US 4,707,531 (Shirahata) which discloses a silyl hydride group and a vinyl group. The resins described above may generally be prepared in a solvent. Dried or solventless MQ silicone resins can be prepared in a manner as described in US 5,319,040 (Wengrovius et al.), US 5,302,685 (Tsumura et al.), and WO 4,935,484 A (Wolfgruber et al.).

An MQD silicone resin is a terpolymer having an R' ₃ SiOi _/2 unit (M unit), an S1O _4/2 unit (Q unit), and an R' ₂ Si0 _2/2 unit (D unit) as described in US 5, 110,890 (Butler). An MQT silicone resin is a terpolymer having an R' ₃ SiOi _/2 unit (M units), an S1O _4/2 unit (Q unit), and an R'SiOv unit (T unit) (MQT resin).

The MQ silicone resin is typically supplied in an organic solvent. Examples of commercially available MQ silicone resins include SilGrip (trade name) SR-545 MQ resin in toluene available from Momentive Performance Materials Japan LLC, and MQOH resins in toluene available from PCR, Inc. (Gainesville, Fla.). These organic solutions for the MQ silicone resins may be used as provided from suppliers or may be dried by any number of techniques known in the art to provide the MQ silicone resins with a nonvolatile content of 100 percent. Suitable drying methods include, but are not limited to, spray drying, in-fumace drying, steam separation drying, and the like.

For example, the amount of the MQ resin to be blended in the pressure-sensitive adhesive layer can be approximately 20 mass% or greater, approximately 25 mass% or greater, or approximately 35 mass% or greater, or approximately 45 mass% or greater, and can be approximately 70 mass% or less, approximately 65 mass% or less, approximately 60 mass% or less, or approximately 55 mass% or less, relative to the total amount of the pressure-sensitive adhesive layers. Among these, an amount of the MQ resin to be blended, which is contained in the first pressure-sensitive adhesive layer to be applied to the wallpaper, is preferably approximately 30 mass% or greater, approximately 40 mass% or greater, approximately 45 mass% or greater, or approximately 50 mass% or greater, and is preferably approximately 70 mass% or less, approximately 60 mass% or less, approximately 55 mass% or less, or approximately 50 mass% or less, from the perspective of applicability to and peelability from the wallpaper, and the like. An amount of the MQ resin to be blended, which is contained in the second pressure-sensitive adhesive layer to be applied to a member such as a hook, is preferably approximately 30 mass% or greater, approximately 40 mass% or greater, approximately 45 mass% or greater or approximately 50 mass% or greater, and is preferably approximately 70 mass% or less, approximately 60 mass% or less, approximately 55 mass% or less, or approximately 50 mass% or less, from the perspective of retention of such a members, and the like.

The modified silicone preferably contains at least one type selected from the group consisting of silicone polyurea block copolymers, silicone polyoxamide block copolymers, and silicone polyoxamide-hydrazide block copolymers, from the perspective of applicability to and peelability from the wallpaper, as well as balance of member retention.

In an embodiment, the silicone polyurea block copolymer contains a reaction product of a polydiorganosiloxane diamine sometimes referred to as a “silicone diamine”) and a poly isocyanate, and, optionally an organic poly amine. The silicone polyurea block copolymer can be used alone, or two or more thereof can be used in combination. A suitable silicone polyurea block copolymer is represented by a repeat unit of Formula I:

In Formula I, Rs are preferably each independently an alkyl moiety from 1 to 12 carbon atoms, such as a trifluoroalkyl or vinyl group, or preferably a moiety which may be substituted with a higher alkenyl group represented by the formula R ² (CFB/ _a CFUCFB, wherein R ² is -(CH ₂ ) _b - or (CH2) _C CH=CH-, a is 1, 2, or 3, b is 0, 3, or 6, and c is 3, 4, or 5), a cycloalkyl moiety having from 6 to 12 carbon atoms, a moiety which may be substituted with an alkyl group, a fluoroalkyl group, and a vinyl group, or preferably an aryl moiety having from 6 to 20 carbon atoms, for example, a moiety that may be substituted with an alkyl group, a cycloalkyl group, a fluoroalkyl group, and a vinyl group, alternatively R is a perfluoroalkyl group as described in US 5,028,679, a fluorine-containing group as described in US 5,236,997, or a perfluoroether containing group as described in US 4,900,474 and US 5,118,775; preferably, at least 50% of the R moieties are methyl groups with the remainder being monovalent alkyl or substituted alkyl groups, alkenyl groups, phenyl groups, or substituted phenyl groups having from 1 to 20 carbon atoms; Zs are each a polyvalent group, preferably an arylene group or aralkylene group having from 6 to 20 carbon atoms; preferably an alkylene or cycloalkylene group of from 6 to 20 carbon atoms, preferably Z is 2,6-toluylene, 4,4’-methylenediphenylene, 3,3'-dimethoxy-4,4’-biphenylene, tetramethyl-m- xylylene, 4,4'-methylenedicyclohexylene, 3,5,5-trimethyl-3-methylene cyclamate xylene, 1,6- hexamethylene, 1,4-cyclo hexylene, 2,2,4-trimethylhexylene, and mixtures thereof; Ys are each independently an alkylene group having from 1 to 10 carbon atoms, preferably an aralkylene group or arylene group of from 6 to 20 carbon atoms; Ds are each selected from the group consisting of hydrogen, an alkyl group of from 1 to 10 carbon atoms, phenyl, and a group that is taken together with B or Y to complete the ring structure to form a heterocycle; and, in Formula I, B is a polyvalent group selected from the group consisting of alkylene aralkylene, cycloalkylene, polyethylene oxide, polypropylene oxide, polyalkylene oxides, such as polytetramethylene oxide, and copolymers and mixtures thereof; m is a number from 0 to approximately 1000; n is a number of at least 1; and p is a number of at least 10, preferably from approximately 15 to approximately 2000, more preferably from 30 to 1500.

Useful silicone polyurea block copolymers are published, for example, in US 5,512,650,

US 5,214,119, US 5,461,134, WO 96/17726 A, WO 96/34028 A, WO 96/34030 A, and WO 97/40103 A. Examples of useful silicone diamines used in the synthesis of the silicone polyurea block copolymer include a polydiorganosiloxane diamine represented by Formula (II) below: Preferably, the number average molecular weight of the polydiorganosiloxane diamine is approximately 700 g/mol or greater:

In Formula II, R, Y, D, and p are each as defined above.

Useful polydiorganosiloxane diamines can include any of the polydiorganosiloxane diamines in the scope of Formula II. Among these, from the perspective of applicability to and peelability from the wallpaper, as well as balance of member retention, a polydiorganosiloxane diamine having a number average molecular weight of approximately 700 g/mol or greater, approximately 1000 g/mol or greater, approximately 3000 g/mol or greater, approximately 5000 g/mol or greater, approximately 10000 g/mol or greater, approximately 15000 g/mol or greater, approximately 20000 g/mol or greater, or approximately 25000 g/mol or greater, and approximately 150000 g/mol or less, approximately 100000 g/mol or less, approximately 80000 g/mol or less, approximately 60000 g/mol or less, approximately 50000 g/mol or less, or approximately 40000 g/mol or less can be suitably used.

Suitable synthesis methods of polydiorganosiloxane diamines and polydiorganosiloxane diamines are published, for example, in US 3,890,269, US 4,661,577, US 5,026,890, US 5,276,122, WO 95/03354 A, and WO 96/35458 A.

Examples of useful polydiorganosiloxane diamines include polydimethylsiloxane diamine, polydiphenylsiloxane diamine, polytrifluoropropylmethylsiloxane diamine, polyphenylmethylsiloxane diamine, polydiethylsiloxane diamine, polydivinylsiloxane diamine, polyvinylmethylsiloxane diamine, poly (5-hexenyl) methylsiloxane diamine, and mixtures or copolymers thereof.

Suitable polydiorganosiloxane diamines are commercially available, for example, from Shin-Etsu Silicones of America Inc. (Torrance, California) and Hides America, Inc. The polydiorganosiloxane diamine is preferably substantially pure and can be synthesized in such a manner as published in US 5,214,119. Such high purity polydiorganosiloxane diamines can be synthesized by reacting a cyclic organosilane and a bis(aminoalkyl) disiloxane in a two step reaction step using an anhydrous aminoalkyl functional silanolate catalyst, such as tetramethylammonium-3-aminopropyl dimethylsilanolate, preferably in an amount of less than 1.15 wt.% based on the total amount of the cyclic organosilane. Particularly preferably, the polydiorganosiloxane diamine is synthesized using cesium and rubidium catalysts, and such synthetic methods are published, for example, in US 5,512,650.

The polydiorganosiloxane diamine component may provide a means to adjust the elastic modulus of the synthesized silicone polyurea block copolymer. In general, high molecular weight polydiorganosiloxane diamines can result in low modulus copolymers, whereas low molecular weight polydiorganosiloxane polyamines may result in high elastic modulus copolymers.

Examples of useful polyamines include polyoxyalkylenediamines including polyoxyalkylenediamines available from the trade names JEFF AMINE (trade name) D-230 (i.e., polyoxypropropylene diamine with a number average molecular weight of 230 g/mol),

JEFF AMINE (trade name) D-400 (i.e., polyoxypropylene diamine having a number average molecular weight of 400 g/mol), JEFF AMINE (trade name) D-2000 (i.e., polyoxypropylene diamine having a number average molecular weight of 2000 g/mol), JEFF AMINE (trade name) D- 4000, JEFF AMINE (trade name) ED-2001, and JEFF AMINE (trade name) EDR-148 (i.e., triethylene glycol diamine) from HUNTSMAN (Houston, Texas); polyoxyalkylene triamines including polyoxyalkylene triamines available from HUNTSMAN under the trade names T-403, T-3000 and T-5000; and alkylenediamines containing ethylenediamine and polyalkylene, available from DuPont (Wilmington, Delaware) under the trade names Dytek (trade name) A and Dytek (trade name) EP.

Any poly amine may provide a means to adjust the elastic modulus of the copolymer. By adjusting the concentration, type, and molecular weight of the organic polyamine, the elastic modulus of the silicone polyurea block copolymer can be adjusted.

In an embodiment, the silicone polyurea block copolymer preferably contains approximately 3 mol or less, more preferably from approximately 0.25 mol to approximately 2 mol. Preferably, the polyamine has a number average molecular weight of approximately 300 g/mol or less.

The polyisocyanate is not particularly limited, and for example, a diisocyanate, a triisocyanate, and the like can be used.

Examples of suitable diisocyanates include aromatic diisocyanates such as 2,6-toluene diisocyanate, 2,5-toluene diisocyanate, 2,4-toluene diisocyanate, m-phenylene diisocyanate, p- phenylene diisocyanate, methylenebis(o-chlorophenyl diisocyanate), methylene diphenylene-4,4’- diisocyanate, polycarbonate diimide-modified methylene diphenylene diisocyanate, (4,4’- diisocyanate-3,3', 5,5'-tetraethyl)diphenylmethane, 4,4-diisothianate-3,3’-dimethoxybiphenyl (o- dianisidine diisocyanate), 5-chloro-2, 4-toluene diisocyanate, and l-chloromethyl-2, 4-diisocyanate benzene; aromatic -aliphatic diisocyanates such as m-xylene diisocyanate and tetramethyl-m- xylene diisocyanate; aliphatic diisocyanates such as 1,4-diisocyanate butane, 1,6-diisocyanate hexane, 1,12 diisocyanate dodecane, and 2-methyl- 1,5 -diisocyanate pentane; and cyclic aliphatic diisocyanates such as methylene dicyclohexylene-4, 4’ -diisocyanate, and 3-isocyanatomethyl- 3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, cyclohexylene- 1,4-diisocyanate.

Any triisocyanates capable of reacting with polyamines, particularly polydiorganosiloxane diamines, are suitable. Examples of such triisocyanates include multifunctional isocyanates produced from biurets, isocyanurates, and adducts. Examples of commercially available polyisocyanates include a portion of a series of polyisocyanates available under the trade names DESMODUR (trade name) and MONDUR (trade name) from Bayer AG, under the trade name Duranate (trade name) from Asahi Kasei Corporation, and under the trade name PAPI (trade name) from Dow Plastics Co.

The polyisocyanate is preferably present in a stoichiometric amount based on the amounts of polydiorganosiloxane diamine and optional polyamine.

The silicone polyurea block copolymer can be synthesized, for example, by a solvent- based reaction, a solventless reaction, or a combination thereof. Effective solvent-based steps are described, for example, in Tyagi et al., “Segmented Organosiloxane Copolymers: 2. Thermal and Mechanical Properties of Siloxane-Urea Copolymers”, Polymer, Vol. 25, December issue (1984) and US 5,214,119 (Leir et al.). Useful methods of manufacturing silicone polyurea block copolymers are also described, for example, inUS 5,512,650, US 5,214,119, US 5,461,134, WO 96/35458 A, WO 98/17726 A, WO 96/34028 A, and WO 97/40103 A.

A pressure-sensitive adhesive composition containing the silicone polyurea block copolymer can be prepared, for example, using a solvent-based reaction, a solventless reaction, or a combination thereof.

In the solvent-based reaction, the MQ resin can be introduced before, during, or after the polyamine and poly isocyanate are introduced into a reaction mixture. The reaction of the polyamine with the polyisocyanate may be carried out in a single solvent or in a mixed solvent. Preferably, the solvent does not react with the polyamine or polyisocyanate. Preferably, the starting material and the final product remain completely miscible in the solvent during the polymerization reaction and after the end of the polymerization reaction. These reactions can be carried out at room temperature or at a temperature up to the boiling point of the reaction solvent. The reaction is preferably carried out at an ambient temperature up to approximately 50°C.

In a substantially solventless reaction, the polyamine and polyisocyanate are mixed with the MQ resin in a reaction vessel, and the polyamine and polyisocyanate react to produce a silicone polyurea block copolymer, and the product can react with the MQ resin to produce a pressure-sensitive adhesive composition. One useful method including solvent-based and solventless reactions is performed by preparing a silicone polyurea block copolymer using a solventless reaction and then mixing the silicone polyurea block copolymer with a solution of the MQ resin in a solvent. Preferably, the silicone polyurea block copolymer-based pressure-sensitive adhesive composition may be synthesized by the combination method described above that produces a mixture of the silicone polyurea block copolymer with the MQ resin.

