A CUSHION LAYER AND A DISCONTINUOUS SHELL LAYER

Cross Reference To Related Application

This application claims the benefit of U.S. Provisional Patent Application No. 62/608678, filed December 21, 2017, the disclosure of which is incorporated by reference herein in its entirety.

BACKGROUND

Pressure sensitive adhesives are well known and used in many industrial applications. It is also known that optimization of such adhesives for a given application requires a balance of properties that are often in opposition to one another. The properties typically desired are peel adhesion strength (at a variety of speeds and temperatures), tack or rapid bonding with minimal pressure, and shear resistance or ability to hold loads for extended time. For example, one often sees that increases in shear resistance are accompanied by reductions in tack and/or peel adhesion strength. Adhesives designed for good tack and peel at room temperature and moderate peel speeds may have poor peel adhesion strength at low peel rates and/or high temperature. Improving the high temperature and/or low speed peel adhesion strength, however, often results in low tack.

The need for a better combination of adhesion performance at room temperature and at high temperature along with better performance on low energy surfaces is common in many applications (e.g., in the automotive and electronics bonding areas) under ever more demanding requirements, particularly where high temperature lifting resistance and relatively low tack are desirable properties. Thus, there continues to be a need for new adhesive articles.

SUMMARY

Provided herein are adhesive articles that include a cushion layer and a discontinuous shell layer. Such two-layer adhesives can provide a unique balance of properties and design control for different applications.

More specifically, provided herein is an adhesive article including: a flexible backing; a first cushion layer permanently bonded to a first surface of the flexible backing, wherein the first cushion layer: has an average thickness of at least 10 micrometers; and includes an acrylate pressure-sensitive adhesive having a Fox Tg (glass transition temperature) of up to -30°C, wherein the acrylate pressure- sensitive adhesive includes a (meth)acrylate copolymer; and a first discontinuous shell layer adjacent the first cushion layer, wherein: the first discontinuous shell layer has an average thickness of up to 25 micrometers (in those areas where the shell layer exists); the ratio of the first cushion layer average thickness to the first shell layer average thickness is at least 2: 1; the first discontinuous shell layer includes an adhesive having a Fox Tg of +lO°C to +50°C; and the first discontinuous shell layer adhesive includes a copolymer having a weight average molecular weight of at least 100,000 Daltons.

The acrylate pressure -sensitive adhesive of the first cushion layer includes a (meth)acrylate copolymer including:

a) one or more (meth)acrylate monomeric units of Formula (I) in an amount of at least 60 percent by weight (wt-%), based on a total weight of monomeric units in the (meth)acrylate copolymer:

wherein:

Ri is hydrogen or a methyl group; and

R ₂ is an alkyl, heteroalkyl, aryl, aralkyl, or alkaryl group; and

b) one or more polar monomeric units in an amount of up to 7 wt-%, based on a total weight of monomeric units in the (meth)acrylate copolymer;

wherein the sum of all monomeric units (monomeric units (a) and (b) plus optional monomeric units) of the first cushion layer (meth)acrylate copolymer equals 100% by weight.

The first discontinuous shell layer adhesive (which may be a pressure-sensitive adhesive) includes a copolymer having a weight average molecular weight of at least 100,000 Daltons, wherein the copolymer includes:

a) one or more low Tg (meth)acrylate monomeric units of Formula (II) in an amount of at least 25 wt-%, based on a total weight of monomeric units in the copolymer:

wherein:

Ri is hydrogen or a methyl group; and

R ₃ is an alkyl, heteroalkyl, aryl aralkyl, or alkaryl group;

b) one or more polar monomeric units in an amount of up to 5 wt-%, based on a total weight of monomeric units in the copolymer; and c) one or more high Tg nonpolar monomeric units in an amount of at least 35 wt-%, based on a total weight of monomeric units in the copolymer;

wherein the sum of all monomeric units (monomeric units (a), (b), and (c) plus optional monomeric units) of the first shell layer copolymer equals 100% by weight.

As used herein, the term“(meth)acrylate” refers to a methacrylate and an acrylate.

As used herein, the term“(meth)acrylamide” refers to a methacrylamide and an acrylamide.

As used herein, the term“adjacent” can be used to refer to two materials, typically in the form of layers, that are in direct contact or that are separated by one or more other materials, such as a flexible backing layer and an adhesive layer with a chemical primer layer therebetween. Often, adjacent materials are in direct contact (e.g., an adhesive layer directly disposed on a flexible backing layer).

As used herein, an asterisk (*) shows the location where a monomeric unit is bonded to another monomeric unit or group.

According to the Pressure-Sensitive Tape Council, pressure-sensitive adhesives (PSAs) are defined to possess the following properties: (1) aggressive and permanent tack, (2) adherence with no more than finger pressure, (3) sufficient ability to hold onto an adherend, and (4) sufficient cohesive strength to be removed cleanly from the adherend. Materials that have been found to function well as PSAs include polymers designed and formulated to exhibit the requisite viscoelastic properties resulting in a desired balance of tack, peel adhesion, and shear holding power. PSAs are characterized by being normally tacky at room temperature (e.g., 20°C). Materials that are merely sticky or adhere to a surface do not constitute a PSA; the term PSA encompasses materials with additional viscoelastic properties.

PSAs are adhesives that satisfy the Dahlquist criterion for tackiness at room temperature and typically exhibit adhesion, cohesion, compliance, and elasticity at room temperature. This criterion defines a pressure sensitive adhesive as an adhesive having a 1 second creep compliance of greater than 1 x 10 ⁶ cm ² /dyne as described in Handbook of Pressure Sensitive Adhesive Technology, Donatas Satas (Ed.), 2 ^nd Edition, p. 172, Van Nostrand Reinhold, New York, NY, 1989. Alternatively, since modulus is, to a first approximation, the inverse of creep compliance, pressure sensitive adhesives may be defined as adhesives having a Young’s modulus of less than 1 x 10 ⁶ dynes/cm ² .

Glass Transition Temperature (Tg) values may also be calculated using the Fox equation. The calculation is based on the weighted average of the individual homopolymer glass transition values. For a copolymer prepared from n different monomers, the inverse of the Tg of the copolymer is equal to the summation of the weight fraction of each component divided by the Tg of that particular component (expressed in absolute temperature units, such as Kelvin). That is, for a copolymer prepared from n components, 1 / Tg of the copolymer is equal to (weight fraction of component one ÷ Tg of component one) + (weight fraction of component two ÷ Tg of component two) + (weight fraction of component 3 ÷ Tg of component 3) + ....+ (weight fraction of component n ÷ Tg of component n). Lists of glass transition temperatures for homopolymers are available from multiple monomer suppliers such as from BASF Corporation (Houston, TX, USA), Polyscience, Inc. (Warrington, PA, USA), and Aldrich (Saint Louis, MO, USA) as well as in various publications such as, for example, Mattioni et al., J. Chem. Inf. Comput. Sci., 2002, 42, 232-240.

As used herein,“alkyl” refers to a monovalent group that is a radical of an alkane and includes straight-chain, branched, cyclic, and bicyclic alkyl groups, and combinations thereof. Unless otherwise indicated, the alkyl groups typically contain from 1 to 24 carbon atoms. There can be at least 2, at least

3, or at least 4 carbon atoms and up to 24, up to 20, up to 18, up to 16, up to 12, up to 10, up to 6, up to

4, or up to 3 carbon atoms. In some embodiments, the alkyl groups contain 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 3 carbon atoms. In certain embodiments, the alkyl groups include 2 to 24 carbon atoms or 4 to 24 carbon atoms. Examples of“alkyl” groups include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, t-butyl, isopropyl, n- octyl, n-heptyl, ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbomyl, and the like.

The term“aryl” refers to a monovalent group that is aromatic and, optionally, carbocyclic. The aryl has at least one aromatic ring. Any additional rings can be unsaturated, partially saturated, saturated, or aromatic. Optionally, the aromatic ring can have one or more additional carbocyclic rings that are fused to the aromatic ring. Unless otherwise indicated, the aryl groups typically contain from 6 to 30 carbon atoms. There can be at least 10, or at least 14 carbon atoms and up to 24, up to 20, up to 18, up to 12, or up to 10 carbon atoms. In some embodiments, the aryl groups contain 6 to 24, 6 to 20, 6 to 18, 6 to 16, 6 to 12, or 6 to 10 carbon atoms. Examples of an aryl group include phenyl, naphthyl, biphenyl, phenanthryl, and anthracyl.

The term“aralkyl” refers to a monovalent group that is an alkyl group substituted with an aryl group (e.g., as in a benzyl group). The term“alkaryl” refers to a monovalent group that is an aryl substituted with an alkyl group (e.g., as in a tolyl group). Unless otherwise indicated, for both groups, the alkyl portion often has 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms, and an aryl portion often has 6 to 24 carbon atoms, 6 to 20 carbon atoms, 6 to 18 carbon atoms, 6 to 16 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms.

The term“heteroalkyl” means an alkyl group having at least one -CEL- replaced with a heteroatom such as NR, O, or S, wherein R is H or an alkyl group. There can be more than one heteroatom such as 1 to 10, 1 to 6, 1 to 4, or 1 to 3 heteroatoms. The number of carbons are the same as described for an alkyl group. The heteroatom can replace any -CEL- in the alkyl group but two heteroatoms are separated by at least one -CEL- group.

In the context of a shell layer, discontinuous means a shell layer that does not form a complete coating such that regions of the cushion layer are exposed due to absence of shell material.

The phrase“permanently bonded” in the context of a bond formed between an adhesive

(particularly a pressure-sensitive adhesive) and a flexible backing means the bond fails cohesively before adhesive failure from the flexible backing is observed when the adhesive is stressed by some means (most commonly a peel or tensile mode).

The term“comprises” and variations thereof do not have a limiting meaning where these terms appear in the description and claims. Such terms will be understood to imply the inclusion of a stated step or element or group of steps or elements but not the exclusion of any other step or element or group of steps or elements. By“consisting of’ is meant including, and limited to, whatever follows the phrase “consisting of.” Thus, the phrase“consisting of’ indicates that the listed elements are required or mandatory, and that no other elements may be present. By“consisting essentially of’ is meant including any elements listed after the phrase and limited to other elements that do not interfere with or contribute to the activity or action specified in the disclosure for the listed elements. Thus, the phrase“consisting essentially of’ indicates that the listed elements are required or mandatory, but that other elements are optional and may or may not be present depending upon whether or not they materially affect the activity or action of the listed elements. Any of the elements or combinations of elements that are recited in this specification in open-ended language (e.g., comprise and derivatives thereof), are considered to additionally be recited in closed-ended language (e.g., consist and derivatives thereof) and in partially closed-ended language (e.g., consist essentially, and derivatives thereof).

The words“preferred” and“preferably” refer to embodiments of the disclosure that may afford certain benefits, under certain circumstances. However, other claims may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred claims does not imply that other claims are not useful and is not intended to exclude other claims from the scope of the disclosure.

In this application, terms such as“a,”“an,” and“the” are not intended to refer to only a singular entity but include the general class of which a specific example may be used for illustration. The terms “a,”“an,” and“the” are used interchangeably with the term“at least one.” The phrases“at least one of’ and“comprises at least one of’ followed by a list refers to any one of the items in the list and any combination of two or more items in the list.

As used herein, the term“or” is generally employed in its usual sense including“and/or” unless the content clearly dictates otherwise.

The term“and/or” means one or all of the listed elements or a combination of any two or more of the listed elements.