In an embodiment, the silicone polyoxamide block copolymer and silicone polyoxamide- hydrazide copolymer contain at least two repeat units of Formula A: Formula A

In Formula A, each R ¹ is independently alkyl, haloalkyl, aralkyl, alkenyl, or aryl, or aryl substituted with alkyl, alkoxy, or halo; each Y is independently alkylene, aralkylene, or a combination thereof; and each G is independently a bond or a divalent residue corresponding to a diamine of Formula R ³ HN-G-NHR ³ from which two NHR ³ groups are removed; each R ³ is independently hydrogen or alkyl, or each R ³ forms a heterocyclic group with G and nitrogen to which both R ³ and G bind; each n is independently an integer from 0 to 1500; each p is independently an integer from 1 to 10; and each q is independently an integer of 1 or greater. At least 50% of q is an integer of 2.

Suitable alkyl groups for R ¹ in Formula A typically have from 1 to 10, from 1 to 6, or from 1 to 4 carbon atoms. Exemplary alkyl groups include, but are not limited to, methyl, ethyl, isopropyl, n-propyl, n-butyl, and iso-butyl. In many cases, suitable haloalkyl groups for R ¹ merely have some of the hydrogen atoms of the corresponding alkyl group substituted with halogen. Exemplary haloalkyl groups include chloroalkyl and fluoroalkyl groups with from 1 to 3 halo atoms and from 3 to 10 carbon atoms. Suitable alkenyl groups for R ¹ often have from 2 to 10 carbon atoms. Exemplary alkenyl groups often have from 2 to 8, from 2 to 6, or from 2 to 4 carbon atoms, such as ethenyl, n-propenyl, and n-butenyl. Suitable aryl groups for R ¹ have from 6 to 12 carbon atoms. Phenyl is an exemplary aryl group. The aryl group can be unsubstituted or can also be substituted with alkyl (e.g., alkyl having from 1 to 10 carbon atoms, from 1 to 6 carbon atoms, or from 1 to 4 carbon atoms), alkoxy (e.g., alkoxy having from 1 to 10 carbon atoms, from 1 to 6 carbon atoms, or from 1 to 4 carbon atoms, or halo (e.g., chloro, bromo, or fluoro). Suitable aralkyl groups for R ¹ typically have an alkylene group with from 1 to 10 carbon atoms and an aryl group with from 6 to 12 carbon atoms. In some of exemplary aralkyl groups, the aryl group is phenyl and the alkylene group has from 1 to 10 carbon atoms, from 1 to 6 carbon atoms, or from 1 to 4 carbon atoms (i.e., the aralkyl structure is alkylene-phenyl where alkylene binds to a phenyl group). In an embodiment, at least 40 percent and preferably at least 50 percent of R ¹ groups in some repeat units of Formula A are methyl. For example, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98%, or at least 99% of R ¹ groups may be methyl. The remaining R ¹ groups can be selected from alkyl, haloalkyl, aralkyl, alkenyl, and aryl having at least two carbon atoms, and aryl substituted with alkyl, alkoxy, and halo.

Each Y in Formula A is independently alkylene, aralkylene, or a combination thereof. Suitable alkylene groups typically have up to 10 carbon atoms, up to 8 carbon atoms, up to 6 carbon atoms, or up to 4 carbon atoms. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, and the like. Suitable aralkylene groups typically have an arylene group with from 6 to 12 carbon atoms bonded to an alkylene group with from 1 to 10 carbon atoms. In some of exemplary aralkylene groups, the arylene moiety is phenylene. That is, the divalent aralkylene group is phenylene-alkylene wherein the phenylene binds to alkylene having from 1 to 10, from 1 to 8, from 1 to 6, or from 1 to 4 carbon atoms. As used herein, for a Y group, “combination thereof’ means a combination of two or more groups selected from an alkylene group and an aralkylene group. For example, the combination can be a single aralkylene bonded to a single alkylene (e.g., alkylene-arylene-alkylene). In one exemplary alkylene-arylene-alkylene combination, the arylene is phenylene and each alkylene has from 1 to 10, from 1 to 6, or from 1 to 4 carbon atoms.

Each G in Formula A is independently a bond or a residue unit corresponding to a diamine compound of Formula R ³ HN-G-NHR ³ from which two amino groups (i.e.,-NHR ³ groups) are removed. When G is a bond, the copolymer is silicone polyoxamide-hydrazide. In an embodiment, G is a bond and each R ³ is hydrogen.

When g is a residue unit, the copolymer is a silicone polyoxamide. The diamine can have a primary or secondary amino group. The R ³ group is hydrogen or alkyl (e.g., from 1 to 10, from 1 to 6, or from 1 to 4 carbon atoms) or R ³ forms a heterocyclic group with G and nitrogen to which both R ³ and G bind (e.g., R ³ HN-G-NHR ³ is piperazine). In most embodiments, R ³ is hydrogen or alkyl. In many embodiments, both amino groups of the diamine are primary amino groups (i.e., both R ³ groups are hydrogen) and the diamine has the formula H2N-G-NH2.

In an embodiment, G is alkylene, heteroalkylene, arylene, aralkylene, or a combination thereof. Suitable alkylene often has from 2 to 10, from 2 to 6, or from 2 to 4 carbon atoms. Exemplary alkylene groups include ethylene, propylene, butylene, and the like. Suitable heteroalkylenes are often polyoxyalkylenes, such as polyoxyethylene having at least two ethylene units, polyoxypropylene having at least two propylene units, or copolymers thereof. Suitable aralkylene groups typically contain an arylene group having from 6 to 12 carbon atoms bonded to an alkylene group having from 1 to 10 carbon atoms. Some of exemplary aralkylene groups are phenylene-alkylenes wherein phenylene binds to alkylene having from 1 to 10 carbon atoms, from 1 to 8 carbon atoms, from 1 to 6 carbon atoms, or from 1 to 4 carbon atoms. As used herein, for a group G, “combination thereof’ means a combination of two or more groups selected from alkylene, heteroalkylene, polydiorganosiloxane, arylene, and aralkylene. For example, the combination can be aralkylene bound to alkylene (e.g., alkylene-arylene-alkylene). In one exemplary alkylene-arylene-alkylene combination, arylene is phenylene and each alkylene has from 1 to 10, from 1 to 6, or from 1 to 4 carbon atoms.

Each subscript n in Formula A is independently an integer from 0 to 1,500. For example, the subscript n may be an integer of up to 1000, up to 500, up to 400, up to 300, up to 200, up to 100, up to 80, or up to 60, up to 40, up to 20, or up to 10. The value of n is often at least 1, at least 2, at least 3, at least 5, at least 10, at least 20, or at least 40. For example, the subscript n may range from 40 to 1500, from 0 to 1000, from 40 to 1000, from 0 to 500, from 1 to 500, from 40 to 500, from 1 to 400, from 1 to 300, from 1 to 200, from 1 to 100, from 1 to 80, from 1 to 40, or from 1 to 20

Each subscript p is independently an integer from 1 to 10. For example, the value of p is often an integer of up to 9, up to 8, up to 7, up to 6, up to 5, up to 4, up to 3, or up to 2. The value of p may range from 1 to 8, from 1 to 6, or from 1 to 4.

Each subscript q is independently an integer of 1 or greater, and at least 50% of q is an integer of 2. In an embodiment, at least 75%, at least 90%, at least 99%, or all of q is an integer of 2

In an embodiment, the silicone polyoxamide block copolymer and silicone polyoxamide- hydrazide block copolymer tend to be free of groups having the Formula:-R ^a -(CO)-NH- wherein R ^a is alkylene. All carbonylamino groups along the main chain of the copolymer material are a part of an oxalylamino group (e.g., a-(CO)-(CO)-NH-group). That is, any carbonyl group along the main chain of the copolymer material binds to another carbonyl group and is a part of an oxalyl group. More specifically, the copolymer contains a plurality of aminoxalylamino groups.

The silicone polyoxamide block copolymer and silicone polyoxamide-hydrazide block copolymer are linear block copolymers (i.e., they contain hard blocks and soft blocks) and can be elastomers. They tend to have better solvent resistance than known polydiorganosiloxane polyoxamides. Some of copolymers are insoluble and are insoluble, for example, in toluene or even tetrahydrofuran. Here, the following method may determine whether the copolymer is “insoluble” in a particular solvent. Approximately 1 g of a sample copolymer was placed in a jar, approximately 100 g of a desired solvent was added, the jar was sealed and placed on a roller at an ambient temperature for approximately 4 hours. If 90% or greater of the original mass is retained after the sample copolymer is dried to a constant weight, the copolymer sample is considered insoluble.

The silicone polyoxamide block copolymer and silicone polyoxamide-hydrazide block copolymer can be prepared, for example, according to the method of the present disclosure. The following method can be used to manufacture a copolymer material containing at least two repeat units of Formula B :

In Formula B, each R ¹ is independently alkyl, haloalkyl, aralkyl, alkenyl, or aryl, or aryl substituted with alkyl, alkoxy, or halo; each Y is independently alkylene, aralkylene, or a combination thereof; and each G is independently a bond or a divalent residue corresponding to a diamine of Formula R ³ HN-G-NHR ³ from which two -NHR ³ groups are removed; each R ³ is independently hydrogen or alkyl, or R ³ forms a heterocyclic group with G and nitrogen to which both R ³ and G bind; and each n is independently an integer from 0 to 1500.

Suitable examples of R ¹ , Y, G, and R ³ are similar to those described above for Formula A.

A first step of the method of the present disclosure may involve the use of a compound of Formula C: _< Formula C

In Formula C, p is an integer from 1 to 10.

The compound of Formula C contains at least one polydiorganosiloxane segment and at least two oxalylamino groups. The R ¹ group, the Y group, and the subscript n are the same as those described for Formula B and p is an integer from 1 to 10. Each R ² group is independently alkyl, haloalkyl or aryl, or aryl substituted with alkyl, alkoxy, halo, or alkoxycarbonyl, or is Formula D bound via N:

N

A R* Formula D

In Formula D, each R ⁴ is independently hydrogen, alkyl, or aryl, or R ⁴ together form a ring.

Suitable alkyl and haloalkyl groups for R ² in Formula C often have from 1 to 10, from 1 to 6, or from 1 to 4 carbon atoms. Tertiary alkyl (e.g., t-butyl) and haloalkyl groups can be used, but often have primary or secondary carbon atoms directly attached (i.e., bonded) to adjacent oxy groups. Exemplary alkyl groups include methyl, ethyl, n-propyl, iso-propyl, n-butyl, and iso-butyl. Exemplary haloalkyl groups include chloroalkyl and fluoroalkyl groups, wherein some (not all) of the hydrogen atoms on the corresponding alkyl group are replaced by halo atoms. For example, the chloroalkyl or fluoroalkyl groups can be chloromethyl, 2-chloroethyl, 2,2,2-trichloroethyl, 3- chloropropyl, 4-chlorobutyl, fluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 3-fluoropropyl, 4- fluorobutyl, and the like. Suitable aryl groups for R ² include those having from 6 to 12 carbon atoms, such as phenyl. The aryl group can be unsubstituted or may be substituted with alkyl (e.g., alkyl having from 1 to 4 carbon atoms such as methyl, ethyl, or n-propyl), alkoxy (e.g., alkoxy having from 1 to 4 carbon atoms such as methoxy, ethoxy, or propoxy); halo (e.g., chloro, bromo, or fluoro) or alkoxycarbonyl (e.g., an alkoxy carbonyl having from 2 to 5 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, orpropoxycarbonyl).

The compound of Formula C can encompass single compounds (i.e., all of the compounds have the same values for p and n) or can include a plurality of compounds (i.e., the compounds have a different value for p, a different value for n, or different values for both p and n). Compounds with different n values have siloxane chains of different lengths. Compounds having a p-value of at least 2 are chain-extended.

In an embodiment, there is a mixture of a first compound of Formula C where the subscript p is equal to 1 and a second compound of Formula C where the subscript p is at least equal to 2. The first compound can encompass a plurality of different compounds having different n values. The second compound can encompass a plurality of compounds having different p values, different n values, or different values for both p and n. The mixture can contain at least 50 mass% of the first compound of Formula C (i.e., p is equal to 1) and 50 mass% or less of the second compound of Formula C (i.e., p is at least equal to 2) based on the total weight of the first and second compounds in the mixture. In some of the mixtures, the first compound is present in an amount of at least 55 mass%, at least 60 mass%, at least 65 mass%, at least 70 mass%, at least 75 mass%, at least 80 mass%, at least 85 mass%, at least 90 mass%, at least 95 mass%, or at least 98 mass%, based on the total amount of the compound of Formula C. The mixture often contains 50 mass% or less, 45 mass% or less, 40 mass% or less, 35 mass% or less, 30 mass% or less, 25 mass% or less, 20 mass% or less, 15 mass% or less, 10 mass% or less, 5 mass% or less, or 2 mass% or less of the second compound.

Different amounts of the chain-extended compound of Formula C in the mixture may affect the final properties of an elastomeric material of Formula B. That is, the amount of the second compound of Formula C (i.e., p is at least equal to 2) can be advantageously varied to provide an elastomeric material with a series of properties. For example, increasing the amount of the second compound of Formula C can adjust the melt rheology (for example, allow the elastomeric material to flow more easily when present as a melt), adjust the flexibility of the elastomeric material, reduce the elastic modulus of the elastomeric material, or realize a combination thereof.

In the first step of the method of the present disclosure, the compound of Formula C and a molar excess of the diamine of Formula E below are combined under reaction conditions: Formula E

The R ³ and G groups in Formula E are similar to those described for Formula B.

The diamine of Formula E can optionally be classified as organic diamines, or as polydiorganosiloxane diamines with organic diamines such as those selected from alkylene diamines, heteroalkylene diamines, arylene diamines, aralkylene diamines, or alkylene-aralkylene diamines. The diamine can have only two amino groups such that the obtained polydiorganosiloxane polyoxamide and polyoxamide-hydrazide are linear block copolymers which are often elastomeric and melt at elevated temperatures and are soluble in some common organic solvents. The diamine does not have polyamines with more than two primary or secondary amino groups. A tertiary amine that does not react with the compound of Formula C may be present.

Exemplary polyoxyalkylene diamines (i.e., G is heteroalkylene in which the heteroatom is oxygen) include, but are not limited to, those commercially available under the trade names JEFF AMINE (trade name) HK-511 (i.e., polyetherdiamine having both oxyethylene and oxypropylene groups and having a number average molecular weight of 220 g/mol), and JEFF AMINE (trade name) ED-2003 (i.e. polyethylene glycol having a number average molecular weight of 2000 g/mol), in addition to the trade names JEFF AMINE (trade name) D-230,

JEFF AMINE (trade name) D-400, JEFF AMINE (trade name) D-2000, and JEFF AMINE (trade name) EDR-148 listed above from HUNTSMAN (Woodlands, TX).

Exemplary alkylene diamines (i.e., G is alkylene) include, but are not limited to, ethylene diamine, propylene diamine, butylene diamine, hexamethylene diamine, 2-methylpentamethylene 1,5-diamine (i.e., commercially available from Dupont (Wilmington, DE) under the trade name DYTEK (trade name) A, 1,3 -pentane diamine (commercially available from Dupont under the trade name DYTEK (trade name) EP), 1,4-cyclohexanediamine, 1,2-cyclohexanediamine (commercially available from Dupont under the trade name DHC-99), 4,4’-bis(aminocyclohexyl) methane, and 3-aminomethyl-3,5,5-trimethylcyclohexylamine.

Exemplary arylene diamines (i.e., G is arylene such as phenylene) include, but are not limited to, m-phenylene diamine, o-phenylene diamine, and p-phenylene diamine. Exemplary aralkylene diamines (i.e., G is aralkylene such as alkylene-phenyl) include, but are not limited to, 4-aminomethyl-phenylamine, 3-aminomethyl-phenylamine, and 2-aminomethyl-phenylamine. Exemplary alkylene-aralkylene diamines (i.e., G is alkylene-aralkylene such as alkylene- phenylene-alkylene) include, but are not limited to, 4-aminomethyl-benzylamine, 3-aminomethyl- benzylamine, and 2-aminomethyl-benzylamine.

Exemplary hydrazines (i.e., G is a bond) include, but are not limited to, hydrazine and N,N'-diaminopiperazine.

In some of preferred embodiments, the diamine of Formula E is selected from the group consisting of hydrazine, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5- diaminopentane, 2-methyl-l,5-pentanediamine, 1,6-diaminohexane, and m-xylylene diamine.

A reaction of the compound of Formula C with a molar excess of the diamine of Formula E affords an amine terminated polymer of Formula F : , .. Formula F

The reaction can be carried out using a plurality of compounds of Formula C, a plurality of diamines, or combinations thereof. A plurality of compounds of Formula C having different number average molecular weights can be combined, under reaction conditions, with a single diamine or a plurality of diamines. For example, the compound of Formula C may encompass a mixture of materials having different n values, having different p values, or having different values for both n and p. The plurality of diamines can encompass, for example, a first diamine that is an organic diamine and a second diamine that is a polydiorganosiloxane diamine. Similarly, a single compound of Formula C can be combined with a plurality of diamines under reaction conditions.

A condensation reaction of a compound of Formula C with a diamine is often carried out at room temperature or at elevated temperatures (e.g., temperatures of up to approximately 250°C). For example, the reaction can often be carried out at room temperature or at a temperature of up to approximately 100°C. In other Examples, the reaction can be carried out at a temperature of at least approximately 100°C, at least approximately 120°C, or at least approximately 150°C. For example, the reaction temperature is often in the range from approximately 100°C to approximately 220°C, in the range from approximately 120°C to approximately 220°C, or in the range from approximately 150°C to approximately 200°C. The condensation reaction is often completed in less than approximately 1 hour, less than approximately 2 hours, less than approximately 4 hours, less than approximately 8 hours, or less than approximately 12 hours.

The reaction may occur in the presence or absence of a solvent. Suitable solvents typically do not react with reactants or products related to the reaction. Furthermore, a suitable solvent can typically maintain all reactants and all products in the solution throughout the process. Exemplary solvents include, but are not limited to, toluene, tetrahydrofuran, dichloromethane, aliphatic hydrocarbons (e.g., alkanes such as hexane), and mixtures thereof.

After completion of the reaction, excess diamine and solvent, if present, are removed. Excess diamines can be removed, for example, by vacuum distillation.

The resulting amine terminated polymer of Formula F is then treated with an oxalate ester to form a repeat unit of Formula F utilizing an amine end group. Useful oxalate esters have Formula G: ... Formula G

The oxalate of Formula G can be prepared, for example, by reacting an alcohol of the formula R ⁵ -OH with oxalyl dichloride. Commercially available oxalates of Formula G (e.g., from Sigma-Aldrich (Milwaukee, WI) and VWR International (Bristol, CT)) include, but are not limited to, dimethyl oxalate, diethyl oxalate, di-n-butyl-oxalate, di-tert-butyl oxalate, bis(phenyl) oxalate, bis(pentafluorophenyl) oxalate, l-(2,6-difluorophenyl)-2-(2,3,4,5,6-pentachlorophenyl) oxalate, and bis(2,4,6-trichlorophenyl) oxalate.

Particularly useful oxalate esters of Formula G include, for example, oxalate esters of phenol, ethanol, butanol, methylethylketone oxime, acetone oxime, and trifluoroethanol.

Any suitable reactor (e.g., a glass container, or a general container equipped with a stirrer) or process can be used to prepare a silicone polyoxamide block copolymer and a silicone polyoxamide-hydrazide block copolymer according to the method of the present disclosure. The reaction can be carried out using a batch process, a semi-batch process, or a continuous process.

Any existing solvent can be removed from the resulting polydiorganosiloxane polyoxamide or polyoxamide-hydrazide at the end of the reaction. This removal process is often carried out at a temperature of at least approximately 100°C, at least approximately 125°C, or at least approximately 150°C. The removal process is typically carried out at a temperature of less than approximately 300°C, less than approximately 250°C, or less than approximately 225°C.

It may be desirable to perform the reaction in the absence of a solvent. In solvents that are not compatible with reactants or products, the reaction will be incomplete and the degree of polymerization will be low.

The pressure-sensitive adhesive layer of the present disclosure can include, as an optional component, for example, an antioxidant, a UV absorber, a light stabilizer, a thermal stabilizer, a dispersant, a plasticizer, a flow improving agent, a surfactant, a leveling agent, a silane coupling agent, a catalyst, a filler, a pigment, and a dye, within the range that does not inhibit the effects of the present disclosure. The wallpaper laminate of the present disclosure has a nonwoven layer or a foamed layer as a core layer. Here, “core layer” is a layer disposed between the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer of the wallpaper laminate, as illustrated in FIG. 1.

The nonwoven layer of the present disclosure has a basis weight of approximately 12 g/m ² or greater from the perspective of applicability to and peelability from the wallpaper, as well as balance of member retention. In one embodiment, the basis weight of the nonwoven layer is approximately 15 g/m ² or greater, approximately 20 g/m ² or greater, approximately 25 g/m ² or greater, approximately 30 g/m ² or greater, approximately 35 g/m ² or greater, approximately 40 g/m ² or greater, approximately 50 g/m ² or greater, approximately 55 g/m ² or greater, approximately 60 g/m ² or greater, or approximately 70 g/m ² or greater and approximately 260 g/m ² or less, approximately 230 g/m ² or less, approximately 200 g/m ² or less, approximately 150 g/m ² or less, or approximately 130 g/m ² or less. The basis weight is calculated from the weight of a 10 cm x 10 cm sample.

In some embodiments, the nonwoven layer includes a nonwoven substrate. The nonwoven substrate may be a nonwoven or nonwoven web manufactured by any of commonly known processes for manufacturing a nonwoven or nonwoven web. In the present disclosure, “nonwoven” refers to a fabric having a structure of individual fibers or filaments, which is randomly and/or unidirectionally incorporated in a matte form, but does not have an identifiable nature like a knitted fabric.

Nonwoven fabric or nonwoven webs can be formed in a variety of processes, such as meltblowing processes, spunbonding processes, spunlacing processes, bonded carded web processes, air laying processes, and wet laying processes. In some embodiments, the nonwoven layer contains a multilayer nonwoven material, for example, having at least one layer of meltblown nonwoven and at least one layer of spunbond nonwoven, or any other suitable combination of nonwoven materials. For example, the nonwoven layer may be a spunbond-meltbond-spunbond, spunbond-spunbond, or spunbond-spunbond-spunbond multilayer material. In an embodiment, a long fiber-based nylon spunbond nonwoven, a polyester-based spunbond nonwoven, and a polyolefin-based spunbond nonwoven are preferred.

In the present disclosure, “meltblowing” means a method of forming a nonwoven fibrous web by extruding a molten fiber-forming material through a plurality of orifices in a die to form fibers while contacting the fibers with air or other attenuating fluid to thin the fibers into fine fibers and then collecting the fine fibers. An exemplary meltblowing process is taught, for example, in US 6,607,624 (Berrigan et al). “Melt blown fibers” means fibers made by meltblowing or meltblowing processes. In the present disclosure, “spunbonding” and “spunbond process” means a method of forming a nonwoven fibrous web by extruding a molten fiber-forming material as continuous or semi-continuous fibers from a plurality of fine capillaries of a spinneret and then collecting the resulting fine fibers. Exemplary spunbonding processes are disclosed, for example, in US3,802,817 (Matsuki et al.). “Spunbond fibers” and “spunbonded fibers” mean fibers manufactured using spunbonding or spunbonding processes. Such fibers are generally continuous fibers and are sufficiently entangled or point-bonded to form a coherent nonwoven fibrous web. Therefore, it is generally not possible to take out one complete spunbond fiber from a mass of such fibers. The fibers may have a shape such as that described in US 5,277,976 (Hogle et al.) which describes fibers having a non-known shape.

In the present disclosure, “carding” and “carding process” refer to a method of forming a nonwoven fibrous web by processing short fibers with a combing or carding unit, wherein short fibers are separated or broken and aligned in a lengthwise direction to form a fibrous nonwoven web generally oriented in the lengthwise direction. Exemplary carding processes and carding machines are taught in, for example, US 5, 114,787 (Chaplin et al.) and US 5,643,397.

In the present disclosure, “bonded carded web” refers to a nonwoven fibrous web formed by a carding process wherein at least a portion of the fibers are bonded together by a method including, for example, thermal point bonding, self-bonding, hot air bonding, ultrasonic bonding, needle punching, calendering, application of spray adhesives, and the like. Further details regarding the manufacture and properties of nonwoven webs and laminates including nonwoven webs can be found, for example, in US 9,469,091 (Henke et al.), which is incorporated herein by reference in its entirety.

In the present disclosure, “air laying” refers to a process in which bundles of small fibers having a typical length from approximately 3 to approximately 52 millimeters (mm) are separated and taken into supplied air and then typically deposited on a forming screen with the aid of vacuum supply. The randomly oriented fibers may then be bonded to each other using, for example, thermal point bonding, self-bonding, hot air bonding, needle punching, calendaring, spray adhesives, and the like. Exemplary air laying processes are taught, for example, in US 4,640,810 (Laursen et al.).

“Wet laying” in the present disclosure refers to a process in which bundles of small fibers having a typical length from approximately 3 to approximately 52 millimeters (mm) are separated and taken into a supplied liquid, and then typically deposited on a forming screen with the aid of vacuum supply. Water is typically a preferred liquid. Randomly deposited fibers may be further entangled (e.g., hydroentangled) or may be bonded to each other using, for example, thermal point bonding, self-bonding, hot air bonding, ultrasonic bonding, needle punching, calendering, application of spray adhesives, or the tike. Exemplary wet laying and bonding processes are taught, for example, in US 5, 167,765 (Nielsen et al.). Exemplary bonding processes are also disclosed, for example, in US 9,139,940 (Berrigan et al).

The fibrous materials providing useful nonwoven layer can be made of natural fibers (e.g., wood or cotton fibers), synthetic fibers (e.g., thermoplastic fibers), or a combination of natural and synthetic fibers.

Exemplary materials for forming thermoplastic fibers include polyolefins (e.g., polyethylene, polypropylene, polybutylene, ethylene copolymers, propylene copolymers, butylene copolymers, and copolymers and blends of these polymers), polyesters, and polyamides.

The nonwoven substrate constituting the nonwoven layer may be formed from fibers or filaments made of any suitable thermoplastic polymer material. Suitable polymeric materials include, but are not limited to, polyolefins, polyisoprenes, polybutadienes, fluorinated polymers, chlorinated polymers, polyamides, polyimides, polyethers, polyethersulfones, polysulfones, copolymers of polyvinyl acetate and vinyl acetate, such as polyethylene-co-polyvinyl alcohol, polyphosphazenes, polyvinyl esters, polyvinyl ethers, polyvinyl alcohols, and polycarbonates.

Suitable polyolefins include, but are not limited to, polyethylene, polypropylene, poly 1- butene, copolymers of ethylene and propylene, alpha olefin copolymers (e.g., copolymers of ethylene or propylene with 1 -butene, 1 -hexene, 1-octene, and 1-decene), polyethylene-co-1- butene, and polyethylene-co-l-butene-co-l-hexene.

Suitable fluorinated polymers include, but are not limited to, polyvinyl fluoride, polyvinylidene fluoride, copolymers of vinylidene fluoride (e.g., polyvinylidene fluoride-co- hexafluoropropylene), and copolymers of chlorotrifluoroethylene (e.g., polyethylene-co- chlorotrifluoroethy lene) .

Suitable polyamides include, but are not limited to, polyiminoadipoyliminohexamethylene, polyiminoadipoyliminodecamethylene, and polycaprolactam Suitable polyimides include polypyromellitimide.

Suitable polyethersulfones include, but are not limited to, polydiphenyl ether sulfone and polydiphenyl sulfone-co-diphenylene oxide sulfone.

Suitable copolymers of vinyl acetate include, but are not limited to, polyethylene-co-vinyl acetate and copolymers in which at least some of the acetate groups are hydrolyzed to produce various polyvinyl alcohols such as polyethylene-co-vinyl alcohol.

The fibers may be, for example, multi-component fibers having a core of a thermoplastic material and a sheath of another thermoplastic material. The sheath may be melted at a lower temperature than the core, providing a partially random bond between the fibers as a mat of fibers is exposed to a sheath melt. A combination of mono-component fibers having different melting points may also be useful for this purpose.