Also, herein, all numbers are assumed to be modified by the term“about” and in certain embodiments, preferably, by the term“exactly.” As used herein in connection with a measured quantity, the term“about” refers to that variation in the measured quantity as would be expected by the skilled artisan making the measurement and exercising a level of care commensurate with the objective of the measurement and the precision of the measuring equipment used. Herein,“up to” a number (e.g., up to 50) includes the number (e.g., 50).

Also, herein, the recitations of numerical ranges by endpoints include all numbers subsumed within that range as well as the endpoints (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

As used herein, the term“room temperature” refers to a temperature of 20°C to 25°C or 22°C to

25°C. The term“in the range” or“within a range” (and similar statements) includes the endpoints of the stated range.

Groupings of alternative elements or embodiments disclosed herein are not to be construed as limitations. Each group member may be referred to and claimed individually or in any combination with other members of the group or other elements found therein. It is anticipated that one or more members of a group may be included in, or deleted from, a group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, the specification is herein deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended claims.

When a group is present more than once in a formula described herein, each group is “independently” selected, whether specifically stated or not. For example, when more than one R group is present in a formula, each R group is independently selected.

Reference throughout this specification to“one embodiment,”“an embodiment,”“certain embodiments,” or“some embodiments,” etc., means that a particular feature, configuration, composition, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. Thus, the appearances of such phrases in various places throughout this specification are not necessarily referring to the same embodiment of the invention. Furthermore, the particular features, configurations, compositions, or characteristics may be combined in any suitable manner in one or more embodiments.

The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present invention. The description that follows more particularly exemplifies illustrative embodiments. In several places throughout the application, guidance is provided through lists of examples, which examples may be used in various combinations. In each instance, the recited list serves only as a representative group and should not be interpreted as an exclusive list. Any of the elements that are positively recited in this specification as alternatives may be explicitly included in the claims or excluded from the claims, in any combination as desired. Although various theories and possible mechanisms may have been discussed herein, in no event should such discussions serve to limit the claimable subject matter.

BRIEF DESCRIPTION OF FIGURES

FIG. 1 is a cross-sectional representation of an embodiment of an adhesive article of the present disclosure (not necessarily to scale).

FIG. 2 is a cross-sectional representation of another embodiment of an adhesive article of the present disclosure (not necessarily to scale).

FIG. 3 is a cross-sectional representation of an embodiment of an adhesive article of the present disclosure showing embedded structures of the shell layer (not necessarily to scale).

DETAILED DESCRIPTION Provided herein are adhesive articles that include a cushion layer and a discontinuous shell layer. The discontinuous shell layer is the outer layer that comes in contact with the target substrate to which the adhesive article is applied. It is thinner and includes an adhesive having a higher glass transition temperature (Tg) than that of the cushion layer.

Selection of the materials for the cushion layer and the shell layer can provide a unique balance of properties for a variety of applications. For example, the two-layer adhesives can provide better combination of adhesion performance at room temperature and at high temperature along with better performance on low energy surfaces. Significantly, in certain embodiments, adhesive articles of the present disclosure demonstrate enhanced adhesion at low peel rates and/or high temperatures while still retaining useful tack, compared to either of the single adhesive layers used alone, which would be lacking in one or both performance attributes. Furthermore, such advantages can be achieved without the need to use a foam in the core or any component of the adhesive article, which is desirable for applications in which optical transparency, incompressibility, or thinner overall constructions are desired. Neither the core not the shell is typically a foam.

The ability to modify the tack very precisely is a highly desirable performance attribute of adhesives, particularly PSAs. Furthermore, to do this with only a nominal impact on the total PSA performance (e.g., shear and peel behavior) would be highly desirable. In one example, the placement and positioning of large graphic films with PSA attachments on a vehicle, such as used in the commercial graphics business, can be quite challenging requiring many different solutions. To aid placement while avoiding immediate PSA adhesion, these solutions range from the application of soap and water to the vehicle prior to adhesion, to more complicated solutions requiring non-tacky ceramic posts to be adhered to the surface of the PSA. Such posts effectively reduce the peel performance of the PSA by reducing area of adhesion onto the vehicle.

The adhesive articles of the present disclosure provide a unique solution to overcome these challenges. The use of a higher Tg adhesive in a shell layer on an underlying PSA not only allows for positioning of the article, but also can enhance the final PSA performance. This can be achieved, for example, by adjusting the area of the underlying PSA covered by the higher Tg adhesive shell layer and thus changing the tack (or rolling ball distance) of the article. Additionally, increasing the Tg of the higher Tg discontinuous shell layer may also decrease the tack (or inversely increase the rolling ball distance).

As shown in FIG. 1, an adhesive article (e.g., tape) 10 of the present disclosure includes a flexible backing 12 having a first surface 14 and a second surface 16, a first cushion layer 20

permanently bonded to the first surface 14 of the flexible backing 12, and a first discontinuous shell layer 22 adjacent the first cushion layer 20. The discontinuous shell layer 22 is composed of structures 23, shown in this embodiment as dots.

Herein, use of the term“first” does not necessarily require that there has to be a second cushion layer and/or a second discontinuous shell layer, although in certain embodiments, the adhesive articles do include a second cushion layer and a second discontinuous shell layer. Thus, as shown in FIG. 2, in certain embodiments, an adhesive article 30 of the present disclosure includes a flexible backing 32 having a first surface 34 and a second surface 36, a first cushion layer 40 permanently bonded to the first surface 34 of the flexible backing 32, a first discontinuous shell layer 42 composed of structures 43 adjacent the first cushion layer 40, as well as a second cushion layer 46 permanently bonded to the second surface 36 (i.e., second side) of the flexible backing 32, and a second discontinuous shell layer 48 composed of structures 49 adjacent the second cushion layer 46.

The ability to tune the adhesive properties of the first shell layer 42 independently of the second shell layer 48 may allow for enhanced peel performance when bonding dissimilar substrates to either surface of the adhesive article. For example, an adhesive article of the present disclosure could include a relatively low Tg first shell layer 42 to position adjacent a first substrate and a relatively high Tg second shell layer 48 to position adjacent a second substrate. The second substrate could be more easily positioned and aligned relative to the first substrate prior to creating a bond.

Herein, reference to a cushion layer includes reference to a first and/or second cushion layer, and reference to a shell layer includes reference to a first and/or second shell layer.

A cushion layer (first and/or second) has an average thickness of at least 10 micrometers. In certain embodiments, a cushion layer has an average thickness of at least 20 micrometers, at least 30 micrometers, or at least 50 micrometers and up to 150 micrometers, up to 125 micrometers, up to 100 micrometers, up to 75 micrometers, or up to 50 micrometers.

A discontinuous shell layer has an average thickness of up to 25 micrometers. Above this thickness the discontinuous shell layer may dominate the behavior of the article and negate the beneficial effects of the bilayer construction. That is, when the discontinuous shell layer is thicker than 25 micrometers, the cushion layer is no longer able to reach the substrate and provide further adhesion. In certain embodiments, a discontinuous shell layer has an average thickness of up to 20 micrometers, up to 12 micrometers, up to 10 micrometers, up to 8 micrometers, up to 6 micrometers, up to 4 micrometers, or up to 2 micrometers.

A ratio of the cushion layer average thickness to the shell layer average thickness is at least 2: 1. In certain embodiments, the ratio of the cushion layer average thickness to the discontinuous shell layer average thickness is at least 3: 1, at least 4: 1, at least 5: 1, at least 10: 1, at least 20: 1, at least 50: 1, or at least 70: 1. In certain embodiments, the ratio of the cushion layer average thickness to the shell layer average thickness is up to 300: 1, up to 200: 1, up to 100: 1, or up to 50: 1..

In certain embodiments, as shown in FIG. 3, an adhesive article 50 that includes a flexible backing 52, a cushion layer 60, and a discontinuous shell layer 62 composed of structures 63, the structures 63 may be embedded in (i.e., pressed into) the matrix of the cushion layer 60. This may allow for a further optimization of the balance between the peel and tack by allowing for the higher tack PSA of the underlying cushion layer 60 to be more accessible to the surface to which the article is adhered and avoiding the possibility of“tenting” between the structures 63 of the discontinuous shell layer 62 (e.g., printed dots). Excessive tenting could result in only the shell layer 62 contacting the surface to which the article is adhered.

Embedding the structures 63 of the discontinuous shell layer 62 into the cushion layer 60 can be accomplished by techniques well known to those skilled in the art. For example, this can be accomplished by sequential coating steps onto a release liner, where the discontinuous shell layer is coated onto the release liner and the cushion layer is coated onto the discontinuous shell layer. The two layers are then transferred to a flexible backing. Alternatively, the construction of a flexible backing, cushion layer, and shell layer can be passed through a nip prior to curing either adhesive in the cushion or shell layer to effectively push the shell layer down into the softer cushion layer.

In certain embodiments, an adhesive article of the present disclosure demonstrates an increase (in certain embodiments, an at least one and a half-fold increase, or an at least two-fold increase) in 180° angle peel adhesion strength at a peel rate of 0.2 inch/minute (0.08 millimeter/second) from

polypropylene at room temperature compared to an adhesive article having the same flexible backing and first cushion layer but without the first shell layer, if measured on the first side of the adhesive article (or the second cushion layer but without the second shell layer, if measured on the second side of the adhesive article).

Herein,“peel rate” refers to the rate of propagation of the peel front relative to the substrate to which the adhesive is applied. That is, the speed of pulling the tape relative to the peel front rate depends on the peel angle. For example, when peeling at an angle of 180 degrees, the peel front rate is one-half the pulling speed.

The relatively thin shell layer that includes the higher Tg adhesive provides an increase in the debonding force required to separate the adhesive from a substrate, in comparison to the debonding force of the lower Tg adhesive of the underlying cushion layer alone. Additionally, the lower Tg adhesive of the cushion layer provides the necessary conformability for good substrate wetting and energy dissipation that would be lacking in the higher Tg adhesive of the overlying shell layer alone. These composite properties are what leads to the significant improvement in bond performance (i.e., peel force/resistance) observed for the adhesive articles of the present disclosure.

In certain embodiments, an adhesive article of the present disclosure demonstrates an increase (in certain embodiments, an at least one and a half-fold increase, or an at least two-fold increase) in 180° angle peel adhesion strength at a peel rate of 0.2 inch/minute (0.08 millimeter/second) from

polypropylene at a temperature of up to 65°C compared to an adhesive article having the same flexible backing and first cushion layer but without the first shell layer, if measured on the first side of the adhesive article (or the second cushion layer but without the second shell layer, if measured on the second side of the adhesive article).

In certain embodiments, an adhesive article of the present disclosure demonstrates an average rolling ball stopping distance according to a Rolling Ball Tack Test (as described in Examples Section) of no more than 25% greater than that of the cushion layer without a discontinuous shell layer. Cushion Laver Acrylate Pressure-Sensitive Adhesive

A cushion layer (first and/or second) includes an acrylate pressure-sensitive adhesive having a Fox Tg of up to -30°C. The Fox Tg can be, for example, up to -35°C, up to -40°C, up to -45°C, or up to -50°C. In certain embodiments, the acrylate pressure-sensitive adhesive of the cushion layer has a Fox Tg of at least -85°C, at least -80°C, at least -75°C, at least -70°C, at least -65°C, or at least -60°C.

In certain embodiments, a cushion layer (meth)acrylate copolymer has a weight average molecular weight of at least 100,000 Daltons, at least 150,000 Daltons, at least 200,000 Daltons, at least 300,000 Daltons, or at least 400,000 Daltons. In certain embodiments, a cushion layer (meth)acrylate copolymer has a weight average molecular weight of up to 2,000,000 Daltons, up to 1,500,000 Daltons, up to 1,000,000 Daltons, up to 700,000 Daltons, or up to 500,000 Daltons.