In some embodiments, a nonwoven or nonwoven web useful in the nonwoven layer according to the present disclosure is at least partially elastic. Examples of polymers for making elastic fibers include thermoplastic elastomers such as ABA block copolymers, polyurethane elastomers, polyolefin elastomers (e.g., metallocene polyolefin elastomers), olefin block copolymers, polyamide elastomers, ethylene vinyl acetate elastomers, and polyester elastomers. ABA block copolymer elastomers are elastomers in which, generally, the A blocks are polystyrenic and the B block is prepared from a conjugated diene (e.g., lower alkylene diene). The A blocks are generally formed mainly from substituted (e.g., alkylated) or unsubstituted styrenic moieties (e.g., polystyrene, poly (alphamethylstyrene), or poly (t-butylstyrene)) and have a number average molecular weight from approximately 4000 to 50000 grams per mol. The B block is generally formed mainly from a conjugated diene (e.g., isoprene, 1,3 -butadiene, or ethylene- butylene monomer) that may be substituted or unsubstituted, and has a number average molecular weight from approximately 5000 to 500000 grams per mol. The A blocks and the B block may be configured in a linear, radial, or star configuration, for example. The ABA block copolymer may contain a plurality of A blocks and/or B blocks, which may be manufactured from the same monomer or different monomers. Typical block copolymers are linear ABA block copolymers in which the A blocks may be the same or different, or block copolymers having four or more blocks that predominantly stop in the A block. A multi-block copolymer may contain a certain proportion of an AB diblock copolymer that tends to form, for example, a more pressure-sensitive adhesive elastomer film segment. Other elastic polymers can be blended with block copolymer elastomers, and various elastic polymers may be blended to provide varying degrees of elastic properties. A number of types of thermoplastic elastomers are commercially available, and examples thereof can include those commercially available from BASF (Florham Park, N. J.) under the trade name “STYROFLEX (trade name)”, those commercially available from Kraton (trade name) Polymers (Houston, Tex.) under the trade name “KRATON (trade name)”, those commercially available from Dow Chemical (Midland, Mich.) under the trade names “PELLETHANE (trade name)”, “INFUSE (trade name)”, “VERSIFY (trade name)”, and “NORDEL (trade name)”, those commercially available from DSM (Heerlen, Netherlands) under the trade name “ARNITEL (trade name)”, those commercially available from E.I. DuPont de Nemours and Company under the trade name “HYTREL (trade name)”, and those commercially available from ExxonMobil (Irving, Tex.) under the trade name “VISTAMAXX (trade name)”, and others.

For example, the nonwoven web can be manufactured by carding, air laying, wet laying, spunlacing, spunbonding, electrospunning, or a melt blowing process such as meltspun or meltblowing, or a combination thereof. Any of the nonwoven webs may be made from a single type of fibers or two or more types of fibers different in thermoplastic polymer type, shape, and/or thickness, and the single fiber type or at least one of the plurality of fiber types may be a multicomponent fiber as described above.

Short fibers may also be present in the web. The presence of short fibers generally results in higher loft (bulk) and lower density webs than webs formed only from meltblown microfibers. Higher loft webs may have less cohesive force at an interface in the nonwoven layer or in a bulk of the nonwoven layer itself, making it easier to separate from one or more pressure-sensitive adhesive layers.

The nonwoven layer may optionally further include one or more layers of scrim. For example, either or both of major surfaces of the nonwoven layer may optionally further include a scrim layer. Scrims are typically reinforcements for woven or nonwoven fabrics made from fibers, and are included in nonwoven articles to provide strength. Suitable scrim materials include, but are not limited to, nylon, polyester, fiberglass, polyethylene, polypropylene, and the like. An average thickness of the scrim may vary. The layer of scrim may optionally be bonded to the nonwoven substrate. Various adhesives can be used to bond the scrim to the nonwoven substrate. Alternatively, the scrim may be thermally bonded to the nonwoven fabric.

The nonwoven webs of the nonwoven layer can also be treated/finished with various techniques to improve properties such as static control, electric polarizability, coloration, flame retardancy, UV stability, absorbency, and other properties that are apparent to those skilled in the art.

Useful nonwoven layers may have any suitable effective fiber diameter (EFD) desired for a particular application. In the present disclosure, “effective fiber diameter” is an apparent diameter of fibers in a fibrous web based on an air permeation test where air at one atmosphere and room temperature is passed through a web sample at a specified thickness and a specified surface velocity (5.3 cm/sec), and a corresponding pressure drop is measured. Based on the measured pressure drop, the effective fiber diameter is calculated in such a manner as described in Davies, C. N., The Separation of Airborne Dust and Particulates, Institution of Mechanical Engineers, London Proceedings, IB (1952). In some embodiments, the fibers of the nonwoven substrate may be approximately 0.1 micrometers or greater approximately 1 micrometer, or greater, approximately 2 micrometers or greater, or approximately 4 micrometers or greater, and approximately 125 micrometers or less, approximately 75 micrometers or less, approximately 50 micrometers or less, approximately 35 micrometers or less, approximately 25 micrometers or less, approximately 20 micrometers or less, approximately 15 micrometers or less, approximately 10 micrometers or less, approximately 8 micrometers or less, or approximately 6 micrometers. For example, the spunbond nonwoven layer typically has an effective fiber diameter of approximately 35 micrometers or less, while the air laid nonwoven layer may have a larger effective fiber diameter of approximately 100 micrometers.

The loft (bulk) of the nonwoven layer can be assessed in solidity. Solidity is determined by dividing a measured value of a bulk density of the nonwoven fibrous web by a density of a material constituting a solid portion of the web. The bulk density of the web can be determined by first measuring the weight of the web (e.g., in a section of 10 cm ^c 10 cm). A measured value of the weight of the web is divided by an area of the web to obtain a basic weight of the web, which is expressed in units of g/m ² . A thickness of the web can be measured by taking (e.g., by die cutting) a disc of a web having a diameter of 135 mm and measuring the web thickness in a state where a 230 g weight having a diameter of 100 mm is centered on the web. The bulk density of the web is determined by dividing the basic weight of the web by the thickness of the web and is expressed in g/m ³ . The solidity is then determined by dividing the bulk density of the nonwoven fibrous web by the density of the material (e.g., polymer) containing solid filaments of the web. A bulk polymer density can be measured by standard means if the supplier does not identify the material density.

The loft is reported as 100% minus solidity (e.g., 7% solidity equals 93% loft). Higher loft is particularly advantageous for nonwoven layers that are pattern embossed. This is because the pressure-sensitive adhesive can flow infiltratively throughout the entire void volume relatively easily during application of thermal energy and/or pressure. In some embodiments, a high loft nonwoven layer can be bonded in an emboss-patteming process to make an array of required recessed portions.

The solidity of the nonwoven layer can be from approximately 2.0% to less than 12.0% (i.e., the loft is from approximately 98.0% to greater than 88.0%). In some embodiments, the solidity of the nonwoven layer can be at most approximately 7.5%, at most approximately 7.0%, or at most approximately 6.5%, and can be at least approximately 5.0%, at least approximately 5.5%, or at least approximately 6.0%.

The foamed layer of the present disclosure may be in the form of a foam having any suitable thickness, composition, and opacity or transparency. The foamed layer can be a monolayer foam or a multilayer foam.

In some embodiments, the foamed layer has a pull tab portion that extends beyond the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer and serves as a handle when the wallpaper laminate is stretched and peeled from the wallpaper. The shape, size, thickness, and transparency of the pull tab portion can be appropriately set in consideration of design, handleability, and the like. In some embodiments, the foamed layer may be a composite in which a film layer is applied to a foam. For example, a composite including a film layer joined to a foam can be formed using any suitable approach including, for example, coextrusion molding of films and foams, comolding, extrusion coating, bonding with a bonding agent, pressure bonding, heat bonding, and combinations thereof if only one member of the film or foam that constitutes the composite is stretched to achieve peeling from the wallpaper, the member should exhibit sufficient physical properties and have sufficient thickness to achieve that purpose.

The foamed layer is typically selected to have mechanical properties suitable for use in the wallpaper laminate. For example, the foamed layer is selected such that it can be stretched (elongated) at least 50 percent in a first direction (e.g., longitudinal direction) without breaking. That is, stretching the foamed layer at least approximately 50 percent without breaking can increase at least one dimension, such as the length of the foamed layer. In some embodiments, the foamed layer can be stretched at least approximately 100 percent, at least approximately 150 percent, at least approximately 200 percent, at least approximately 300 percent, at least approximately 400 percent, or at least approximately 500 percent without breaking. The foamed layer can often be stretched up to 1200 percent, up to approximately 1000 percent, up to approximately 800 percent, up to approximately 750 percent, or up to approximately 700 percent without breaking. These relatively large elongation values can promote stretch peeling of the wallpaper laminate after being applied to the wallpaper.

A Young's modulus of the foamed layer can be an indicator of the resistance of the foamed layer to stretching. In some embodiments, the Young's modulus of the foamed layer can be approximately 520 MPa or less, approximately 345 MPa or less, approximately 170 MPa or less, approximately 70 MPa or less, approximately 20 MPa or less, approximately 7 MPa or less, or approximately 3.4 MPa or less. A lower limit of the Young's modulus of the foamed layer is not particularly limited, and can be, for example, approximately 0.1 MPa or greater, approximately 0.5 MPa or greater, approximately 1.0 MPa or greater, approximately 1.5 MPa or greater, or approximately 2.0 MPa or greater. The Young's modulus can be measured using the ASTM D790- 07 or ASTM D882-02 method.

The foamed layer can be prepared, for example, from polyolefins (e.g., polyethylenes such as high density polyethylene, low density polyethylene, linear low density polyethylene, and linear ultra low density polyethylene, polypropylenes, and polybutylenes), vinyl copolymers (e.g., polyvinyl chloride and polyvinyl acetate), olefin copolymers (e.g. ethylene/methyl acrylate copolymers, ethylene/vinyl acetate copolymers, and ethylene/propylene copolymers), acrylonitrile- butadiene-styrene copolymers, (meth)acrylic polymers and copolymers, polyurethanes, and combinations and formulations thereof. Exemplary formulations can include, for example, polypropylene/polyethylene formulations, polyurethane/polyolefin formulations, polyurethane/polycarbonate formulations, and polyurethane/poly ester formulations. Other suitable formulations may include, for example, formulations of thermoplastic polymers, elastomeric polymers, and combinations thereof. Suitable formulations include, for example, styrene -butadiene copolymers, polychloroprene (i.e. neoprene), nitrile rubber, butyl rubber, polysulfide rubber, cis- 1,4-polyisoprene, ethylene-propylene terpolymers (e.g., EPDM rubber), silicone rubber, silicone polyurea block copolymers, polyurethane rubber, natural rubber, (meth)acrylate rubber, thermoplastic rubber (e.g., styrene-butadiene block copolymers, styrene-isoprene-styrene block copolymers, styrene-ethylene/butylene-styrene block copolymers, and styrene-ethylene/propylene- styrene block copolymers), thermoplastic polyolefin rubber materials, and combinations thereof.

Useful foamed layers are typically flexible, for example, can increase the degree of surface contact between the first pressure-sensitive adhesive layer disposed on the foamed layer and the wallpaper surface. The foamed layer can achieve an elongation from approximately 50 percent to approximately 600 percent (i.e., the foamed layer is stretchable, at least, from approximately 50 percent to approximately 600 percent). An elongation at break of the foamed layer is preferably sufficiently high so as to maintain a state in which the foamed layer is not lost during detachment of the wallpaper laminate from the wallpaper to which the wallpaper laminate is applied.

The foamed layer can often be selected to optimize properties such as flexibility and resiliency. Flexible and resilient polymeric foams are suitable for intended uses in which the wallpaper laminate is applied to wallpapers having recesses and protrusions.

The foamed layer preferably has an foaming ratio of approximately 5 times or greater, approximately 10 times or greater, or approximately 15 times or greater, and approximately 50 times or less, approximately 40 times or less, or approximately 35 times or less, from the perspective of applicability to and peelability from the wallpaper, as well as balance of member retention. The foaming ratio of the foamed layer was determined as follows: an apparent density was measured by a method in accordance with JIS K7222, and a reciprocal thereof was determined as the foaming ratio.

The foamed layer can have any suitable thickness. Suitable foamed layers often have a thickness of at least 100 micrometers, at least 200 micrometers, at least 300 micrometers, at least 400 micrometers, at least 500 micrometers, at least 600 micrometers, or at least 700 micrometers. The thickness may be up to 5.0 mm, up to 4.0 mm, up to 3.0 mm, or up to 2.0 mm. In some embodiments, the foamed layer can be in a multilayer configuration, wherein each layer of the foamed layer can contribute to a variety of properties, such as density, elongation rate, tensile strength, and combinations thereof. Useful polyethylene vinyl acetate copolymer foams are available from Voltek, Division of Sekisui America Corporation (Lawrence, Massachusetts) under the trade names VOLEXTRA (trade name) and VOLARA (trade name) series.

When the foamed layer is in the form of a composite in which a film layer is applied to a foam, the foamed layer can be in a variety of forms, including, for example, a monolayer or multilayer film, a porous film, and combinations thereof. The film layer can include one or greater fillers (e.g., calcium carbonate). The film layer can be a continuous layer or a discontinuous layer. The multilayer film is preferably integrally joined together in the form of a composite film, a laminate film, and combinations thereof. The multilayer film can be prepared using any suitable method including, for example, co-molding, co-extmsion molding, extrusion coating, bonding with a bonding agent, pressure bonding, heat bonding, and combinations thereof.

In embodiments in which the foamed layer includes at least one foam and at least one film layer, the film layer can contain poly(alkylene) copolymers derived from at least two different alkene monomers. The poly (alkylene) copolymer can be a reaction product of an alkene mixture containing 1) a first alkene selected from ethene, propene, and mixtures thereof and 2) a second alkene monomer selected from 1,2-alkenes having from 4 to 8 carbon atoms. For example, the second alkene monomer often has 4, 6, or 8 carbon atoms. That is, the alkene mixture contains 1) ethene, propene, or a mixture thereof and 2) butene, hexane, octane, or a mixture thereof. These copolymers may be prepared using metallocene catalysts. Mixtures or combinations of these copolymers can also be used.