The acrylate pressure-sensitive adhesive of the cushion layers (first and/or second) includes a (meth)acrylate copolymer that includes:

a) one or more (meth)acrylate monomeric units of Formula (I):

wherein:

Ri is hydrogen or a methyl group; and

R2 is an alkyl, heteroalkyl, aryl, aralkyl, or alkaryl group; and b) one or more polar monomeric units.

The one or more (meth)acrylate monomeric units (a) of Formula (I) are present in a cushion layer (meth)acrylate copolymer in an amount of at least 60 wt-%, at least 65 wt-%, at least 70 wt-%, at least 75 wt-%, or at least 80 wt-%, based on a total weight of monomeric units in the (meth)acrylate copolymer. In certain embodiments, a cushion layer (meth)acrylate copolymer includes one or more (meth)acrylate monomeric units (a) of Formula (I) in an amount of up to 99.5 wt-%, up to 95 wt-%, up to 90 wt-%, or up to 85 wt-%, based on a total weight of monomeric units in the (meth)acrylate copolymer.

The one or more polar monomeric units (b) are present (i.e., they are present in an amount of greater than 0 wt-%) in a cushion layer (meth)acrylate copolymer in an amount of up to 7 wt-%, up to 6 wt-%, up to 5 wt-%, or up to 4 wt-%, based on a total weight of monomeric units in the (meth)acrylate copolymer. In certain embodiments, a cushion layer (meth)acrylate copolymer includes one or more polar monomeric units (b) in an amount of at least 0.5 wt-%, at least 1 wt-%, at least 1.5 wt-%, at least 2 wt-%, at least 2.5 wt-%, or at least 3 wt-%, based on a total weight of monomeric units in the

(meth)acrylate copolymer.

Herein, the sum of all monomeric units (a) and (b) and any optional monomeric units of the cushion layer (meth)acrylate copolymer equals 100% by weight.

In Formula (I) of the monomeric units of the cushion layer (meth)acrylate copolymer, R is an alkyl, heteroalkyl, aryl, aralkyl, or alkaryl group. Alkyl groups often have 1 to 24 carbon atoms, 4 to 24 carbon atoms, 4 to 20 carbon atoms, 2 to 20 carbon atoms, 4 to 12 carbon atoms, 2 to 12 carbon atoms, or 2 to 10 carbon atoms. Heteroalkyl groups often have 2 to 24, 4 to 24 carbon atoms, 4 to 20 carbon atoms, or 4 to 12 carbon atoms. Aryl groups often have 6 to 24 carbon atoms, 6 to 20 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms. Aralkyl and alkaryl groups often have an aryl or arylene portion with 6 to 20 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms and an alkyl or alkylene portion with 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms.

In certain embodiments of Formula (I) of the monomeric units of the cushion layer

(meth)acrylate copolymer, R is an alkyl group having 1 to 24 carbon atoms. In certain embodiments of Formula (I) of the monomeric units of the cushion layer (meth)acrylate copolymer, R is an alkyl group having 4 to 24 carbon atoms.

In certain embodiments, if the monomeric unit of Formula (I) of the cushion layer (meth)acrylate copolymer includes R groups having at least 8 carbon atoms (e.g., an alkyl group having at least 8 carbon atoms), these monomeric units are present in an amount of at least 20 wt-%, at least 25 wt-%, at least 30 wt-%, at least 35 wt-%, at least 40 wt-% or even higher, based on a total weight of monomeric units in the (meth)acrylate copolymer. In some embodiments, all the monomeric units (a) of Formula (I) have at least 8 carbon atoms. That is, the amount of these monomer units can be in a range of 20 wt-% to 99.5 wt-% based on a total weight of monomeric units in the (meth)acrylate copolymer. The amount is often up to 99 wt-%, up to 95 wt-%, up to 90 wt-%, up to 85 wt-%, up to 80 wt-%, up to 75 wt-%, up to 70 wt-%, up to 65 wt-%, or up to 60 wt-%.

In certain embodiments, a cushion layer (meth)acrylate copolymer includes one or more (meth)acrylate monomeric units of Formula (I) derived from monomers such as 2-ethylhexyl

(meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl

(meth)acrylate, cyclohexyl (meth)acrylate, hexyl (meth)acrylate, 2-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isobomyl (meth)acrylate, norbomyl (meth)acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate, 2-methylbutyl (meth)acrylate, and combinations thereof. In certain embodiments, a cushion layer (meth)acrylate copolymer includes one or more (meth)acrylate monomeric units of Formula (I) derived from monomers selected from the group of 2-ethylhexyl acrylate, n-butyl acrylate, isooctyl acrylate, 2-octyl acrylate, and combinations thereof. Various isomer mixtures of the alkyl (meth)acrylates can be used as those described, for example, in PCT Patent Application Publication WO 2012/088126 (Clapper et ah). In certain embodiments, a cushion layer (meth)acrylate copolymer includes one or more polar monomeric units that are derived from polar monomers. As used herein, the term“polar monomer” refers to a monomer having a single ethylenically unsaturated group and a polar group selected from the group of a hydroxyl group, an acidic group, a basic group (such as a primary amido group, a secondary amido group, a tertiary amido group, an amino group). In contrast, herein“nonpolar monomer” does not include such polar groups.

The polar group can be in the form of a salt. For example, the acidic group can be in the form of an anion and can have a cationic counter ion. In many embodiments, the cationic counter ion is an alkaline metal ion (e.g., sodium, potassium, or lithium ion), an alkaline earth ion (e.g., calcium, magnesium, or strontium ion), an ammonium ion, or an ammonium ion substituted with one or more alkyl or aryl groups. The various amido or amino groups can be in the form of a cation and can have an anionic counter ion. In many embodiments, the anionic counter ion is a halide, acetate, formate, sulfate, phosphate, or the like.

Useful acid-f mctional monomers include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and combinations thereof. Anhydrides, such as maleic anhydride and methacrylic acid anhydride can also be used.

Useful hydroxyl-functional monomers typically have a hydroxyl equivalent weight of less than 400. The hydroxyl equivalent molecular weight is defined as the molecular weight of the monomeric compound divided by the number of hydroxyl groups in the monomeric compound. Useful monomers of this type include 2-hydroxyethyl acrylate and methacrylate, 3-hydroxypropyl acrylate and methacrylate, 2-hydroxypropyl acrylate and methacrylate, 4-hydroxybutyl acrylate and methacrylate, 2- hydroxyethylacrylamide, and 3-hydroxypropylacrylamide. Additionally, hydroxyl functional monomers based on glycols derived from ethylenoxide or propyleneoxide can also be used. Various combinations of such monomers can be used, if desired.

Polar monomers may also include amido groups, such as primary amido groups including (meth)acrylamide, and secondary amido groups including N-alkyl (meth)acrylamides (e.g., N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-tert-octyl

(meth)acrylamide, or N-octyl (meth)acrylamide), and tertiary amido groups including N-vinyl caprolactam, N-vinyl-2-pyrrolidone, (meth)acryloyl morpholine, and N,N-dialkyl (meth)acrylamides (e.g., N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-dipropyl (meth)acrylamide, and N,N-dibutyl (meth)acrylamide).

Polar monomers may also include an amino group such as various N,N -dialky laminoalkyl (meth)acrylates and N,N-dialky laminoalkyl (meth)acrylamides. Examples include, but are not limited to, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, N,N- dimethylaminopropyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, N,N- diethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylamide, N,N-diethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylamide. In certain embodiments, a cushion layer (meth)acrylate copolymer comprises one or more polar monomeric units derived from polar monomers selected from the group of (meth)acrylic acid,

(meth)acrylamide, alkyl-substituted (meth)acrylamides (e.g., N,N-dimethyl acrylamide), and combinations thereof.

One or more other monomeric units may be included in a cushion layer (meth)acrylate copolymer of the present disclosure.

In certain embodiments, a cushion layer (meth)acrylate copolymer further includes optional monomers such as vinyl acetate monomeric units. Generally, vinyl acetate is used as a scavenger of residual (meth)acrylate monomers as described in U.S. Pat. No. 8,263,718 (Ellis). Typically, such vinyl monomeric units are present in an amount of up to 7 wt-%, based on the total weight of monomeric units in the copolymer. For example, the amounts can be up to 5 wt-%, up to 3 wt-%, up to 2 wt-%, or up to 1 wt-%. The amount, if present, is often at least 0.1 wt-%, at least 0.2 wt-%, at least 0.5 wt-%, or at least 1 wt-%,

In addition to a (meth)acrylate copolymer, in certain embodiments, a cushion layer acrylate pressure-sensitive adhesive further includes one or more additives selected from the group of colorants, fillers, flame retardants, antioxidants, UV-stabilizers, viscosity modifiers, and combinations thereof. For example, antioxidants and/or UY stabilizers such as hydroquinone monomethyl ether (4-methoxyphenol, MeHQ), and that available under the trade name IRGANQX 1010 (tetrakis(methylene(3,5-di-tert-butyl- 4-hydroxyhydrocinnaniate))methane) from BASF Corp., can be mixed into the cushion layer

(meth)acrylate copolymer to increase its temperature stability. If used, an antioxidant and/or stabilizer is typically used in the range of 0.01 wt-% to 1.0 wt-%, based on the total weight of the acrylate pressure- sensitive adhesive. For example, the amounts can be at least 0.01 wt-%, 0.02 wt-%, at least 0.05 wt-%, at least 0.1 wt-%, or at least 0.2 wt-% and up to 1.0 wt-%, up to 0.8 wt-%, up to 0.6 wt-%, or up to 0.5 wt-%.

In certain embodiments, a cushion layer acrylate pressure-sensitive adhesive includes tackifiers and/or plasticizers in a combined amount of no more than 20 wt-%. The amount can be up to 18 wt-%, up to 16 wt-%, up to 15 wt-%, up to 12 wt-%, or up to 10 wt-%. The amount can be at least 0.1 wt-%, at least 0.2 wt-%, at least 0.5 wt-%, at least 1 wt-%, at least 2 wt-%, or at least 5 wt-%. In certain embodiments, a cushion layer acrylate pressure-sensitive adhesive includes substantially no tackifiers and/or plasticizers. In this context,“substantially no” means less than 1 wt-%, less than 0.5 wt-%, or less than 0.1 wt-%, based on the total weight of the acrylate pressure-sensitive adhesive.

The copolymers and adhesives of the cushion layer may be prepared by any conventional polymerization method (such as solution polymerization or emulsion polymerization) including thermal bulk polymerization under adiabatic conditions, as is disclosed in U.S. Pat. Nos. 5,637,646 (Ellis) and 5,986,011 (Ellis et ah). Other methods of preparing (meth)acrylate copolymers include the continuous free radical polymerization methods described in U.S. Pat. Nos. 4,619,979 (Kotnour et al.) and 4,843,134 (Kotnour et al.), the polymerization within a polymeric package as described in U.S. Pat. No. 5,804,610 (Hamer et al.), and the on-web polymerization process as described in U.S. Pat. No. 4,181,752 (Martens et al.). Alternatively, the copolymers and adhesives of the cushion layer may be prepared as exemplified in the Examples Section.

Shell Layer Adhesive

A discontinuous shell layer (first and/or second) includes an adhesive (in certain embodiments, a pressure-sensitive adhesive) that has a Fox Tg of +10°C to +50°C. In certain embodiments, the adhesive of the discontinuous shell layer has a Fox Tg of up to +40°C, up to +30°C, or up to +20°C and at least +l5°C, at least +20°C, or at least +25°C.