The wallpaper laminate of the present disclosure including the nonwoven layer described above as the core layer has an embossed pattern as illustrated in FIGS. 2 to 4. The embossed pattern may be on only one side of the wallpaper laminate or may be on either side. The embossed pattern is preferably on both sides, from the perspective of applicability to and peelability from the wallpaper, as well as balance of member retention. When the embossed pattern is on both sides, the same pattern may be formed on both sides as illustrated in FIG. 2, or different patterns may be used.

The wallpaper typically has recesses and protrusions, for example, in order to impart a design, is formed of a fragile foam, and is formed using a variety of materials (e.g., plasticizer- containing polyvinyl chloride resin and polyolefin resin). The wallpaper laminate according to the present disclosure, which includes a nonwoven layer, has an embossed pattern, and thus can provide a structure well balanced in adhesiveness and peelability, in which a good retention force can be exerted with respect to such a wallpaper, and, when the laminate is peeled from the wallpaper, the wallpaper laminate can be peeled from the wallpaper while damage such as tearing is reduced or suppressed without any pressure-sensitive adhesive residue. Among the embossed patterns, from the perspective of applicability to and peelability from the wallpaper, as well as balance of member retention, an embossed pattern having an islands-in-the-sea structure in which the embossed portion is a sea portion and the non-embossed portion is an island portion, as illustrated in FIGS. 2 to 4.

The island portions as the non-embossed portions may be formed non-continuously as illustrated in FIG. 3, or may be formed continuously in a direction (e.g., in an x-direction of FIG.

4) as illustrated in FIG. 4. In some embodiments, the embossed portions may be formed non- continuously in the island portions as the non-embossed portions.

If the island portions as the non-embossed portions are formed non-continuously as illustrated in FIG. 3, for example, an array of the island portions in the y-direction and an adjacent array of the island portions in the y-direction may be arranged such that the island portions in both the arrays are asymmetric, as illustrated in FIG. 3, or may be arranged such that the island portions in both the arrays may be symmetric.

The shape of the island portion when the wallpaper laminate is viewed from above can be a substantially polygonal shape (e.g., a substantially triangular shape, a substantially square shape, a substantially rectangular shape, a substantially regular pentagonal shape, a substantially hexagonal shape, a substantially regular octagonal shape, a substantially trapezoidal shape, a substantially diamond-like shape, a substantially star-like shape, or a substantially lattice-like shape), a substantially oval shape, or a substantially straight shape (a substantially striped shape), in addition to the substantially circular shape as illustrated in FIG. 3 and the substantially wave shape as illustrated in FIG. 4, or a combination of these shapes may be used.

FIG. 2 is a schematic cross sectional view of a wallpaper laminate according to an embodiment of the present disclosure having an embossed pattern with a release liner removed. A wallpaper laminate 200 in FIG. 2 includes, in order, a first pressure-sensitive adhesive layer 203, a nonwoven layer 205 as a core layer, and a second pressure-sensitive adhesive layer 207. In an embossed portion and a periphery thereof, the nonwoven layer and the pressure-sensitive adhesive layer are thermally welded by embossing with heating.

Sizes of a shortest pitch spacing b between an island portion and an island portion adjacent thereto and a length a of an emboss top at a position corresponding to the pitch spacing b may be the same or different. From the perspective of releasability of an embossing roll, a and b preferably satisfy the formula A > b. Here, “pitch spacing” in the present disclosure contemplates a distance from a bottommost portion of an island portion to a bottommost portion of an island portion adjacent thereto.

A shape of a top of the island portion may be substantially flat, as illustrated in FIG. 2, or may be substantially convex or substantially concave. The pitch spacing b may be the same or different throughout the entire area. As illustrated in FIG. 2, the pitch spacings b on both upper and lower sides of the laminate may be the same, or different from each other. The pitch spacing b is preferably approximately 0.01 mm or greater approximately 0.05 mm, or greater, or approximately 0.1 mm or greater, and preferably approximately 3.0 mm or less, approximately 2.0 mm or less, or approximately 1.0 mm or less, from the perspective of applicability to and peelability from the wallpaper, as well as balance of member retention.

A depth h of the emboss may be the same or different throughout the entire area in the thickness direction of the laminate. As illustrated in FIG. 2, the depths h of the emboss on both the upper and lower sides of the laminate may be the same, or may be different from each other. The depth h of the emboss can be, for example, approximately 0.01 mm or greater, approximately 0.05 mm or greater, or approximately 0.1 mm or greater, and can be approximately 3.0 mm or less, approximately 2.0 mm or less, or approximately 1.0 mm or less, for example, from the perspective of applicability to and peelability from the wallpaper, as well as balance of member retention.

Here, the depth h of the emboss contemplates a distance from a bottommost portion of the embossed portion to a top of the non-embossed portion.

In the wallpaper laminate of the present disclosure, other layers such as a print layer, a decorative layer, and a masking layer may be optionally disposed between the respective layers (for example, between the pressure-sensitive adhesive layer and the core layer) as long as the effects of the present disclosure are not impaired. Other layers may be applied to the entire surface or partially.

An example of a method of manufacturing the wallpaper laminate of the present disclosure will be indicated below, but the manufacture method is not limited to this method. As the release liner, pressure-sensitive adhesive layer, and core layer (nonwoven layer or foamed layer) employed in this method, those described above can be used similarly.

The pressure-sensitive adhesive can be disposed on the core layer by any known method. For example, the core layer may be directly coated with the pressure-sensitive adhesive, or, for example, the release liner may be coated with the pressure-sensitive adhesive to form a separate layer and then the separate layer may be laminated to the core layer. The latter method is preferred from the perspective of penetration resistance of the pressure-sensitive adhesive into the nonwoven fabric or foam.

A method of applying the pressure-sensitive adhesive to the core layer or the release liner is not particularly limited, and examples of usable methods include solvent coating methods, aqueous coating methods, or hot melt coating methods such as notch bar coating, knife coating, roll coating, reverse roll coating, gravure coating, wire wound rod coating, slot orifice coating, slot die coating, and extrusion coating. After the pressure-sensitive adhesive is applied to the core layer or the release liner, an optional step such as drying or curing may be applied as necessary.

As a method of coating the release liner with the pressure-sensitive adhesive to form a separate layer, there can be indicated a method involving coating a release layer of a release liner with a pressure-sensitive adhesive to form a pressure-sensitive adhesive layer, and then bonding a separate release liner via the release layer to obtain an intermediate member 900 including, in order, a release liner 901, a pressure-sensitive adhesive layer 903, and a release liner 904 as illustrated in FIG. 9; or a method involving coating one of release layers of a release liner having a release layer on both sides with a pressure-sensitive adhesive to form a pressure-sensitive adhesive layer while winding them into a roll to obtain a roll body 1000 as illustrated in FIG. 10. The former intermediate member can be suitably used in a non-continuous batch manufacture method, and the latter roll body can be suitably used in a continuous manufacture method.

Both the intermediate member and the roll body can constitute a portion of the final wallpaper laminate. That is, either one of the two release liners of the intermediate member constitutes the first release liner or the second release liner; the pressure-sensitive adhesive layer can constitute the first pressure-sensitive adhesive layer or the second pressure-sensitive adhesive layer; the release liner of the roll body can constitute the first release liner or the second release liner; and the pressure-sensitive adhesive layer can constitute the first pressure-sensitive adhesive layer or the second pressure-sensitive adhesive layer.

Here, the two release liners included in the intermediate member (i.e., the first release liner and the second release liner) may be the same type of release liners or different types of release liners. In an embodiment, the first release liner and the second release liner are both release liners having a fluorine-based release layer, or the first release liner and the second release liner are both release liners having non-fluorine-based and non-silicone-based release layers. Alternatively, the first release liner and the second release liner can be a release liner having a fluorine-based release layer and a release liner having a non-fluorine-based and non-silicone-based release layer, respectively, or a release liner having a non-fluorine-based and non-silicone-based release layer and a release liner having a fluorine-based release layer, respectively. It is also possible to use release liners having different fluorine-based release layers (or release liners having different nonfluorine and non-silicone-based release layers) as the first release liner and the second release liner.

When the core layer is coated with the pressure-sensitive adhesive, a wallpaper laminate can be obtained by applying an additional release liner onto the pressure-sensitive adhesive layer applied to both sides of the core layer, and applying embossing, cutting, or the like as necessary. A thickness of the pressure-sensitive adhesive layer can be set to be approximately 1 pm or greater, approximately 5 pm or greater, or approximately 10 pm or greater, and approximately 100 pm or less, approximately 80 pm or less, or approximately 50 pm or less. Here, the thickness of the pressure-sensitive adhesive layer is an average value of the thicknesses at at least five arbitrary positions in the pressure-sensitive adhesive layer having a laminate configuration as measured in a cross section in the thickness direction of the laminate configuration using a scanning electron microscope. Such a thickness measurement method can be used similarly for each layer (e.g., substrate and release layer) constituting the laminate described above.

When an intermediate member having a configuration as illustrated in FIG. 9 is used, a wallpaper laminate can be obtained by removing the one release liner 904, applying the pressure- sensitive adhesive layer 903 and the release liner 901 to both sides of the core layer via the pressure-sensitive adhesive layer 903, and applying embossing, cutting, or the like as necessary.

In a case where a roll body having a configuration as illustrated in FIG. 10 is used, a wallpaper laminate can be obtained by unwinding a release liner 1001 and a pressure-sensitive adhesive layer 1003 from the roll body 1000, applying them to both surfaces of the core layer via the pressure-sensitive adhesive layer 1003, and applying embossing, cutting, or the like as necessary.

Embossing is not particularly limited, and may be performed, for example, by passing a wallpaper laminate through at least one patterned (e.g., engraved) embossing roll having an uneven region corresponding to desired arrays of embossed portions; alternatively, embossing may be performed by pressing a wallpaper laminate disposed in at least one patterned (e.g. engraved) embossing die having an uneven region corresponding to desired arrays of embossed portions. The former embossing method is referred to as a rotary embossing method, and the latter embossing method may be referred to as a heat press embossing method. Especially, the rotary embossing method is preferred from the perspective of productivity. When the rotary embossing method is used, it is preferable to use the non-fluorine and non-silicone-based release layer described above as the release layer of the intermediate member or the roll body. Such a release layer can reduce or suppress post-manufacture failures, such as unintended peeling or warping of the release liner, in the wallpaper laminate formed using the rotary embossing method, as compared with the fluorine- based release layer.

Embossing temperature and pressure can be appropriately set according to the types or thicknesses of the release liner, the pressure-sensitive adhesive layer, and the core layer, the size or shape of the embossed pattern required, and the like. For example, the embossing temperature can be approximately 70°C or higher, approximately 80°C or higher, approximately 90°C or higher, or approximately 100°C or higher, and can be approximately 220°C or lower, approximately 200°C or lower, approximately 180°C or lower, or approximately 150°C or lower. The embossing pressure can be approximately 50 N/cm ² or greater, approximately 100 N/cm ² or greater, approximately 150 N/cm ² or greater, approximately 200 N/cm ² or greater, or approximately 250 N/cm ² or greater, and can be approximately 1 kN/cm ² or less, approximately 800 N/cm ² or less, approximately 600 N/cm ² or less, or approximately 500 N/cm ² or less. The wallpaper laminate of the present disclosure can express various favorable performances even when such embossing is applied.

The resulting wallpaper laminate may be cut as necessary. The cutting is not particularly limited, and a publicly known cutting such as laser cutting, die cutting, stamping, crimping, or a combination thereof can be employed.

For example, the wallpaper laminate of the present disclosure can be used in various ways. In some embodiments, the wallpaper laminate is applied, attached, or pressed onto an adherend (e.g., a wallpaper and a member that constitutes an article to be applied to the wallpaper). In this way, the wallpaper laminate contacts the adherend. If a release liner is present, the release liner is removed before the wallpaper laminate is applied, attached, or pressed onto the adherend. In some embodiments, at least a portion of the adherend may be wiped with isopropyl alcohol before the wallpaper laminate is applied, attached, or pressed onto the adherend.

In order to detach the wallpaper laminate from the adherend, at least a portion of the wallpaper laminate may be peeled from the adherend (e.g., peeled or stripped in a 90 degree direction relative to the adherend), or at least a portion of the wallpaper laminate may be elongated (e.g., elongated in parallel to the adherend) and peeled from the adherend. In an embodiment where a pull tab is present, the user can grasp the pull tab and use it to elongate and peel or remove the wallpaper laminate from the wallpaper. In some embodiments, an angle of elongation of the pull tab is typically 35° or less with respect to the wallpaper. Since the wallpaper laminate of the present disclosure employs a pressure-sensitive adhesive layer containing a modified silicone, the wallpaper laminate can be peeled from the wallpaper even if the angle is, for example, greater than 35° and 90° or less.

FIG. 5 illustrates a hook member as an article to which the wallpaper laminate according to an embodiment of the present disclosure is applied, and illustrates a schematic diagram when the hook member is detached from the wallpaper. According to FIG. 5, for example, when attempting to peel the hook member from the wallpaper by grasping a curved hook portion of the hook member, the pressure-sensitive adhesive layer applied to the non-embossed portion can be peeled sequentially from the wallpaper while it is peeled from the non-embossed portion and stretched, so that the hook member can be detached from the wallpaper. In some embodiments, the wallpaper laminate of the present disclosure is used in a state where it is pasted, via the second pressure-sensitive adhesive layer, to a base surface having at least one recessed portion, which is located on a back side of an article provided with a base after removal of the second release liner. The back surface of the article that is pasted to a wall surface or the like in use typically exhibits a substantially flat shape in order to improve adhesiveness with the pressure-sensitive adhesive layer. When the back surface of the article has a substantially flat shape, the pressure-sensitive adhesive layer pasted to the back surface is pasted to the wallpaper while being supported on the entire back surface of the article, so that it is possible to adhere it to the wallpaper on the entire surface of the supported pressure-sensitive adhesive layer. As a result, the pressure-sensitive adhesive layer adheres well to both the wallpaper and the article and thus it may be difficult to detach the wallpaper laminate from the wallpaper or article.