A discontinuous shell layer (first and/or second) includes a copolymer having a weight average molecular weight of at least 100,000 Daltons. In certain embodiments, a shell layer copolymer has a weight average molecular weight of at least 150,000 Daltons, at least 200,000 Daltons, at least 250,000 Daltons, at least 300,000 Daltons, at least 350,000 Daltons, or at least 400,000 Daltons. In certain embodiments, a first shell layer copolymer has a weight average molecular weight of up to 2,000,000 Daltons, up to 1,500,000 Daltons, up to 1,000,000 Daltons, up to 700,000 Daltons, or up to 500,000 Daltons.

The discontinuous shell layer adhesive may be a pressure-sensitive adhesive.

The discontinuous shell layer adhesive copolymer includes:

a) one or more low Tg (meth)acrylate monomeric units of Formula (II) (which may be the same or different than that of the cushion layer):

wherein:

Ri is hydrogen or a methyl group; and

R ₃ is an alkyl, heteroalkyl, aryl aralkyl, or alkaryl group;

b) one or more polar monomeric units (which may be the same or different than that of the cushion layer); and

c) one or more high Tg nonpolar monomeric units.

Herein, a low Tg monomeric unit is derived from a low Tg monomer, wherein a homopolymer of such monomer has a Tg of no greater than 0°C.

Herein, a high Tg monomeric unit is derived from a high Tg monomer, wherein a homopolymer of such monomer has a Tg of greater than 0°C. The one or more low Tg (meth)acrylate monomeric units (a) of Formula (I) are present in a shell layer copolymer in an amount of at least 25 wt-%, at least 30 wt-%, at least 35 wt-%, or at least 40 wt-%, based on a total weight of monomeric units in the copolymer. In certain embodiments, a shell layer copolymer includes one or more low Tg (meth)acrylate monomeric units (a) of Formula (I) in an amount of up to 64.5 wt-%, up to 60 wt-%, up to 55 wt-%, or up to 50 wt-%, based on a total weight of monomeric units in the copolymer.

The one or more polar monomeric units (b) are present (i.e., they are present in an amount of greater than 0 wt-%) in a shell layer copolymer in an amount of up to 5 wt-%, up to 4.5 wt-%, up to 4 wt-%, or up to 3.5 wt-%, based on a total weight of monomeric units in the copolymer. In certain embodiments, a shell layer copolymer includes one or more polar monomeric units (b) in an amount of at least 0.5 wt-%, at least 1 wt-%, at least 1.5 wt-%, or at least 2 wt-%, based on a total weight of monomeric units in the copolymer.

The one or more high Tg nonpolar monomeric units (c) are present in a shell layer copolymer in an amount of at least 35 wt-%, at least 40 wt-%, at least 45 wt-%, or at least 50 wt-%, based on a total weight of monomeric units in the copolymer. In certain embodiments, a shell layer copolymer includes one or more high Tg nonpolar monomeric units in an amount of up to 74.5 wt-%, up to 70 wt-%, up to 65 wt-%, or up to 60 wt-%, based on a total weight of monomeric units in the copolymer.

Herein, the sum of all monomeric units (a), (b), and (c) and any optional monomeric units of the shell layer copolymer equals 100% by weight.

In Formula (II) of the monomeric units of the shell layer copolymer, R ₃ is an alkyl, heteroalkyl, aryl, aralkyl, or alkaryl group. In certain embodiments of Formula (II) of the monomeric units of the shell layer copolymer, R ₃ is an alkyl group having 2 to 24 carbon atoms. In certain embodiments of Formula (II), R3 is an alkyl group having 4 to 24 carbon atoms, 4 to 20 carbon atoms, 2 to 20 carbon atoms, 4 to 12 carbon atoms, 2 to 12 carbon atoms, or 2 to 10 carbon atoms. In other embodiments, R3 is a heteroalkyl, aryl, aralkyl, or alkaryl group. Heteroalkyl groups often have 2 to 24, 4 to 24 carbon atoms, 4 to 20 carbon atoms, or 4 to 12 carbon atoms. Aryl groups often have 6 to 24 carbon atoms, 6 to 20 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms. Aralkyl and alkaryl groups often have an aryl or arylene portion with 6 to 20 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms and an alkyl or alkylene portion with 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms.

In certain embodiments, a shell layer copolymer includes one or more low Tg (meth)acrylate monomeric units of Formula (II) derived from monomers 2-ethylhexyl (meth)acrylate, ethyl acrylate, n- butyl acrylate, isobutyl acrylate, hexyl (meth)acrylate, 2-octyl acrylate, isooctyl acrylate, isononyl acrylate, isostearyl acrylate, 2-methylbutyl acrylate, and combinations thereof. In certain embodiments, a shell layer copolymer includes one or more low Tg (meth)acrylate monomeric units of Formula (I) derived from monomers selected from the group of 2-ethylhexyl acrylate, n-butyl acrylate, isooctyl acrylate, 2-octyl acrylate, and combinations thereof. Various isomer mixtures of the alkyl (meth)acrylates can be used as those described, for example, in PCT Patent Application Publication WO

2012/088126 (Clapper et al.).

In certain embodiments, a shell layer copolymer includes one or more polar monomeric units derived from polar monomers as described above for the cushion layer.

In certain embodiments, a cushion layer (meth)acrylate copolymer includes one or more polar monomeric units having an acid group and an adjacent shell layer copolymer includes one or more polar monomeric units having a basic group. Alternatively, in certain embodiments, a cushion layer

(meth)acrylate copolymer includes one or more polar monomeric units having a basic group and an adjacent shell layer copolymer includes one or more polar monomeric units having an acid group. This complementary orientation of acid- and base-containing monomeric units can enhance the adhesion between a cushion layer and a shell layer. Monomers with basic groups are often nitrogen-containing monomers such as those with a primary amido group, secondary amido group, or amino group.

In certain embodiments, a shell layer copolymer includes one or more polar monomeric units derived from monomers selected from the group of (meth)acrylic acid, (meth)acrylamide, alkyl- substituted (meth)acrylamides (e.g., N,N-dimethyl acrylamide), and combinations thereof.

In certain embodiments, a shell layer copolymer includes one or more high Tg nonpolar monomeric units derived from monomers selected from the group of styrene, substituted styrene (e.g., methyl styrene), isobomyl (meth)acrylate, methyl (meth)acrylate, tert-butyl (meth)acrylate, iso-butyl methacrylate, cyclohexyl (meth)acrylate, norbomyl (meth)acrylate, and combinations thereof. In certain embodiments, a shell layer copolymer includes one or more high Tg nonpolar monomeric units derived from monomers selected from the group of styrene, isobomyl (meth)acrylate, norbomyl acrylate, methyl (meth)acrylate, tert-butyl (meth)acrylate, iso-butyl methacrylate, cyclohexyl (meth)acrylate, and combinations thereof.

One or more other monomeric units may be included in a shell layer copolymer of the present disclosure.

In certain embodiments, a shell layer copolymer further comprises optional monomers such as vinyl acetate monomeric units. In certain embodiments, such vinyl acetate monomeric units are present in an amount of up to 7 wt-%, up to 5 wt-%, up to 3-wt-%, or up to 2 wt-%, based on the total weight of monomeric units in the copolymer.

In addition to a copolymer as described herein, in certain embodiments, a shell layer adhesive further includes one or more additives selected from the group of colorants, fillers, flame retardants, antioxidants, UV-stabilizers (e.g., UV-fluorescent molecules), viscosity modifiers, and combinations thereof. For example, antioxidants and/or UV stabilizers such as hydroquinone monomethyl ether (4- methoxyphenol, MeHQ), and that available under the trade name IRGANOX 1010

(tetrakis(methylene(3,5-di-tert-biityl-4-hydrQxyhydrQcinn amate))methane) from BASF Corp., can be mixed into the cushion layer (meth)acrylate copolymer to increase its temperature stability. If used, an antioxidant and/or stabilizer is typically used in the range of 0.01 wt-% to 1.0 wt-%, based on the total weight of the adhesive.

In certain embodiments, a shell layer adhesive includes tackifiers and/or plasticizers in a combined amount of no more than 20 wt-%. In certain embodiments, a shell layer adhesive includes substantially no tackifiers and/or plasticizers. In this context,“substantially no” means less than 1 wt-%, less than 0.5 wt-%, or less than 0.1 wt-%, based on the total weight of the adhesive.

In certain embodiments, a discontinuous shell layer includes a plurality of adhesive structures, which may be disposed in a random pattern or nonrandom pattern (e.g., parallel lines or dots arranged on an ordered lattice). Typically, the structural shapes are discrete (meaning that the shapes are not connected or not all connected).

The adhesive structures may have a single shape, a variety of shapes, or may be arranged in such a way that they form an image (e.g., logos or indicia). Examples of suitable structure shapes include hemispheres, prisms (such as square prisms, rectangular prisms, cylindrical prisms and other similar polygonal features), pyramids, ellipses, and the like.

The adhesive structures can be deposited by such methods as knife coating, roll coating, gravure coating, rod coating, curtain coating, and air knife coating. The adhesive structures may also be deposited by known methods such as screen printing or inkjet printing, or by contact printing. A variety of contact printing techniques are suitable, as is well known by one of skill in the art. Among the useful direct contact printing techniques are flexographic printing, patterned roll coating, letterpress printing, lithography, stencil printing, and the like.

in certain embodiments, the adhesive structures have a total surface area that is less than the surface area of the cushion layer on which the structures are disposed. The surface area occupied by the adhesive structures and the size of the individual structures themselves can vary depending upon the intended use of the adhesive article.

In certain embodiments, the total surface area of the adhesive structures occupies up to 95%, up to 90%, or up to 80%, of the surface area of the cushion layer on which they are disposed in certain embodiments, the total surface area of the adhesive structures occupies at least 5%, at least 10%, or at least 2.0%, of the surface area of the first cushion layer.

The copolymers and adhesives of the shell layer may be prepared by any conventional polymerization method (such as solution polymerization or emulsion polymerization) including thermal bulk polymerization under adiabatic conditions, as is disclosed in, for example, U.S. Pat. Nos. 5,637,646 (Ellis) and 5,986,011 (Ellis et ak). Other methods of preparing (meth)acrylate copolymers include the continuous free radical polymerization methods described in U.S. Pat. Nos. 4,619,979 (Kotnour et al.) and 4,843,134 (Kotnour et ak), the polymerization within a polymeric package as described in U.S. Pat. No. 5,804,610 (Hamer et ak), and the on-web polymerization process as described in U.S. Pat. No. 4,181,752 (Martens et ak). Alternatively, the copolymers and adhesives of the shell layer may be prepared as exemplified in the Examples Section. Backings and Adhesive Articles

The adhesive articles of the present disclosure may be in the form of a tape or a die-cut article (e.g., labels, shaped graphic components).

Referring to FIG. 1, an adhesive article (e.g., tape) 10 includes a flexible backing 12, a first cushion layer 20 permanently bonded to a first surface 14 of the flexible backing 12, and a first discontinuous shell layer 22 adjacent the first cushion layer 20. Such articles can be single-sided adhesive articles (e.g., tapes or labels). In certain embodiments, such an adhesive article may further include a low adhesion backsize (a LAB) (not shown) on a second surface 16 of the flexible backing 12. A LAB is typically used in a tape on the surface of a backing opposite the surface on which the adhesive is disposed to allow a tape to unwind easily. Suitable LAB materials are described, for example, in U.S. Pat. No. US 6,919,405 (Kinning et ak).