On the other hand, the article of the present disclosure includes a recessed portion 612, as illustrated in FIG. 6(e), on the base surface of the article that adheres to the pressure-sensitive adhesive layer. For example, when the wallpaper laminate is pasted, via the pressure-sensitive adhesive layer, so as to cover the recessed portion 612 illustrated in FIG. 6(e), the pressure- sensitive adhesive layer is supported by the base surface 610 except the recessed portion 612. Because the pressure-sensitive adhesive layer in this state is supported by a part of the base surface, the pressure-sensitive adhesive force between the article and the pressure-sensitive adhesive layer is weaker than the pressure-sensitive adhesive layer supported on the entire surface of the base surface. As a result, the article pasted to the wallpaper via the wallpaper laminate can be easily detached in two stages, as illustrated in FIG. 8. For an article having such a base surface, the wallpaper laminate of the present disclosure can be suitably used. Of these, the wallpaper laminate of the present disclosure including a nonwoven layer as the core layer and having an embossed pattern can be more suitably used because the retention force of the article is excellent and the two-stage detachment of the article can be performed more easily.

The wallpaper laminate of the present disclosure may be applied to the entire surface of the base surface of the article or may be applied to a part of the base surface.

In some embodiments, the configuration of an article having a base surface with at least one recessed portion includes a configuration in which a projection (e.g., a hook portion) sized to be serve as a tab for peeling, as illustrated in FIG. 5, is not disposed on an article surface opposite the wallpaper side. Articles having such a configuration can include, for example, clips, white boards, frames, photographic panels, and mirrors, as illustrated in FIGS. 6 and 7.

Here, a shape of the projection is not particularly limited, and examples thereof include angular and round. In an embodiment, from the perspective of retention force, dimensions of an angular projection having a hook portion can be approximately 15 mm or greater, approximately 20 mm or greater, or approximately 25 mm or greater. An upper limit of the dimensions is not particularly limited, but can be approximately 70 mm or less, approximately 60 mm or less, or approximately 55 mm or less. In addition, a diameter of a round projection having a hook portion can be approximately 20 mm or greater, approximately 30 mm or greater, or approximately 40 mm or greater, from the perspective of retention force, and an upper limit can be approximately 70 mm or less, approximately 60 mm or less, or approximately 50 mm or less. A height (length in the thickness direction) of these angular and round projections varies depending on the shape of the hook portion, but generally, the height can be in the range from approximately 5 mm or greater, approximately 7 mm or greater, or approximately 10 mm or greater to approximately 30 mm or less, approximately 20 mm or less, or approximately 15 mm or less, at the highest point.

FIG. 6 illustrates a substantially circular clip 600 with no projection on the surface as an article to which the wallpaper laminate of the present disclosure can be applied. The clip 600 is attached with a base 601 and a clamping portion 603 via a support member 605. The clip may include a member, such as a spring, formed integrally with or separately from the support member.

For round clips as illustrated in FIGS. 6 and 7, the diameter can be approximately 20 mm or greater, approximately 30 mm or greater, or approximately 40 mm or greater, and approximately 70 mm or less, approximately 60 mm or less, or approximately 50 mm or less.

Also, the height (length in the thickness direction) varies depending on the shape of the clip, but, generally, the height (length in the thickness direction) can be in the range from approximately 5 mm or greater, approximately 6 mm or greater, or approximately 7 mm or greater to approximately 20 mm or less, approximately 15 mm or less, or approximately 10 mm or less.

If a clip having such a structure is detached from the wallpaper, typically the sides of the clip will be pinched with thumb and index finger or the like to be detached. Because the recessed portion 612 is formed in the base surface 601 of the clip 600, even the difficult-to-pinch clip 600 can be easily detached from the wallpaper. Here, the “recessed portion” in the base surface of the present disclosure does not encompass a recessed portion formed for other purposes, such as a recessed portion in a joint portion 607 provided to join the base 601 and the clamping portion 603 of the clip as illustrated in FIG. 6.

The shape, size, and number of the recessed portion and depth of the recessed portion can be set appropriately in consideration of the retaining performance of the article to the wallpaper and the peelability performance from the wallpaper, depending on the intended use.

Examples of the shape of the recessed portion can include substantially polygonal shapes (e.g., a substantially triangular shape, a substantially square shape, a substantially rectangular shape, a substantially regular pentagonal shape, a substantially hexagonal shape, a substantially regular octagonal shape, a substantially trapezoidal shape, a substantially diamond-like shape, and a substantially star-like shape), a substantially circular shape, a substantially oval shape, a substantially semicircular shape, and a substantially semi-oval shape. These shapes can be used alone, or two or more thereof can be used in combination. In a case where the shape of the recessed portion is substantially polygonal, a comer portion may have a curved shape.

The size of the recessed portions can vary depending on the size of the article. For example, the size of the recessed portion can be set as a proportion of the total area of the recessed portion 612 with respect to the total area of the base surface 610 including the recessed portion 612 when viewing the base surface 610 side as illustrated in FIG. 6(e). The proportion of the total area can be, for example, approximately 10% or greater, approximately 20% or greater, approximately 30% or greater, approximately 40% or greater, or approximately 50% or greater, and approximately 95% or less, approximately 90% or less, approximately 80% or less, approximately 70% or less, or approximately 60% or less.

The number of the recessed portions may be, for example, 1 or greater, 2 or greater, 4 or greater, or 6 or greater. An upper limit value of the number of the recessed portions is not particularly limited, and can be, for example, 1000 or less, 700 or less, 500 or less, 300 or less, 100 or less, 80 or less 60, or less, 50 or less, 40 or less, 30 or less, or 20 or less.

A depth of the recessed portion can bet, for example, approximately 0.5 mm or greater, approximately 1 mm or greater, approximately 2 mm or greater, approximately 3 mm or greater, approximately 4 mm or greater, or approximately 5 mm or greater. An upper limit of the depth is not particularly limited but can be, for example, approximately 1 cm or less, approximately 9 mm or less, approximately 8 mm or less, approximately 7 mm or less, approximately 6 mm or less, or approximately 5 mm or less. Here, “depth of the recessed portion” means a distance from the bottommost portion of the recessed portion to the base surface.

FIG. 7 illustrates a substantially circular clip 700 of another embodiment having a configuration without any projection on a surface thereof. This clip 700 has a configuration in which a base 701 and a clamping portion 703 are integrated. The clip has a hooking portion 707 between the base 701 and the clamping portion 703 to aid in clamping an object.

A base surface 710 on the back side of the clip in FIG. 7 has a first recessed portion 712 and a second recessed portion 714. For example, when the wallpaper laminate is applied to cover only these recessed portions, the other recessed portions are not included as the “recessed portion” in the base surface. However, when the wallpaper laminate is applied to cover the entire base surface 710, for example, the other recessed portions are treated as a third recessed portion 722, a fourth recessed portion 724, a fifth recessed portion 726, and a sixth recessed portion 728.

The method of forming a recessed portion is not particularly limited, and examples thereof include injection molding, cutting, and 3D printing. The wallpaper laminate of the present disclosure and article including the laminate are applied to the wallpaper via the first pressure-sensitive adhesive layer. Because such a pressure- sensitive adhesive layer contains the modified silicone described above, it is applicable to and peelable from various wallpapers.

The material of the wallpaper is not particularly limited, and examples thereof can include polyvinyl chloride resins, polyolefin resins, silicone resins, and (meth)acrylate resins. These materials may contain a plasticizer. These wallpaper materials can be used alone, or two or more thereof can be used in combination. For example, an anti-soil layer such as a silicone resin or a protective layer of a polyolefin resin or a (meth)acrylate resin may be applied to the foam of the polyvinyl chloride resin.

The polyolefin resin is at least one type, for example, a single resin such as polyethylene (low density polyethylene (LDPE) or high density polyethylene (HDPE)), polypropylene, polybutene, polybutadiene, or polyisoprene, a copolymer of alpha olefins having 4 or greater carbon atoms (linear low density polyethylene (LLDPE)); an ethylene (meth)acrylic acid-based copolymer such as an ethylene-acrylic acid copolymer, an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, or an ethylene-methacrylic acid copolymer; an ethylene-vinyl acetate copolymer (EVA), an ethylene-vinyl acetate copolymer saponified product, an ethylene- vinyl alcohol copolymer, or an ionomer.

The wallpaper can be a foam or a non-foam. The surface of the wallpaper may be provided with an uneven pattern by embossing or the like. Because the pressure-sensitive adhesive layer of the wallpaper laminate of the present disclosure contains the modified silicone described above, the pressure-sensitive adhesive layer can be applied to and peeled from even a frangible wallpaper such as a foam, and a wallpaper having an uneven pattern due to which the pressure-sensitive adhesive tends to peel off.

The wallpaper laminate of the present disclosure having a nonwoven layer as the core layer is configured to be provided with an embossed pattern, to employ a nonwoven layer having a specific basis weight, a specific pressure-sensitive adhesive layer and a specific release liner, so that, when the laminate is pulled in a direction of, for example, approximately 90 degrees with respect to the wallpaper surface, the laminate can be peeled or stripped from the wallpaper without tearing the wallpaper, and can be applied to and peeled from the wallpaper which is an adherend. Furthermore, the wallpaper laminate of the present disclosure having a foamed layer as the core layer is configured to employ a specific pressure-sensitive adhesive layer and a specific release liner, so that, when the laminate is elongated in a parallel direction, for example, with respect to the wallpaper surface, the laminate can be elongated and peeled from the wallpaper without tearing the wallpaper, and can be applied and peeled from the wallpaper that is an adherend. In some embodiments, the wallpaper laminate of the present disclosure exhibits a retention force of approximately 7000 minutes or longer, approximately 8000 minutes or longer, approximately 9000 minutes or longer, or approximately 10000 minutes or longer in a retention force test which will be described below. An upper limit of the retention force is not particularly limited and can be, for example, approximately 50000 minutes or shorter, approximately 30000 minutes or shorter, or approximately 20000 minutes or shorter.

In some embodiments, the adhesive force of the wallpaper laminate of the present disclosure to the wallpaper is approximately 1.0 N/25 mm or greater, approximately 1.3 N/25 mm or greater, or approximately 1.5 N/25 mm or greater, and approximately 10 N/25 mm or less, approximately 9.5 N/25 mm or less, approximately 9.0 N/25 mm or less, or approximately 8.0 N/25 mm or less in a 90 degree peel strength test which will be described below.

Examples

Specific embodiments of the present disclosure will be exemplified in the following examples, but the present invention is not limited to these embodiments. All parts and percentages are based on mass unless otherwise specified. The numerical value essentially includes errors due to a measurement principle and a measurement apparatus. The numerical value is indicated by a significant number that has undergone a normal rounding treatment.

Experimental Example 1

In Experimental Example 1, a wallpaper laminate prepared using the same release liners as first and second release liners was reviewed. Note that, in Table 3, a difference in embossed pattern was further reviewed, and, in Tables 4 to 6, a difference in nonwoven fabric was further reviewed. Table 1 shows various materials used in Experimental Example 1. Here, “Mw” in the table refers to a weight average molecular weight, “Ra” means a surface roughness, “Sdr” means a “developed area ratio”, “DEHP” means di-2-ethylhexyl phthalate, and “DINP” means a plasticizer dinonyl phthalate.

Table 1

The sample produced was evaluated as follows.

Retention force test: retention force on wallpaper

After washing a wallpaper and a stainless steel panel with isopropyl alcohol, a retention force test was performed as follows:

(1) A double-sided tape (ST-416, available from 3M, St. Paul, Minnesota) was pasted to one side of a stainless steel (SUS304BA) panel of 50 mm ^c 100 mm ^c 1.0 mm. A release paper was peeled from the double-sided tape, and then the wallpaper was pasted onto the double-sided tape while the wallpaper was firmly held down with fingers so as not to be wrinkled. (2) Each of laminates for evaluation was cut to 25 mm ^c 30 mm, and one of release liners in the laminate for evaluation was removed. Then, the laminate was pasted to a stainless steel (SUS304BA) panel of 30 mm ^c 50 mm ^c 1.0 mm, and pressed firmly with fingers. Here, a hole of f 5 mm is provided near a substantially center of one end in the lengthwise direction (long side direction) of the stainless steel panel.

(3) The other release liner of the laminate was removed, and the laminate was pasted to the wallpaper pasted to the stainless steel panel in (1) above such that an end portion provided with the hole of f 5 mm was located at a lower end.

(4) The laminate was pressed for 5 seconds at a static load of approximately 15 kg to obtain a test panel. All test panels were cured for 24 hours at room temperature (23 ± 1°C, 50 ± 5% relative humidity).

(5) After 24 hours, a 200 g weight was hung in the hole located at the lower end of the test panel at room temperature (23 ± 1°C, 50 ± 5% relative humidity), and the retention time for each test panel was recorded.

In the table, for example, “> 10080” means that the retention force is longer than 10080 minutes, and “< 720” means that the retention force is shorter than 720 minutes.

90 Degree peel strength test: adhesive force to wallpaper

After washing the wallpaper and stainless steel panel with isopropyl alcohol, a 90 degree peel strength test was performed as follows:

(1) A double-sided tape (ST-416, available from 3M) was pasted to one side of a stainless steel (SUS304BA) panel of 50 mm ^c 100 mm ^c 1.0 mm. After the release paper of the doublesided tape was peeled, the wallpaper was pasted to the double-sided tape, firmly held down with fingers so as not to be wrinkled, and rolled back and forth one time from the top of the wallpaper at a speed of 300 mm/minute using a 7 kg steel roller to obtain a test substrate.

(2) One of the release liners was removed from a laminate for evaluation having dimensions of 25 mm ^c 40 mm at room temperature (23 ± 1°C and 50 ± 5% relative humidity), and then the laminate was pasted to a wallpaper surface of the test substrate, and rolled back and forth one time at a speed of 300 mm/minute using a 7 kg steel roller, and then pressure bonded.

(3) As a backing material (lining material), a fine paper (180 gsm, MCSPA1R4, available from Epson Corporation) having dimensions of 30 mm ^c 100 mm x 0.21 mm was overlaid on one side of the test sample (a pressure-sensitive adhesive layer surface of the laminate for evaluation) after removal of the other release liner of the laminate for evaluation, and rolled back and forth one time at a speed of 300 mm/minute using a 7 kg steel roller to obtain a test sample.