Alternatively, in certain embodiments, an adhesive article of the present disclosure includes a second cushion layer permanently bonded to a second surface (i.e., second side) of the flexible backing, and a second discontinuous shell layer adjacent the second cushion layer. Such double-sided adhesive articles (e.g., tapes) may further include a release liner disposed on one of the first shell layer and/or the second shell layer. Release liners, which are removed before use of the adhesive article, include any suitable flexible material without specific limitations. Suitable release liners are commercially available and well known to one of skill in the art.

The flexible backings of the present disclosure may be any of a wide variety that are typically used in adhesive articles, particularly adhesive tapes. In certain embodiments, a flexible backing includes a material selected from the group of paper (e.g., Kraft paper) and polymeric films (e.g., polypropylene, polyethylene, polyurethane, polyester (e.g., polyethylene terephthalate), ethylene vinyl acetate, polyvinyl chloride (vinyl), cellulose acetate, and ethyl cellulose). The backing materials can be in the form of a nonwoven web, extruded film, metal foil or sheet backing (for example, retro-reflective or graphic film sheets).

Various well-known techniques of applying the cushion and shell layers can be used, including various wet coating methods (direct or indirect) and dry laminating methods, although dry laminating methods may not be as desirable as wet coating methods (e.g., knife coating, roll coating, gravure coating, rod coating, curtain coating, and air knife coating).

Every interface in an adhesive article is a potential failure interface which can diminish the ultimate potential strength of the adhesive bond. By utilizing the complementary orientation of acid- and base-containing monomeric units in the cushion and shell layers as described above, it is possible to enhance the interfacial bond between these layers to reduce or eliminate the possibility of bond failure at this two-layer interface. In other embodiments, techniques to enhance this bond include e-beam crosslinking the total tape construction after both layers are applied to a backing, UV post-curing the adhesives to directly crosslink the cushion and shell layers, and directly polymerizing one layer on top of the other to promote interpenetrating networks at the two-layer interface.

In still other embodiments, a cushion layer and/or shell layer comprises a surface treatment (e g., plasma treatment, corona treatment, or chemical primer) to enhance adhesion to each other. Thus, the cushion layer and the shell layer may be separated by one or more other materials, such as a chemical primer layer. Alternatively, in certain embodiments, a shell layer is directly disposed on a cushion layer (e.g., without a chemical primer). In certain embodiments, a surface of the flexible backing includes a surface treatment (e.g., plasma treatment, corona treatment, or chemical primer) to enhance adhesion of a cushion layer. Tims, the flexible backing and the cushion layer may be separated by one or more other materials, such as a chemical primer layer. Alternatively, in certain embodiments, a cushion layer is directly disposed on a surface of the flexible backing (e.g., without a chemical primer). Suitable surface treatments are well known to those skilled in the art and include coronas, plasmas, and flames, as described, for example in U.S. Pat. No. 4,828,871 (Strobel; PSA adhesion improved by plasma) and International Pub. No. WO 2012/152710 (Tesa; PSA adhesion improved by corona or flame).

Various combinations of these techniques can be used if desired to enhance adhesion between a cushion layer and a shell layer or between a flexible backing and a cushion layer.

EMBODIMENTS

Embodiment 1 is an adhesive article comprising:

a flexible backing;

a first cushion layer permanently bonded to a first surface of the flexible backing, wherein the first cushion layer:

has an average thickness of at least 10 micrometers; and

comprises an acrylate pressure-sensitive adhesive having a Fox Tg of up to -30°C, wherein the acrylate pressure-sensitive adhesive comprises a (meth)acrylate copolymer comprising:

a) one or more (meth)acrylate monomeric units of Formula (I) in an amount of at least 60 wt-% (at least 65 wt-%, at least 70 wt-%, at least 75 wt-%, or at least 80 wt- %), based on a total weight of monomeric units in the (meth)acrylate copolymer:

wherein:

Ri is hydrogen or a methyl group; and

R2 is an alkyl, heteroalkyl, aryl, aralkyl, or alkaryl group; and

b) one or more polar monomeric units in an amount of up to 7 wt-% (up to 6 wt- %, up to 5 wt-%, or up to 4 wt-%), based on a total weight of monomeric units in the (meth)acrylate copolymer;

wherein the sum of all monomeric units of the first cushion layer (meth)acrylate copolymer equals 100% by weight; and

a first discontinuous shell layer adjacent the first cushion layer, wherein:

the first discontinuous shell layer has an average thickness of up to 25 micrometers; the ratio of the first cushion layer average thickness to the first shell layer average thickness is at least 2: 1;

the first discontinuous shell layer comprises an adhesive (in certain embodiments the adhesive is a pressure-sensitive adhesive) having a Fox Tg of +lO°C to +50°C; and

the first discontinuous shell layer adhesive comprises a copolymer having a weight average molecular weight of at least 100,000 Daltons, wherein the copolymer comprises:

a) one or more low Tg (meth)acrylate monomeric units of Formula (II) in an amount of at least 25 wt-% (at least 30 wt-%, at least 35 wt-%, or at least 40 wt-%), based on a total weight of monomeric units in the copolymer:

wherein:

Ri is hydrogen or a methyl group; and

R ₃ is an alkyl, heteroalkyl, aryl, aralkyl, or alkaryl group;

b) one or more polar monomeric units in an amount of up to 5 wt-% (up to 4.5 wt-%, up to 4 wt-%, or up to 3.5 wt-%), based on a total weight of monomeric units in the copolymer; and

c) one or more high Tg nonpolar monomeric units in an amount of at least 35 wt-% (at least 40 wt-%, at least 45 wt-%, or at least 50 wt-%), based on a total weight of monomeric units in the copolymer;

wherein the sum of all monomeric units of the first shell layer copolymer equals 100% by weight. Embodiment 2 is the adhesive article of embodiment 1 wherein the acrylate pressure-sensitive adhesive of the first cushion layer has a Fox Tg of at least -85°C.

Embodiment 3 is the adhesive article of embodiment 1 or 2 wherein the first cushion layer has an average thickness of up to 150 micrometers (or up to 100 micrometers, or up to 50 micrometers).

Embodiment 4 is the adhesive article of any one of the previous embodiments wherein the first shell layer has an average thickness of up to 20 micrometers (or up to 12 micrometers, or up to 10 micrometers, or up to 8 micrometers, or up to 6 micrometers, or up to 4 micrometers, or up to 2 micrometers).

Embodiment 5 is the adhesive article of any one of the previous embodiments wherein the ratio of the first cushion layer average thickness to the first shell layer average thickness is at least 3: 1 (or at least 4: 1, or at least 5: 1, or at least 10: 1, or at least 20: 1, or at least 50: 1, or at least 70: 1).

Embodiment 6 is the adhesive article of any one of the previous embodiments wherein the ratio of the first cushion layer average thickness to the first shell layer average thickness is up to 300: 1 (or up to 200: 1, or up to 100: 1).

Embodiment 7 is the adhesive article of any one of the previous embodiments wherein the adhesive of the first shell layer has a Fox Tg of up to +40°C (or up to +30°C, or up to +20°C).

Embodiment 8 is the adhesive article of any one of the previous embodiments wherein the first cushion layer (meth)acrylate copolymer comprises one or more (meth)acrylate monomeric units of Formula (I) in an amount of up to 99.5 wt-% (or up to 95 wt-%, or up to 90 wt-%, or up to 85 wt-%), based on a total weight of monomeric units in the (meth)acrylate copolymer.

Embodiment 9 is the adhesive article of any one of the previous embodiments wherein the first cushion layer (meth)acrylate copolymer comprises one or more polar monomeric units in an amount of at least 0.5 wt-% (or at least 1 wt-%, or at least 1.5 wt-%, or at least 2 wt-%, or at least 2.5 wt-%, or at least 3 wt-%), based on a total weight of monomeric units in the (meth)acrylate copolymer.

Embodiment 10 is the adhesive article of any one of the previous embodiments wherein the first cushion layer (meth)acrylate copolymer comprises one or more (meth)acrylate monomeric units of Formula (I) wherein R2 is an alkyl group having 1 to 24 carbon atoms.

Embodiment 11 is the adhesive article of embodiment 10 wherein the first cushion layer (meth)acrylate copolymer comprises one or more (meth)acrylate monomeric units of Formula (I) derived from monomers selected from the group of 2-ethylhexyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, cyclohexyl (meth)acrylate, hexyl (meth)acrylate, 2-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isobomyl (meth)acrylate, norbomyl (meth)acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate, 2- methylbutyl (meth)acrylate, and combinations thereof (in certain embodiments, these monomers are selected from the group of 2-ethylhexyl acrylate, n-butyl acrylate, isooctyl acrylate, 2-octyl acrylate, and combinations thereof). Embodiment 12 is the adhesive article of any one of the previous embodiments wherein the first cushion layer (meth)acrylate copolymer comprises one or more polar monomeric units derived from monomers selected from the group of (meth)acrylic acid, (meth)acrylamide, alkyl-substituted

(meth)acrylamides (e.g., N,N-dimethyl acrylamide), and combinations thereof.

Embodiment 13 is the adhesive article of any one of the previous embodiments wherein the first shell layer copolymer comprises one or more (meth)acrylate monomeric units of Formula (II) in an amount of up to 64.5 wt-% (or up to 60 wt-%, or up to 55 wt-%, or up to 50 wt-%), based on a total weight of monomeric units in the copolymer.

Embodiment 14 is the adhesive article of any one of the previous embodiments wherein the first shell layer copolymer comprises one or more polar monomeric units in an amount of at least 0.5 wt-% (or at least 1 wt-%, or at least 1.5 wt-%, or at least 2 wt-%), based on a total weight of monomeric units in the copolymer.

Embodiment 15 is the adhesive article of any one of the previous embodiments wherein the first shell layer copolymer comprises one or more high Tg nonpolar monomeric units in an amount of up to 74.5 wt-% (or up to 70 wt-%, or up to 65 wt-%, or up to 60 wt-%), based on a total weight of monomeric units in the copolymer.

Embodiment 16 is the adhesive article of any one of the previous embodiments wherein the first shell layer copolymer comprises one or more low Tg (meth)acrylate monomeric units of Formula (II) wherein R ₃ is an alkyl group having 2 to 24 carbon atoms (in certain embodiments, 4 to 24 carbon atoms).

Embodiment 17 is the adhesive article of embodiment 16 wherein the first shell layer copolymer comprises one or more low Tg (meth)acrylate monomeric units of Formula (II) derived from monomers selected from the group of 2-ethylhexyl (meth)acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl (meth)acrylate, 2-octyl acrylate, isooctyl acrylate, isononyl acrylate, isostearyl acrylate, 2- methylbutyl acrylate, and combinations thereof (in certain embodiments, the monomers are selected from the group of 2-ethylhexyl acrylate, n-butyl acrylate, isooctyl acrylate, 2-octyl acrylate, and combinations thereof).

Embodiment 18 is the adhesive article of any one of the previous embodiments wherein the first shell layer copolymer comprises one or more polar monomeric units derived from monomers selected from the group of (meth)acrylic acid, (meth)acrylamide, alkyl-substituted (meth)acrylamides (e.g., N,N- dimethyl acrylamide), and combinations thereof.