(4) The test sample was cured at room temperature (23 ± 1°C, 50 ± 5% relative humidity) for two days.

(5) Adhesive force when the test sample was peeled was measured using a universal material tester (TENSILON, available from A & D Company, Limited (Toshima-ku, Tokyo, Japan)) while the fine paper, as the backing material, was pulled at a speed of 300 mm/minute in a 90 degree direction.

Damage-free peel test: confirmation of wallpaper damage and pressure-sensitive adhesive residue

After washing the wallpaper and stainless steel panel with isopropyl alcohol, a damage- free peel test was performed as follows:

(1) A double-sided tape (ST-416, available from 3M) was pasted to one side of a stainless steel (SUS304BA) panel of 50 mm ^c 100 mm ^c 1.0 mm. After the release paper of the doublesided tape was peeled, the wallpaper was pasted to the double-sided tape. The wallpaper was pressed firmly with fingers so as not to be wrinkled.

(2) Each of laminates for evaluation was cut to 25 mm ^c 30 mm, one of the release liner in the laminate for evaluation was peeled, and then the laminate was pasted to a small hook and firmly pressed with fingers.

(3) The other release liner of the laminate was peeled, and the small hook was pasted to the wallpaper pasted to the stainless steel panel in (1) above.

(4) The small hook pasted on the wallpaper was pressed for 5 seconds at a static load of approximately 15 kg to obtain a test panel. All test panels were cured for 1 week at room temperature (23 ± 1°C, 50 ± 5% relative humidity).

(5) After curing, the hook was peeled from the wallpaper by hand, and degrees of damage to the wallpaper, pressure-sensitive adhesive residue on the wallpaper, and soil were visually observed and evaluated based on each of the criteria which will be indicated below. Here, scores 0 to 1 can be evaluated as acceptable levels and scores 2 to 3 can be evaluated as unacceptable levels.

Degree of damage to wallpaper

0: The wallpaper was not damaged.

1: The wallpaper was slightly damaged (less than 10%).

2: The wallpaper was extensively damaged (from 10% to 50%).

3 : The wallpaper was more extensively damaged (from greater than 50% to 100%).

Degree of pressure-sensitive adhesive residue

0: No pressure-sensitive adhesive was left on the wallpaper.

1: The pressure-sensitive adhesive was left slightly on the wallpaper (less than 10%).

2: The pressure-sensitive adhesive was left extensively on the wallpaper (from 10% to

50%). 3 : The pressure-sensitive adhesive was left more extensively on the wallpaper (from greater than 50% to 100%).

Degree of soil

0: No soil was observed.

1 : Soil was observed slightly in a limited area.

2: Soil was observed slightly in all areas.

3 : Soil was clearly observed.

Wettability test: wettability of pressure-sensitive adhesive to wallpaper

After washing the wallpaper with isopropyl alcohol, a wettability test was performed as follows:

(1) A laminate for evaluation was cut to 25 mm ^c 30 mm, pasted to a wallpaper (EB7112) and pressed for 5 seconds at a static load of approximately 15 kg.

(2) The test sample was conditioned on dry ice for 30 minutes and then immediately slit with a razor, and a cross sectional region at an interface between the pressure-sensitive adhesive layer and the wallpaper was observed.

(3) A cross sectional field of view in this cross sectional region was observed using a digital microscope VHX-1000 (available from Keyence Corporation (Osaka-shi, Osaka, Japan)), and the interface between the pressure-sensitive adhesive layer and the wallpaper was digital- imaged.

(4) The wettability (surface contact rate) of the pressure-sensitive adhesive of the laminate for evaluation with respect to the wallpaper surface was calculated based on Formula X below:

Wettability (%)= (contact length of pressure-sensitive adhesive ^c 100)/surface length of wallpaper

Formula X

Here, the surface length of the wallpaper refers to a length of the wallpaper surface forming the interface between the pressure-sensitive adhesive layer and the wallpaper in the cross sectional field of view of the observed test sample. The contact length of the pressure-sensitive adhesive is a value obtained by measuring each length of the wallpaper surface where the pressure- sensitive adhesive layer is not in contact with the wallpaper at the interface between the pressure- sensitive adhesive layer and the wallpaper in the same cross sectional field of view of the test sample also observed, combining the measured lengths, and subtracting the combined value of the lengths of the non-contact areas with respect to the wallpaper of the pressure-sensitive adhesive layer from the surface length of the wallpaper. The measurement was repeated four times and an average value of the measured values is shown in the table.

Analysis of wallpaper

The surface roughness (Ra) and developed area ratio (Sdr) of each of the wallpapers shown in Table 1 were analyzed in accordance with IS025178 using a wide area three- dimensional measuring apparatus (VR-5200, available from Keyence Corporation (Osaka-shi, Osaka, Japan)). In the analysis, the wallpaper was applied onto a stage of the apparatus to observe an area of 24 mm ^c 19 mm.

Surface components of the wallpaper were analyzed using an FT-IR measurement apparatus (Nicolet 6700, available from Thermo), and a concentration of a plasticizer in the wallpaper was analyzed using a GC-MS measurement apparatus (7890A + 5975C, Agilent, available from Technologies).

Example 1

An MQ resin and a modified silicone were added to a 225 ml glass bottle in the prescribed amounts shown in Table 2, and the mixture was subjected to a hybrid mixer (ARE-250, available from Thinky Corporation (Chiyoda-ku, Tokyo, Japan), shaken for 5 minutes at 2000 rpm, and then shaken for at least 12 hours with a roller set to approximately 25 rpm to obtain a pressure-sensitive adhesive composition.

The release liner FD-75 was coated with the pressure-sensitive adhesive composition with a wet gap from 0.25 to 0.26 mm to prepare a pressure-sensitive adhesive layer having a thickness from approximately 0.050 to approximately 0.065 mm. The coated pressure-sensitive adhesive sample was dried in an oven at 70°C for 10 minutes.

A laminate sample was obtained by placing the pressure-sensitive adhesive sample on both sides of a nonwoven layer such that the pressure-sensitive adhesive layer faced the nonwoven layer. This laminate sample was passed through a heat press machine equipped with an embossing die patterned in a substantially hexagonal shape at a pressure of approximately 0.3 kN/cm ² for 1 second at 115°C, and then die cut to a size of 25 ^c 30 mm to obtain a laminate for evaluation. The embossed pattern of the obtained laminate was a substantially hexagonal islands-in-the-sea structure (in which an embossed portion was a sea portion and a non-embossed portion was an island portion). Pitch spacing (pitch spacing b in FIG. 2) of the non-embossed portion (island portion) was from approximately 0.6 to approximately 0.7 mm, and depth of the emboss (emboss depth h in FIG. 2) was approximately 0.1 mm. Examples 2, 4, and 12 to 14

Laminates for evaluation of Examples 2,4, and 12 to 14 were obtained in the same manner as in Example 1 with the exception that a release liner 1 prepared using a precursor polymer 1 which will be described below was used and that the formulation was changed to the formulations in Table 2.

Precursor polymer 1

STA, ISA, and AEBP were mixed such that blending proportions of these monomers were 50.0 parts by mass, 50.0 parts by mass, and 0.2 parts by mass, respectively. The monomer mixture was diluted with a mixed solvent of ethyl acetate/n-heptane (50 mass%/50 mass%) such that a monomer concentration was 50 mass%. Furthermore, V-601 was added as an initiator in a proportion of 0.20 parts by mass based on an alkyl (meth)acrylate monomer component, and the inside of the system was purged with nitrogen for 2 minutes. The reaction was then allowed to proceed for 48 hours in a thermostatic bath at 65°C to obtain a viscous solution precursor polymer 1

Release Liner 1

The precursor polymer 1 was diluted to 1 mass% with a toluene/MEK mixed solvent (50 mass%/50 mass%). A polyester film (EMBLET (trade name) S-50) was coated with the diluted solution using a bar coater (# 04). The solvent was then evaporated to form a release precursor layer having a thickness of approximately 0.1 micrometers.

A release liner 1 was produced by curing the release precursor layer by irradiating the polyester film having the release precursor layer with one pass of ultraviolet light, using an ultraviolet irradiation apparatus (F300, medium pressure mercury lamp (H bulb), Heraeus (Hanau, Hessen, Germany) at a line speed of 20 m/min in a nitrogen gas atmosphere. At the time of irradiation, an amount of ultraviolet light per pass as measured with an actinometer, UV POWER PUCK (trade name) II (available from EIT) was 350 mJ/cm ² (UVA: 168 mJ/cm ² , UVB: 158 mJ/cm ² , and UVC: 24 mJ/cm ² ). Here, for the release liners, for example, the release liner 1 is abbreviated as “Liner 1” in the table. Also, “NSNF-based” in the table means non-fluorine-based and non-silicone-based.

Examples 3, 5 to 7, and 9 to 11

The laminates for evaluation of Examples 3, 5 to 7, and 9 to 11 were obtained in the same manner as in Example 1 with the exception that the formulation was changed to the formulations in Table 2. Here, for Example 11, the nonwoven fabric was also changed to S0703 WDO. Example 8

Aerosil (trade name) R812 and an MQ resin were added to a 225 ml glass bottle and mixed for 5 minutes at 2000 rpm using a hybrid mixer (ARE-250, available from Thinky Corporation (Chiyoda-ku, Tokyo, Japan)). Next, a modified silicone was added, and the mixture was subjected to a hybrid mixer, and shaken for 5 minutes at 2000 rpm, and then shaken with a roller set to approximately 25 rpm for at least 12 hours to obtain a pressure-sensitive adhesive composition.

A laminate for evaluation of Example 8 was obtained in the same manner as in Example 1 with the exception that this pressure-sensitive adhesive composition was used. Comparative Example 1

Dowsil (trade name) 4584 was added to a 225 ml glass bottle, and toluene and Dowsil (trade name) NC-25 was added thereto. The mixture was subjected to a hybrid mixer (ARE-250, available from Thinky Corporation (Chiyoda-ku, Tokyo, Japan), shaken for 5 minutes at 2000 rpm, and then shaken for at least 12 hours with a roller set to approximately 25 rpm to obtain a pressure-sensitive adhesive composition.

A laminate for evaluation of Comparative Example 1 was obtained in the same manner as in Example 1 with the exception that this pressure-sensitive adhesive composition was used and that the nonwoven fabric was changed to T0703 WDO.

The evaluations described above were performed on the laminates for evaluation of Examples 1 to 14 and Comparative Example 1, and the results are shown in Table 2.

Table 2

Examples 15 to 20

Laminates for evaluation of Examples 15 to 20 were obtained in the same manner as in Example 2 with the exception that the formulations shown in Table 3 and the embossed pattern having an islands-in-the-sea structure (in which the embossed portion was a sea portion and the non-embossed portion was an island portion) were employed. Note that, in the embossed patterns shown in Table 3, the pitch spacing of the non-embossed portions (island portions) corresponds to the pitch spacing b in FIG. 2 and the depth of the emboss corresponds to the emboss depth h in FIG. 2.

The evaluations described above were performed on the laminates for evaluation of Examples 15 to 20, and the results are shown in Table 3.

Table 3

Examples 21 to 24

The laminates for evaluation of Examples 21 to 24 were obtained in the same manner as in Example 17 with the exception that the nonwoven fabric was changed to the nonwoven fabrics shown in Table 4.

The evaluations described above were performed on the laminates for evaluation of Examples 21 to 24, and the results are shown in Table 4.

Table 4

Examples 25 to 29

The laminates for evaluation of Examples 25 to 29 were obtained in the same manner as in Example 17 with the exception that the nonwoven fabric was changed to the nonwoven fabrics shown in Table 5.

The evaluations described above were performed on the laminates for evaluation of Examples 25 to 29, and the results are shown in Table 5.

Table 5

Examples 30 to 34

The laminates for evaluation of Examples 30 to 34 were obtained in the same manner as in Example 17 with the exception that the nonwoven fabric was changed to the nonwoven fabrics shown in Table 6.

The evaluations described above were performed on the laminates for evaluation of Examples 30 to 34, and the results are shown in Table 6.

Table 6

Experimental Example 2

In Experimental Example 2, a release liner (sometimes referred to as an “NSNF release liner”) having a non-fluorine-based and non-silicone-based release layer, which was applicable to a pressure-sensitive adhesive layer containing a modified silicone, was reviewed.

Various materials used in Experimental Example 2 are shown in Table 7. Here, for HCA- 32, the reaction conditions and purification method disclosed in Method 2 on page 8 to 9 (column 14, line 63 to column 15, line 8) of US 8,137,807 were used to synthesize HCA-32 (2-tetradecyl octadecyl acrylate) from an esterification reaction of 2-tetradecyl- 1-octadecanol (iso-C32 alcohol) with aery loyl chloride.

Table 7

Precursor polymers 2 to 9

Precursor polymers 2 to 9 were obtained in the same manner as for the precursor polymer 1 described above, with the exception that the formulation was changed to the formulation shown in Table 8.

Table 8

Release liners 2 to 9

Release liners 2 to 9 were obtained in the same manner as for the release liner 1 described above, with the exception that the precursor polymers 2 to 9 shown in Table 8 were used in the release liners 2 to 9, respectively. Here, for the precursor polymers 8 and 9, these precursor polymers were diluted to 1.06 mass% with a toluene/MEK/n-heptane mixed solvent (34 mass%/33 mass%/33 mass%).

Preparation of pressure-sensitive adhesive tape using release liner produced

Samples of tape to be evaluated were prepared in the following two ways.

(1) Apply pressure-sensitive adhesive solution onto release liner produced (direct application)

A pressure-sensitive adhesive solution was prepared by mixing 50 parts by mass of SPU33K and 50 parts by mass of XR37-B1795. The release liner produced was coated with the pressure-sensitive adhesive solution, and dried at 105°C for 10 minutes. The dried pressure- sensitive adhesive layer had a thickness of approximately 50 micrometers. A pressure-sensitive adhesive tape was obtained by applying the release liner FD-75 onto the pressure-sensitive adhesive layer.

(2) Apply release liner produced onto pressure-sensitive adhesive layer (dry lamination)

The release liner FD-75 was coated with the above described pressure-sensitive adhesive solution, and dried at 105°C for 10 minutes. The dried pressure-sensitive adhesive layer had a thickness of approximately 50 micrometers. A pressure-sensitive adhesive tape was obtained by applying the release liner produced onto the pressure-sensitive adhesive layer.