Embodiment 19 is the adhesive article of any one of the previous embodiments wherein the first shell layer copolymer comprises one or more high Tg nonpolar monomeric units derived from monomers selected from the group of styrene, substituted styrene (e.g., methyl styrene), isobomyl (meth)acrylate, methyl (meth)acrylate, tert-butyl (meth)acrylate, iso-butyl methacrylate, cyclohexyl (meth)acrylate, norbomyl (meth)acrylate, and combinations thereof (in certain embodiments, these monomers are selected from the group of styrene, isobomyl (meth)acrylate, norbomyl acrylate, methyl (meth)acrylate, tert-butyl (meth)acrylate, iso-butyl methacrylate, cyclohexyl (meth)acrylate, and combinations thereof).

Embodiment 20 is the adhesive article of any one of the previous embodiments wherein the first cushion layer (meth)acrylate copolymer further comprises vinyl acetate monomeric units in an amount of up to 7 wt-%, based on the total weight of monomeric units in the copolymer.

Embodiment 21 is the adhesive article of any one of the previous embodiments wherein the first shell layer copolymer further comprises vinyl acetate monomeric units in an amount of up to 7 wt-%, based on the total weight of monomeric units in the copolymer.

Embodiment 22 is the adhesive article of any one of the previous embodiments wherein the first cushion layer (meth)acrylate copolymer comprises one or more polar monomeric units having an acid group and the first shell layer copolymer comprises one or more polar monomeric units having a basic group.

Embodiment 23 is the adhesive article of any one of the previous embodiments wherein the first cushion layer (meth)acrylate copolymer comprises one or more polar monomeric units having a basic group and the first shell layer copolymer comprises one or more polar monomeric units having an acidic group.

Embodiment 24 is the adhesive article of any one of the previous embodiments wherein the first cushion layer (meth)acrylate copolymer has a weight average molecular weight of at least 100,000 Daltons (or at least 200,000 Daltons, or at least 400,000 Daltons).

Embodiment 25 is the adhesive article of any one of the previous embodiments wherein the first cushion layer (meth)acrylate copolymer has a weight average molecular weight of up to 2,000,000 Daltons (or up to 1,000,000 Daltons, or up to 700,000 Daltons, or up to 500,000 Daltons).

Embodiment 26 is the adhesive article of any one of the previous embodiments wherein the first shell layer copolymer has a weight average molecular weight of up to 2,000,000 Daltons (or up to 1,000,000 Daltons, or up to 700,000 Daltons, or up to 500,000 Daltons).

Embodiment 27 is the adhesive article of any one of the previous embodiments wherein the first shell layer copolymer has a weight average molecular weight of at least 200,000 Daltons (or at least 300,000 Daltons, or at least 400,000 Daltons).

Embodiment 28 is the adhesive article of any one of the previous embodiments wherein the first cushion layer acrylate pressure-sensitive adhesive further comprises one or more additives selected from the group of colorants, fillers, flame retardants, antioxidants, UV-stabilizers, viscosity modifiers, and combinations thereof.

Embodiment 29 is the adhesive article of any one of the previous embodiments wherein the first shell layer adhesive further comprises one or more additives selected from the group of colorants (e.g., UV-fluore scent molecules), fillers, flame retardants, antioxidants, UV-stabilizers, viscosity modifiers, and combinations thereof. Embodiment 30 is the adhesive article of any one of the previous embodiments wherein the first cushion layer acrylate pressure-sensitive adhesive includes tackifiers and/or plasticizers in a combined amount of no more than 20 wt-%.

Embodiment 31 is the adhesive article of embodiment 30 wherein the first cushion layer acrylate pressure-sensitive adhesive includes substantially no tackifiers and/or plasticizers.

Embodiment 32 is the adhesive article of any one of the previous embodiments wherein the first shell layer adhesive includes tackifiers and/or plasticizers in a combined amount of no more than 20 wt- /

/O.

Embodiment 33 is the adhesive article of embodiment 32 wherein the first shell layer adhesive includes substantially no tackifiers and/or plasticizers.

Embodiment 34 is the adhesive article of any one of the previous embodiments wherein the flexible backing comprises a material selected from the group of paper (e.g., Kraft paper) and polymeric films (e.g., polypropylene, polyethylene, polyurethane, polyester (e.g., polyethylene terephthalate), ethylene vinyl acetate, cellulose acetate, and ethyl cellulose).

Embodiment 35 is the adhesive article of any one of the previous embodiments wherein the fi rst surface of the flexible backing comprises a surface treatment (e.g., plasma treatment, corona treatment, or chemical primer).

Embodiment 36 is the adhesive article of any one of the previous embodiments wherein the first cushion layer is directly disposed on the first surface of the flexible backing (e.g., without a chemical primer).

Embodiment 37 is the adhesive article of any one of the previous embodiments wherein the first cushion layer comprises a surface treatment (e.g., plasma treatment, corona treatment, or chemical primer).

Embodiment 38 is the adhesive article of any one of the previous embodiments wherein the fi rst shell layer is directly disposed on the first cushion layer (e.g , without a chemical primer).

Embodiment 39 is the adhesive article of any one of embodiments 1 through 38 which is a die- cut article.

Embodiment 40 is the adhesive article of any one of embodiments 1 through 38 which is a tape.

Embodiment 41 is the adhesive article of any one of the previous embodiments which demonstrates an increase (in certain embodiments, an at least one and a half-fold increase, or an at least two-fold increase) in 180° angle peel adhesion strength at a peel rate of 0.2 inch/minute (0.08 millimeter/second) from polypropylene at room temperature compared to an adhesive article having the same flexible backing and first cushion layer but without the first shell layer.

Embodiment 42 is the adhesive article of embodiment 41 which demonstrates an increase (in certain embodiments, an at least one and a half-fold increase, or an at least two-fold increase) in 180° angle peel adhesion strength at a peel rate of 0.2 inch/minute (0.08 millimeter/second) from polypropylene at a temperature of up to 65°C compared to an adhesive article having the same flexible backing and first cushion layer but without the first shell layer.

Embodiment 43 is the adhesive article of embodiment 41 or 42 which demonstrates an average rolling ball stopping distance of no more than 25% greater than that of the cushion layer without a shell layer according to a Rolling Ball Tack Test.

Embodiment 44 is the adhesive article of any one of the previous embodiments wherein the first discontinuous shell layer comprises a plurality of adhesive structures.

Embodiment 45 is the adhesive article of embodiment 44 wherein the plurality of adhesive structures is disposed in a random pattern or nonrandom pattern.

Embodiment 46 is the adhesive article of embodiment 44 or 45 wherein the adhesive structures have a single, a variety of shapes, or are arranged in such a way that they form an image (e.g., logos or indicia).

Embodiment 47 is the adhesive article of embodiment 45 or 46 wherein the adhesive structures have a total surface area that is less than the first cushion layer.

Embodiment 48 is the adhesive article of embodiment 47 wherein the total surface area of the adhesive structures occupies up to 95% (or up to 90%, or up to 80%) of the surface area of the first cushion layer.

Embodiment 49 is the adhesive article of embodiment 47 or 48 wherein the total surface area of the adhesive structures occupies at least 5% (or at least 10%, or at least 20%) of the surface area of the first cushion layer.

Embodiment 50 is the adhesive article of any one of the previous embodiments further comprising a LAB on a second surface of the flexible backing.

Embodiment 51 is the adhesive article of any one of embodiments 1 through 49 further comprising:

a second cushion layer permanently bonded to a second surface of the flexible backing, wherein the second cushion:

has an average thickness of at least 10 micrometers; and

comprises an acrylate pressure-sensitive adhesive having a Fox Tg of up to -30°C, wherein the acrylate pressure-sensitive adhesive comprises a (meth)acrylate copolymer comprising:

a) one or more (meth)acrylate monomeric units of Formula (I) in an amount of at least 60 wt-% (at least 65 wt-%, at least 70 wt-%, at least 75 wt-%, or at least 80 wt-%), based on a total weight of monomeric units in the

(meth)acrylate copolymer:

wherein:

Ri is hydrogen or a methyl group; and

R ₂ is an alkyl, heteroalkyl, aryl, aralkyl, or alkaryl group; and b) one or more polar monomeric units in an amount of up to 7 wt-% (up to 6 wt- %, up to 5 wt-%, or up to 4 wt-%), based on a total weight of monomeric units in the (meth)acrylate copolymer;

wherein the sum of all monomeric units of the second cushion layer

(meth)acrylate copolymer equals 100% by weight; and

a second discontinuous shell layer adjacent the second cushion layer, wherein:

the second discontinuous shell layer has an average thickness of up to 25 micrometers; the ratio of the second cushion layer average thickness to the second shell layer average thickness is at least 2: 1;

the second discontinuous shell layer comprises an adhesive (in certain embodiments, the adhesive is a pressure-sensitive adhesive) having a Fox Tg of +lO°C to +50°C; and

the second discontinuous shell layer adhesive comprises a copolymer having a weight average molecular weight of at least 100,000 Daltons, wherein the copolymer comprises:

a) one or more low Tg (meth)acrylate monomeric units of Formula (II) in an amount of at least 25 wt-% (at least 30 wt-%, at least 35 wt-%, or at least 40 wt-%), based on a total weight of monomeric units in the copolymer:

wherein:

Ri is hydrogen or a methyl group; and

R ₃ is an alkyl, heteroalkyl, aryl, aralkyl, or alkaryl group; b) one or more polar monomeric units in an amount of up to 5 wt-% (up to 4.5 wt-%, up to 4 wt-%, or up to 3.5 wt-%), based on a total weight of monomeric units in the copolymer; and

c) one or more high Tg nonpolar monomeric units in an amount of at least 35 wt-% (at least 40 wt-%, at least 45 wt-%, or at least 50 wt-%), based on a total weight of monomeric units in the copolymer;

wherein the sum of all monomeric units of the second shell layer copolymer equals 100% by weight.

Embodiment 52 is the adhesive article of embodiment 51 further comprising a release liner disposed on one of the first shell layer and/or the second shell layer.

Embodiment 53 is the adhesive article of embodiment 51 or 52 wherein the acrylate pressure- sensitive adhesive of the second cushion layer has a Fox Tg of at least -85°C.

Embodiment 54 is the adhesive article of any one or embodiments 51 through 53 wherein the second cushion layer has an average thickness of up to 150 micrometers (or up to 100 micrometers, or up to 50 micrometers).

Embodiment 55 is the adhesive article of any one of embodiments 51 through 54 wherein the second shell layer has an average thickness of up to 20 micrometers (or up to 12 micrometers, or up to 10 micrometers, or up to 8 micrometers, or up to 6 micrometers, or up to 4 micrometers, or up to 2 micrometers).

Embodiment 56 is the adhesive article of any one of embodiments 51 through 55 wherein the ratio of the second cushion layer average thickness to the second shell layer average thickness is at least 3: 1 (or at least 4: 1, or at least 5: 1, or at least 10: 1, or at least 20: 1, or at least 50: 1, or at least 70: 1).

Embodiment 57 is the adhesive article of any one of embodiments 51 through 56 wherein the ratio of the second cushion layer average thickness to the second shell layer average thickness is up to 300: 1 (or up to 200: 1, or up to 100: 1).

Embodiment 58 is the adhesive article of any one of embodiments 51 through 57 wherein the adhesive of the second shell layer has a Fox Tg of up to +40°C (or up to +30°C, or up to +20°C).

Embodiment 59 is the adhesive article of any one of embodiments 51 through 58 wherein the second cushion layer (meth)acrylate copolymer comprises one or more (meth)acrylate monomeric units of Formula (I) in an amount of up to 99.5 wt-% (or up to 95 wt-%, or up to 90 wt-%, or up to 85 wt-%), based on a total weight of monomeric units in the (meth)acrylate copolymer.