The following evaluations were performed on the produced adhesive tapes, and the results are shown in Tables 9 to 12.

Peel strength test: peel strength of pressure-sensitive adhesive layer to release layer of release liner produced

The release liner FD-75 was peeled from the pressure-sensitive adhesive tape, and a polyester film (COSMOSHINE (trade name) A4100) was pasted to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape. Next, the polyester film and the SUS panel were bonded together via a double-sided tape. The peel strength when the release liner produced (NSNF release liner) was peeled in a 180 degree direction at a peeling rate of 300 mm/minute was measured using a precision universal tester (Shimadzu Corporation (Kyoto-shi, Kyoto, Japan)). Table 9 shows test results of the adhesive tapes prepared by direct application. Table 10 shows test results when the adhesive tapes prepared by direct application were aged for several weeks in an environment at 50°C and 80% RH. Table 11 shows test results of the adhesive tapes prepared by direct application and the adhesive tapes prepared by dry lamination.

Residual adhesive force test

After testing the peel strength, the polyester film with a pressure-sensitive adhesive layer, which was left on the SUS panel, was peeled from the double-sided tape, and the pressure- sensitive adhesive layer exposed to the polyester film was pasted to the SUS304 (BA) panel. After it was left to stand for 30 minutes at room temperature, the adhesive force when the polyester film was peeled at a peeling rate of 300 mm/min in the 180 degree direction was measured as residual adhesive force using a precision universal tester Autograph AG-X (Shimadzu Corporation (Kyoto- shi, Kyoto, Japan)). Note that, in Table 12, the residual adhesive force of the adhesive tapes produced by the direct application method (1) described above using two fluorine-based release liners (FD-75) is shown as Reference Example 1.

Table 9: Direct application

It could be confirmed, from the results in Table 9, that, for example, a light-peeling release liner (peel strength: less than 0.3 N/25 mm) and a heavy-peeling release liner with a peel strength of 0.3 N/25 mm could be produced separately. Table 10: Direct application, 50°C, 80% RH

Table 11 Table 12: Residual adhesive force for directly applied product

From the results in Table 12, it could be confirmed that the residual adhesive force of the pressure-sensitive adhesive layer in the NSNF release liner was equivalent to that of the fluorine- based release liner of Reference Example 1. Experimental Example 3

In Experimental Example 3, a wallpaper laminate prepared using a release liner having a non-fluorine-based and non-silicone-based release layer and a release liner having a fluorine-based release layer was reviewed. Various materials used in Experimental Example 3 are shown in Table 13.

Table 13

Example 59

An MQ resin and a modified silicone were added to a 225 ml glass bottle in the prescribed amounts shown in Table 14, and the mixture was subjected to a hybrid mixer (ARE-250, available from Thinky Corporation (Chiyoda-ku, Tokyo, Japan), shaken for 5 minutes at 2000 rpm, and then shaken for at least 12 hours with a roller set to approximately 25 rpm to obtain a pressure-sensitive adhesive composition.

The fluorine-based release liner FD-75 was coated with the pressure-sensitive adhesive composition with a wet gap from 0.25 to 0.26 mm to prepare a pressure-sensitive adhesive layer having a thickness from approximately 0.050 to approximately 0.065 mm. A coated pressure- sensitive adhesive sample 1 was dried in an oven at 70°C for 10 minutes.

Similarly, a liner 1, which was the NSNF release liner described above was coated with the pressure-sensitive adhesive composition, with a wet gap from 0.25 to 0.26 mm to prepare a pressure-sensitive adhesive layer with a thickness from approximately 0.050 to approximately 0.065 mm. A coated pressure-sensitive adhesive sample 2 was dried in an oven at 70°C for 10 minutes.

A laminate sample was obtained by placing the pressure-sensitive adhesive sample 1 on one side of the nonwoven layer and the pressure-sensitive adhesive sample 2 on the other side of the nonwoven layer so that the pressure-sensitive adhesive layer faced the nonwoven layer. This laminate sample was passed through a heat press machine equipped with an embossing die patterned in a substantially hexagonal shape at a pressure of approximately 0.3 kN/cm ² for 1 second at 115°C, and then die cut to a size of 50 ^c 100 mm to obtain a laminate for evaluation. The embossed pattern of the obtained laminate had a substantially hexagonal islands-in-the-sea structure, in which the pitch spacing of the non-embossed portion (island portion) was from approximately 0.6 to approximately 0.7 mm, and the depth of the emboss was approximately 0.1 mm. On the laminate for evaluation of Example 59, the retention force test, the damage-free peel test, and the following test were performed, and the results are shown in Table 14.

Peel strength test: peel strengths before and after embossing The peeling forces before and after embossing of the NSNF release liner (liner 1) of the laminate for evaluation was evaluated as follows:

(1) A test piece with a width of 25 mm and a length of 100 mm was collected using the laminate for evaluation before and after embossing.

(2) The fluorine-based release liner FD-75 was peeled. (3) After washing the stainless steel (SUS304BA) panel with isopropyl alcohol, the pressure-sensitive adhesive layer surface of the test piece was pasted to the stainless panel surface.

(4) A peel strength when the NSNF release liner (liner 1) of the test piece was peeled in the 180 degree direction at a speed of 300 mm/minute was measured using a universal material tester (TENSILON, available from A & D Company, Limited (Toshima-ku, Tokyo, Japan)). Table 14

Experimental Example 4

In Experimental Example 4, a wallpaper laminate produced using a rotary embossing method was reviewed.

Various materials used in Experimental Example 4 are shown in Table 15.

Table 15

Used was a release liner 11 produced in the same manner as for the release liner 9, with the exception that the substrate of the release liner 9 was changed to EMBLET (trade name) SD- 75; and that the substrates of the release liner 10 produced in the same manner as for the release liner 9 and the release liner 9 were changed to EMBLET (trade name) SD-100, other than the fluorine-based release liner FD-75. Example 60

An MQ resin and a modified silicone were added to a 225 ml glass bottle in the prescribed amounts shown in Table 16, and the mixture was subjected to a hybrid mixer (ARE-250, available from Thinky Corporation (Chiyoda-ku, Tokyo, Japan), shaken for 5 minutes at 2000 rpm, and then shaken for at least 12 hours with a roller set to approximately 25 rpm to obtain a pressure-sensitive adhesive composition a.

A pressure-sensitive adhesive layer was prepared by coating the release liner 10 with the pressure-sensitive adhesive composition a to give a coating amount shown in Table 16. The coated pressure-sensitive adhesive sample was dried in an oven at 70°C for 10 minutes.

A laminate sample was obtained by placing the pressure-sensitive adhesive sample on both sides of a nonwoven layer such that the pressure-sensitive adhesive layer faced the nonwoven layer. The laminate sample was passed through a heat press machine equipped with an embossing die patterned in a substantially hexagonal shape under the embossing conditions shown in Table 17 to obtain a laminate for evaluation. The embossed pattern of the obtained laminate had a substantially hexagonal islands-in-the-sea structure, in which the pitch spacing of the non- embossed portion (island portion) was from approximately 0.6 to approximately 0.7 mm, and the depth of the emboss was approximately 0.1 mm.

Examples 61 to 64

The laminates for evaluation of Examples 61 to 64 were obtained in the same manner as in Example 60, with the exception that the embossing conditions using the rotary embossing method in Example 61; and that, in Examples 62 to 64, the release liner 10 was changed to the release liner 11 and the embossing conditions shown in Table 17 were employed.

Examples 65 to 67

The laminates for evaluation of Examples 65 to 67 were obtained in the same manner as in Example 60 with the exception that the pressure-sensitive adhesive composition a and coating amount were changed to the pressure-sensitive adhesive composition b and coating amount shown in Table 16; that the release liner was changed to FD-75; and that the embossing conditions shown in Table 17 were employed. Table 16

Failures, such as peeling of the release liner, were visually observed immediately after production of the laminates for evaluation of Examples 60 to 67 by the rotary embossing method and at the time of cutting thereof, and evaluated based on the following criteria, and the results are shown in Table 17. In Table 17, the pressure-sensitive adhesive layer located on the top surface of the laminate is referred to as “first pressure-sensitive adhesive layer”, and the pressure-sensitive adhesive layer located on the bottom surface is referred to as a “second pressure-sensitive adhesive layef’. Here, “top surface” of the laminate refers to a surface located on the top roll side of a rotary embossing apparatus, and “bottom surface” refers to a surface located on the bottom roll side of the rotary embossing apparatus.

At the time of embossing:

A: No lifting or peeling of the release fdm was found.

B: Lifting or peeling was found in a portion of the release film.

C: The majority of the release film was floating or peeling off.

D: The release film is completely peeled.

At the time of cutting:

A: No lifting or peeling of the release fdm was found.

B: Lifting or peeling was found in a portion of the release film.

C: The majority of the release film was floating or peeling off.

D: The release film is completely peeled. Table 17

Experimental Example 5

In Experimental Example 5, the peelability of an article having a recessed portion on a base surface to which the wallpaper laminate was applied was reviewed.

Example 68

A clip made of ABS resin having the configuration illustrated in FIG. 6 was prepared. Here, a diameter of a circular portion illustrated in FIG. 6(b) of this clip was approximately 3.8 cm, the area of the circular portion was approximately 11 cm ² , and a height in the lengthwise direction in FIG. 6(c) was approximately 1.1 cm.

The laminate of Example 11 having an embossed pattern in which SPU33K was used as the modified silicone or the laminate of Example 10 having an embossed pattern in which SPO20K was used as the modified silicone was prepared. One of the release liners of the laminate was removed, and the laminate was pasted to a base surface 610 of the clip via the pressure- sensitive adhesive layer so as to cover eight recessed portions 612 in FIG. 6(e) but not to cover a joint portion 607.

A wallpaper (No. SP9924 in the catalog “SP 2015-2017”, Sangetsu Corporation (Nagoya- shi, Aichi, Japan)) was washed with isopropyl alcohol. Then, the other release liner of the laminate was removed, and the laminate was pasted to the wallpaper. The clip was then pressed at 10 kg for 5 seconds and then left to stand for 1 hour.

For both the laminates, when the clip was pinched with fingers, and the clip pasted was detached, only the clips could be detached, as illustrated in FIG. 8. The laminate could then be detached from the wallpaper.

Reference Example 2

A clip made of ABS resin was prepared, which was identical with the configuration illustrated in FIG. 6, with the exception that the base surface, excluding the joint portion, was substantially flat.

The laminate of Example 10 or Example 11 was pasted to this clip in the same manner as in Example 68, and the same operation as in Example 68 was performed.

For both the laminates, when the clip was pinched with fingers in order to detach the pasted clip, more effort was required because the clip was more difficult to detach than in Example 68. When the clip was successfully detached, the laminate was attached integrally onto the back surface of the clip.

Example 69

A clip made of ABS resin having the configuration illustrated in FIG. 7 was prepared. Here, a diameter of a circular portion on the front face of this clip was approximately 3.8 cm, an area of the circular portion was approximately 11 cm ² , and a lateral width in FIG. 7(a) was approximately 0.7 cm.

The laminate of Example 11 having an embossed pattern in which SPU33K was used as the modified silicone or the laminate of Example 10 having an embossed pattern in which SPO20K was used as the modified silicone was prepared. One of the release liners of the laminate was removed, and the laminate was pasted to a base surface 710 of the clip via the pressure- sensitive adhesive layer so as to cover a second recessed portion 714, a fifth recessed portion 726, and a sixth recessed portion 728 in FIG. 7.

A wallpaper (No. SP9924 in the catalog “SP 2015-2017”, Sangetsu Corporation (Nagoya- shi, Aichi, Japan)) was washed with isopropyl alcohol. Then, the other release liner of the laminate was removed, and the laminate was pasted to the wallpaper. The clip was then pressed at 10 kg for 5 seconds and then left to stand for 1 hour.

For both the laminates, when the clip was pinched with fingers, and the clip pasted was detached, only the clips could be detached, as illustrated in FIG. 8. The laminate could then be detached from the wallpaper.

Reference Example 3

A clip made of ABS resin was prepared, which was identical with the configuration illustrated in FIG. 7, with the exception that the portions of the second recessed portion 714, the fifth recessed portion 726, and the sixth recessed portion 728 in FIG. 7 had a substantially flat shape.

The laminate of Example 10 or Example 11 was pasted to this clip in the same manner as in Example 69, and the same operation as in Example 69 was performed.

For both the laminates, when the clip was pinched with fingers in order to detach the pasted clip, more effort was required because the clip was more difficult to detach than in Example 69. When the clip was successfully detached, the laminate was attached integrally onto the back surface of the clip.

It will be apparent to those skilled in the art that various modifications can be made to the embodiments and the examples described above without departing from the basic principles of the present invention. In addition, it will be apparent to those skilled in the art that various improvements and modifications of the present invention can be carried out without departing from the spirit and the scope of the present invention.

Reference Signs List

100: Wallpaper laminate

101: First release liner

103: First pressure-sensitive adhesive layer

105: Core layer (nonwoven layer or foamed layer)

107: Second pressure-sensitive adhesive layer 109: Second release liner

200: Wallpaper laminate with release liner removed 203 : First pressure-sensitive adhesive layer 205: Core layer (nonwoven layer)

207: Second pressure-sensitive adhesive layer 600: Clip 601: Base

603 : Clamping portion 605: Support member 607: Joint portion 610: Base surface 612: Recessed portion 700: Clip (integral)

701: Base

703 : Clamping portion 707: Hooking portion 710: Base surface 712: First recessed portion 714: Second recessed portion 722: Third recessed portion 724: Fourth recessed portion 726: Fifth recessed portion 728: Sixth recessed portion 801: Wallpaper 803: Wallpaper laminate 805: Article

900: Intermediate member

901: Release liner (first or second release liner)

903 : Pressure-sensitive adhesive layer (first or second pressure-sensitive adhesive layer) 904: Release liner 1000: Roll body

1001: Release liner (first or second release liner)

1003: Pressure-sensitive adhesive layer (first or second pressure-sensitive adhesive layer) a: Length of emboss top b: Pitch spacing h: Depth of emboss