Embodiment 60 is the adhesive article of any one of embodiments 51 through 59 wherein the second cushion layer (meth)acrylate copolymer comprises one or more polar monomeric units in an amount of at least 0.5 wt-% (or at least 1 wt-%, or at least 1.5 wt-%, or at least 2 wt-%, or at least 2.5 wt- %, or at least 3 wt-%), based on a total weight of monomeric units in the (meth)acrylate copolymer. Embodiment 61 is the adhesive article of any one of embodiments 51 through 60 wherein the second cushion layer (meth)acrylate copolymer comprises one or more (meth)acrylate monomeric units of Formula (I) wherein R ₂ is an alkyl group having 1 to 24 carbon atoms.

Embodiment 62 is the adhesive article of embodiment 61 wherein the second cushion layer (meth)acrylate copolymer comprises one or more (meth)acrylate monomeric units of Formula (I) derived from monomers selected from the group of 2-ethylhexyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, cyclohexyl (meth)acrylate, hexyl (meth)acrylate, 2-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isobomyl (meth)acrylate, norbomyl (meth)acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate, 2- methylbutyl (meth)acrylate, and combinations thereof (in certain embodiments, these monomers are selected from the group of 2-ethylhexyl acrylate, n-butyl acrylate, isooctyl acrylate, 2-octyl acrylate, and combinations thereof).

Embodiment 63 is the adhesive article of any one of embodiments 51 through 62 wherein the second cushion layer (meth)acrylate copolymer comprises one or more polar monomeric units derived from monomers selected from the group of (meth)acrylic acid, (meth)acrylamide, alkyl-substituted (meth)acrylamides (e.g., N,N-dimethyl acrylamide), and combinations thereof.

Embodiment 64 is the adhesive article of any one of embodiments 51 through 63 wherein the second shell layer copolymer comprises one or more (meth)acrylate monomeric units of Formula (I) in an amount of up to 64.5 wt-% (or up to 60 wt-%, or up to 55 wt-%, or up to 50 wt-%), based on a total weight of monomeric units in the copolymer.

Embodiment 65 is the adhesive article of any one of embodiments 51 through 64 wherein the second shell layer copolymer comprises one or more polar monomeric units in an amount of at least 0.5 wt-% (or at least 1 wt-%, or at least 1.5 wt-%, or at least 2 wt-%), based on a total weight of monomeric units in the copolymer.

Embodiment 66 is the adhesive article of any one of embodiments 51 through 65 wherein the second shell layer copolymer comprises one or more high Tg nonpolar monomeric units in an amount of up to 74.5 wt -% (or up to 70 wt-%, or up to 65 wt-%, or up to 60 wt-%), based on a total weight of monomeric units in the copolymer.

Embodiment 67 is the adhesive article of any one of embodiments 51 through 66 wherein the second shell layer copolymer comprises one or more low Tg (meth)acrylate monomeric units of Formula (II) wherein R ₃ is an alkyl group having 2 to 24 carbon atoms (in certain embodiments, 4 to 24 carbon atoms).

Embodiment 68 is the adhesive article of embodiment 67 wherein the second shell layer copolymer comprises one or more low Tg (meth)acrylate monomeric units of Formula (II) derived from monomers selected from 2-ethylhexyl (meth)acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl (meth)acrylate, 2-octyl acrylate, isooctyl acrylate, isononyl acrylate, isostearyl acrylate, 2- methylbutyl acrylate, and combinations thereof (in certain embodiments, the monomers are selected from the group of 2-ethylhexyl acrylate, n-butyl acrylate, isooctyl acrylate, 2-octyl acrylate, and combinations thereof).

Embodiment 69 is the adhesive article of any one of embodiments 51 through 68 wherein the second shell layer copolymer comprises one or more polar monomeric units derived from monomers selected from the group of (meth)acrylic acid, (meth)acrylamide, alkyl-substituted (meth)acrylamides (e.g., N,N-dimethyl acrylamide), and combinations thereof.

Embodiment 70 is the adhesive article of any one of embodiments 51 through 69 wherein the second shell layer copolymer comprises one or more high Tg nonpolar monomeric units derived from monomers selected from the group of styrene, substituted styrene (e.g., methyl styrene), isobomyl (meth)acrylate, methyl (meth)acrylate, tert-butyl (meth)acrylate, iso-butyl methacrylate, cyclohexyl (meth)acrylate, norbomyl (meth)acrylate, and combinations thereof (in certain embodiments, these monomers are selected from the group of styrene, isobomyl (meth)acrylate, norbomyl acrylate, methyl (meth)acrylate, tert-butyl (meth)acrylate, iso-butyl methacrylate, cyclohexyl (meth)acrylate, and combinations thereof).

Embodiment 71 is the adhesive article of any one of embodiments 51 through 70 wherein the second cushion layer (meth)acrylate copolymer further comprises vinyl acetate monomeric units in an amount of up to 7 wt-%, based on the total weight of monomeric units in the copolymer.

Embodiment 72 is the adhesive article of any one of embodiments 51 through 71 wherein the second shell layer copolymer further comprises vinyl acetate monomeric units in an amount of up to 7 wt-%, based on the total weight of monomeric units in the copolymer.

Embodiment 73 is the adhesive article of any one of embodiments 51 through 72 wherein the second cushion layer (meth)acrylate copolymer comprises one or more polar monomeric units having an acid group and the second shell layer copolymer comprises one or more polar monomeric units having a basic group.

Embodiment 74 is the adhesive article of any one of embodiments 51 through 73 wherein the second cushion layer (meth)acrylate copolymer comprises one or more polar monomeric units having a basic group and the second shell layer copolymer comprises one or more polar monomeric units having an acidic group.

Embodiment 75 is the adhesive article of any one of embodiments 51 through 74 wherein the second cushion layer (meth)acrylate copolymer has a weight average molecular weight of at least 100,000 Daltons (or at least 200,000 Daltons, or at least 400,000 Daltons).

Embodiment 76 is the adhesive article of any one of embodiments 51 through 75 wherein the second cushion layer (meth)acrylate copolymer has a weight average molecular weight of up to 2,000,000 Daltons (or up to 1,000,000 Daltons, or up to 700,000 Daltons, or up to 500,000 Daltons).

Embodiment 77 is the adhesive article of any one of embodiments 51 through 76 wherein the second shell layer copolymer has a weight average molecular weight of up to 2,000,000 Daltons (or up to 1,000,000 Daltons, or up to 700,000 Daltons, or up to 500,000 Daltons). Embodiment 78 is the adhesive article of any one of embodiments 51 through 77 wherein the second shell layer copolymer has a weight average molecular weight of at least 200,000 Daltons (or at least 300,000 Daltons, or at least 400,000 Daltons).

Embodiment 79 is the adhesive article of any one of embodiments 51 through 78 wherein the second cushion layer acrylate pressure-sensitive adhesive further comprises one or more additives selected from the group of colorants, fillers, flame retardants, antioxidants, UV-stabilizers, viscosity modifiers, and combinations thereof.

Embodiment 80 is the adhesive article of any one of embodiments 51 through 79 wherein the second shell layer adhesive further comprises one or more additives selected from the group of colorants (e.g., UV-fluorescent molecules), fillers, flame retardants, antioxidants, UV-stabilizers, viscosity modifiers, and combinations thereof.

Embodiment 81 is the adhesive article of any one of embodiments 51 through 80 wherein the second cushion layer acrylate pressure-sensitive adhesive includes tackifiers and/or plasticizers in a combined amount of no more than 20 wt-%.

Embodiment 82 is the adhesive article of embodiment 81 wherein the second cushion layer acrylate pressure-sensitive adhesive includes substantially no tackifiers and/or plasticizers.

Embodiment 83 is the adhesive article of any one of embodiments 51 through 82 wherein the second shell layer adhesive includes tackifiers and/or plasticizers in a combined amount of no more than 20 wt-%.

Embodiment 84 is the adhesive article of embodiment 83 wherein the second shell layer adhesive includes substantially no tackifiers and/or plasticizers.

Embodiment 85 is the adhesive article of any one of embodiments 51 through 84 wherein the second cushion layer is directly disposed on the second surface of the flexible backing (e.g., without a chemical primer).

Embodiment 86 is the adhesive article of any one of embodiments 51 through 85 wherein the second cushion layer comprises a surface treatment (e.g., plasma treatment, corona treatment, or chemical primer).

Embodiment 87 is the adhesive article of any one of embodiments 51 through 86 wherein the second shell layer is directly disposed on the second cushion layer (e.g., without a chemical primer).

Embodiment 88 is the adhesive article of any one of embodiments 51 through 87 which demonstrates an increase (in certain embodiments, an at least one and a half-fold increase, or an at least two-fold increase) in 180° angle peel adhesion strength at a peel rate of 0.2 inch/minute (0.08 millimeter/second) from polypropylene at room temperature compared to an adhesive article having the same flexible backing and second cushion layer but without the second shell layer.

Embodiment 89 is the adhesive article of embodiment 88 which demonstrates an increase (in certain embodiments, an at least one and a half-fold increase, or an at least two-fold increase) in 180° angle peel adhesion strength at a peel rate of 0.2 inch/minute (0.08 millimeter/second) from polypropylene at a temperature of up to 65°C compared to an adhesive article having the same flexible backing and second cushion layer but without the second shell layer.

Embodiment 90 is the adhesive article of embodiment 88 or 89 which demonstrates an average rolling ball stopping distance of no more than 25% greater than that of the cushion layer without a shell layer according to a Rolling Ball Tack Test.

Embodiment 91 is the adhesive article of any one of embodiments 51 through 90 wherein the second discontinuous shell layer comprises a plurality of adhesive structures.

Embodiment 92 is the adhesive article of embodiment 91 wherein the plurality of adhesive structures is disposed in a random pattern or nonrandom pattern.

Embodiment 93 is the adhesive article of embodiment 91 or 92 wherein the adhesive structures have a single, a variety of shapes, or are arranged in such a way that they form an image (e.g., logos or indicia).

Embodiment 94 is the adhesive article of any one of embodiments 91 through 93 wherein the adhesive structures have a total surface area that is less than the second cushion layer.

Embodiment 95 is the adhesive article of embodiment 94 wherein the total surface area of the adhesive structures occupies up to 95% (or up to 90%, or up to 80%) of the surface area of the second cushion layer.

Embodiment 96 is the adhesive article of embodiment 94 or 95 wherein the total surface area of the adhesive structures occupies at least 5% (or at least 10%, or at least 20%) of the surface area of the second cushion layer.

EXAMPLES

Objects and advantages of this disclosure are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this disclosure.

Unless otherwise noted, all parts, percentages, ratios, etc. in the examples and the rest of the specification are by weight, and all reagents used in the examples were obtained, or are available, from general chemical suppliers such as, for example, Sigma-Aldrich, Saint Louis, MO, or may be synthesized by conventional methods.

The following abbreviations are used in this section: mL=milliliter, sec=seconds, min=minutes, h=hours, g=gram, mg=milligram, mmol=millimole, °C=degrees Celsius, °F=degrees Fahrenheit.

Materials

Test Methods

Peel Adhesion Strength

Peel adhesion strength was measured at various peel rates on the tapes prepared as described below. Stainless steel and polypropylene test panels, measuring 2 inches (5.1 centimeters) wide by 6 inches (15.2 centimeters) long were cleaned by wiping once with 2-butanone, once with heptane, and three times with acetone, all using a lint free tissue. The test panels were then allowed to dry at least 10 minutes before use. Adhesive tape specimens measuring 1 inch (2.54 centimeters) wide by between 6 inches (15.2 centimeters) to 7 inches (17.8 centimeters) long were applied to the panels then rolled down using a 2 kilogram (4.5 pound) hard rubber roller back and forth two times over the adhered tape specimens. To the free end of the adhesive tape was attached a strip of polyester backed PSA tape (3M 8403 HD, 3M Company, St. Paul, MN) measuring approximately 15 inches (38.1 centimeters) long which was folded back on itself to create a leader approximately 7 inches (17.8 centimeters) long. The test panel with tape specimen attached thereto was conditioned at 65°C for 24 hours, and then equilibrated at 24°C and 50% relative humidity for at least 16 hours prior to testing. Next, the test panel/tape specimen was secured in the lower grip of a tensile tester (Model 3365 Dual Column Table Frame, obtained from Instron, Norwood, MA) equipped with a 500 Newton load cell, and the tape leader was folded back and secured in the top grip to form a 180° peel angle. The tensile tester was programed to automatically step through the various peel rates on a single tape specimen. Peel force was measured across 8 logarithmic peel rate steps from 8.47 millimeters per second (mm/sec) to 0.00847 mm/sec. The data acquisition rate was 10 data points per second. At each peel rate, the peel force was measured for a set acquisition time and the reported value is the average over the acquisition time. The first and last 10% of collected data points were not included in the calculation for each acquisition time.

The tensile tester was also equipped with a temperature control chamber (Model 3119-609, obtained from Instron, Norwood, MA) to allow testing at temperatures other than room temperature. When using the environmental chamber, test specimens were equilibrated in the chamber for at least 10 minutes prior to testing. The results were reported in Newtons/centimeter (N/cm).

Rolling Ball Tack

Tack was evaluated using a rolling ball tack test according to ASTM D3121-17, with the following modifications. The tape specimens were not conditioned in a humidity controlled environment prior to testing. The tape specimens were held in place with a strip of double-sided pressure sensitive adhesive tape (3M 665, 89 micrometers total thickness, 3M Company, St. Paul, MN) running the length of the specimen between the tape backing and the flat aluminum plate used as the work surface for testing. Chrome plated steel ball bearings conforming to ASTM A295/A295M-14 and measuring 11 millimeters in diameter and weighing 5.593 +/- .003 grams were used. A RBT-100 rolling ball tack test ramp from Cheminstruments (Fairfield, OH) was employed. The rolling ball distance was taken as the average of four tests run on a single tape specimen.

Shell Laver Thickness

The thickness of the discontinuous shell layer pattern features was measured by optical interferometry using a Model WYKO NT 9800 Optical Profiling System (Bruker Corporation, Billerica, MA) in three different locations across the sample. At each measurement location, three features were included in the field of view. A plane fit was applied to the lower, background region and the peak height was taken as the highest point within the region of interest for each printed feature.

Gel Permeation Chromatography (GPC)

The molecular weight distribution of the compounds was characterized using conventional gel permeation chromatography (GPC). The GPC instrumentation, which was obtained from Waters Corporation (Milford, MA, USA), included a high pressure liquid chromatography pump (Model 1515HPLC), an auto-sampler (Model 717), a UV detector (Model 2487), and a refractive index detector (Model 2410). The chromatograph was equipped with two 5 micrometer PLgel MIXED-D columns (available from Varian Incorporated, Palo Alto, CA). Samples of polymeric solutions were prepared by dissolving polymer or dried polymer materials in tetrahydrofuran at a concentration of 0.5 percent (weight/volume) and filtering through a 0.2 micrometer polytetrafluoroethylene filter (available from VWR International, West Chester, PA). The resulting samples were injected into the GPC and eluted at a rate of 1 milliliter per minute through the columns which were maintained at 35°C. The system was calibrated with polystyrene standards using a linear least squares fit analysis to establish a calibration curve. The weight average molecular weight (Mw) and the polydispersity index (weight average molecular weight divided by number average molecular weight) were calculated for each sample against the standard calibration curve.

Glass Transition Temperature (Tg)

Fox Glass Transition Temperature (Tg) is a calculated value using the Fox equation. The calculation is based on the weighted average of the individual homopolymer glass transition values. For a copolymer prepared from n different monomers, the inverse of the Tg of the copolymer is equal to the summation of the weight fraction of each component divided by the Tg of that particular component. That is, for a copolymer prepared from n components, 1 / Tg of the copolymer is equal to (weight fraction of component one ÷ Tg of component one) + (weight fraction of component two ÷ Tg of component two) + (weight fraction of component 3 ÷ Tg of component 3) + ....+ (weight fraction of component n ÷ Tg of component n).

Preparation of Shell Favers 1-6 (S I -S6)

Shell Fayers 1-6 were prepared by solution polymerization in a bottle as follows. The materials and amounts shown in Table 1 were placed in a glass bottle. VAZO 52 was provided as 0.5 part by weight of a 20 wt-% solution in ethyl acetate and IOTG was provided as 0.2 part by weight of a 50 wt-% solution. For S5 and S6, 0.28 part by weight of a 50 wt-% solution of TDDM in ethyl acetate was used in place of IOTG. The amounts shown in Table 1 represent the amount of solid material employed in the compositions. Sixty-six (66) parts by weight of ethyl acetate was also added to the bottle. The solutions were purged with nitrogen for four minutes before securely sealing the bottles, placing them in a rotating water bath at 60°C for 24 hours, then allowing them to cool to ambient temperature to obtain adhesive polymer solutions having a solids content of approximately 60 wt-%. The resulting adhesive polymer solutions were used to evaluate the polymers for their molecular weights and glass transition temperatures as described in the test methods. The monomer compositions, molecular weights, and glass transition temperatures (Tg) are shown in Table 1.

Preparation of Cushion Faver 1 (Cl) Cushion Layer 1, containing the materials and amounts shown in Table 1, can be prepared by solution polymerization in a manner similar to that described above for preparing Shell Layers 1 to 4.

The solvent was a mixture of ethyl acetate and heptane. The resulting adhesive polymer solution was used to evaluate the polymer to determine the molecular weight and glass transition temperature as described in the test methods.

Preparation of Cushion Laver 2 (C2)

Cushion Layer 2 was prepared in a manner similar to that described above for preparing Cushion Layer 1. With The resulting adhesive polymer solution was used to evaluate the polymer for its molecular weight and glass transition temperature as described in the test methods. The monomer composition, molecular weight, and glass transition temperature (Tg) are shown in Table 1.

Coating Methods

Cushion Laver 1 (C 1 ) Coating

The Cushion Layer 1 adhesive polymer solution prepared as described above was coated onto the release treated side of a 0.002 inch (51 micrometers) thick, siliconized polyester release liner using a knife coating station having a gap setting of 0.014 inch (356 micrometers) greater than the release liner thickness. The films were coated and dried at 20 feet/minute (6.1 meters/minute) by passing them through three heating zones. Zone 1: having temperature of l20°F (49°C) and a length of 9 feet (2.7 meters); Zone 2: having temperature of l40°F (60°C) and a length of 9 feet (2.7 meters); and Zone 3: having temperature of 2lO°F (99°C) and a length of 18 feet (5.4 meters). The average measured coating weight after drying was 45.6 grams/square meter, which corresponded to a coating thickness of approximately 0.0019 inch (48 micrometers). The exposed adhesive surface of the adhesive coated release liner was then laminated to the treated side of a PPET film using two in-line nip rollers.

Cushion Laver 2 (C2) Coating

Cushion Layer 2 Coating was prepared in a manner similar to that described above for preparing Cushion Layer 1 Coating with the following modification. A gap setting of 0.007 inch (178 micrometers) was used. The estimated dried coating thickness was approximately 0.0019 inch (48 micrometers). The exposed adhesive surface of the adhesive coated release liner was then laminated to the treated side of a PPET film using two in-line nip rollers.

Discontinuous Shell Laver Coating (S 1 -S4) onto Cushion Laver 1 (Cl)

Shell Layer adhesive polymer solutions 1-4, diluted to 20 wt-% solids in a final solvent combination of ethyl acetate: l-propoxy-2 -propanol / 17:83 (w:w), were flexographically printed in a discontinuous pattern using a 3.0 billion cubic micrometers (bcm)/900 lines per inch (lpi) ceramic anilox roller at 50 feet/minute directly onto the exposed cushion layer surface of the Cl coated PPET film samples prepared as described above after removal of the release liner therefrom. The flexographic plates were manufactured from DUPONT CYREL DPR 67 (DuPont Packaging Graphics, Wilmington, DE) and patterned by Southern Graphics Systems Inc. (SGS, Brooklyn Park, MN) consisting to provide different area coverage patterns of 100 micrometer diameter circular dots arranged on a hexagonal lattice. The flexographic printing plate was attached on 0.060 inch 3M E1060H FLEXOGRAPHIC PLATE MOUNTING TAPE (3M, St. Paul, MN). The dot diameters ranged in size from 50 micrometers to 150 micrometers, with gaps between printed features ranging from 25 micrometers to 400 micrometers. Similar experiments resulted in a dot thickness of between 0.1 and 0.3 micrometer when measured as described in the test method“Shell Layer Thickness.” The coatings reported here are believed to have the same thicknesses since the same coating process was employed. The printed surface area coverage ranged from 20% to 80%. The resulting patterned printed article was dried at 2l5°F (l02°C) by passing it through a five-foot long forced air oven at 50 feet/minute then laminated to a 0.002 inch (51 micrometers) thick release coated polyester release liner film using two in-line nip rollers. This multilayer article was then crosslinked by electron beam (ebeam) from the release liner side using an accelerated electron source (Model CB-300 ELECTROCURTAIN, from Energy Sciences, Incorporated, Wilmington, MA) at an accelerating voltage of 220 kiloVolts. Samples were conveyed through the ebeam unit using a polyester carrier at a speed of 25.9 feet/minute (9 meters/minute), to provide a dose of 6 MegaRads. Samples of cushion layer 1 and cushion layer 2, each alone between PPET and release liner films, were also irradiated to provide comparative examples. The resulting tape constructions were evaluated for peel adhesion strength, and in some cases rolling ball tack, as described in the test methods. The results are shown in Tables 2-4.

Discontinuous Shell Laver Coating (S5 and S6) onto Cushion Laver 2

A discontinuous shell layer coating was provided on cushion layer 2 in the same manner as described for“Discontinuous Shell Layer Coating (S1-S4) onto Cushion Layer 1 (Cl)” to provide a dot pattern having the same characteristics with the following modifications. The ebeam dose used was 10 MegaRads. This resulting tape was evaluated for peel adhesion strength as described in the test methods. The results are shown in Tables 2-4.

Compositions

Table 1 : Cushion and Shell Layer Compositions

Results

Table 2: Peel Adhesion Strength - at 24°C on Polypropylene

CE: Comparative Example; NA: not applicable

Table 3: Peel Adhesion Strength - at 65°C on Polypropylene

CE: Comparative Example; NA: not applicable Table 4: Tack - Rolling Ball Distance

CE: Comparative Example; NA: not applicable The complete disclosures of the patents, patent documents, and publications cited herein are incorporated by reference in their entirety as if each were individually incorporated. To the extent that there is any conflict or discrepancy between this specification as written and the disclosure in any document that is incorporated by reference herein, this specification as written will control. Various modifications and alterations to this disclosure will become apparent to those skilled in the art without departing from the scope and spirit of this disclosure. It should be understood that this disclosure is not intended to be unduly limited by the illustrative embodiments and examples set forth herein and that such examples and embodiments are presented by way of example only with the scope of the disclosure intended to be limited only by the claims set forth herein as follows.