Background

In electronic devices, particularly mobile electronic devices (e.g., handheld or wearable electronic devices), pressure sensitive adhesives (PSAs) are typically used to bond the cover glass (or lens) to the underlying display module of an electronic device, bond the touch sensor to the cover glass and display, or bond the lower components of the display to the housing. The pressure-sensitive adhesives used in mobile electronic devices are usually optically clear adhesives (OCAs). For these applications (commonly referred to as electronics bonding or e-bonding), PSAs and OCAs should have sufficiently high adhesive strength to properly maintain good adhesion to those components, not only when the mobile electronic devices are operating under normal conditions, but also when they are deformed by external forces (e.g,, bending, folding, flexing) or subjected to traumatic forces (e.g., dropping of the mobile electronic device onto a hard surface). Regarding deformation, the components of the electronic de vices may be deformed when users sit in chairs while the electronic devices are in their pockets or press down on the electronic device with their hips. Under such conditions, tire pressure sensitive adhesives should have a strength of adhesion that can maintain the adhesion to, for example, the cover glass (sometimes referred to as anti-lifting properties). Regarding traumatic forces, the pressure sensitive adhesives should have a drop/impact resistance that can maintain adhesion of the components even when large instantaneous impacts are applied to the portable electronic devices when dropped.

Adhesives that can dissipate energy and resist delamination forces associated with high strain events (e.g., flexing and folding) and high strain rate events, such as that experienced during a device drop, have gained increasing significance for the electronic device industry. The ability to produce pressure sensitive adhesives that resist de-bonding (via interfacial or cohesive failure modes) during these high impact and dynamic deformations has become a highly desired property, inclusive of traditional performance metrics such as good peel strength, shear strength, tensile adhesion, and creep resistance, amongst others, and thus has become a commercially attractive performance criterion for continued product differentiation within this competitive and fast paced market space.

Given the electronics industry’s trend towards device simplification (i.e., combining layers and/or layer functions) and reducing bonding area and overall device thickness, (and moreover demanding enhanced flexibility), there exists a growing need for adhesive compositions that have good impact resistance, compliance, and elastic recovery. Summary

An adhesive composition is provided that contains a polymeric material prepared using a polymerizable composition that contains a polyether-containing macromer (i.e., monomer). More specifically, the polyether-containing macromer has a urea (-NH-(C=0)-NH-) or carbamate (-NH- (C=0)-0-) linkage between a polyether group and a (meth)acryloyl group. Additionally, an article that contains the adhesive composition is provided. The articles can be an adhesive tape or can be part of another article such as, for example, an electronic device that is impact resistant and/or flexible and/or foldable. In some embodiments, the adhesive composition is clear (such as optically clear, if desired).

In a first aspect, an adhesive composition is provided that contains a polymeric material derived from a polymerizable composition comprising various polymerizable components. The polymerizable components include a) a polyether-containing macromer, b) an alkyl (meth)acrylate, and c) an optional polar monomer, and d) a crosslinking agent. The polyether-containing macromer is of Formula (I).

CH ₂ =CHR ¹ -(C=0)-0-R ² -NH-(C=0)-X ¹ -Q ¹

(I)

In Formula (I), the group R ¹ is hydrogen or methyl, the group R ² is an alkylene having 1 to 4 carbon atoms, the group X ¹ is -O- or -NH-, and Q ¹ is a polyether group. The polyether-containing macromer has a urea (-NH-(C=0)-NH-) or carbamate (-NH-(C=0)-0-) linkage between the (meth)acrylolyoxy group (CH ₂ =CHR ¹ -(C=0)-0-) and the polyether group (Q ¹ ).

In some embodiments of the first aspect, the adhesive composition contains a first polymer and a second polymer. The first polymer is derived from a first polymerizable composition comprising 1) an alkyl (meth)acrylate and 2) an optional polar monomer. The second polymer is derived from a second polymerizable composition comprising 1) a polyether macromer of Formula (I) as described above, 2) an alkyl (meth)acrylate, 3) an optional polar monomer, and 4) a crosslinking agent.

In other embodiments of the first aspect, the adhesive composition comprises a polymerized product of a second polymerizable composition that includes a) a syrup composition comprising a partially polymerized product of a first polymerizable composition, b) a polar monomer if the syrup composition is free of the optional polar monomer or if additional polar monomer is desired, c) a polyether macromer of Formula (I) as described above, and d) a crosslinking agent. The syrup composition comprises 1) 1 to 20 weight percent solute polymer based on a total weight of the syrup, the solute polymer being a first polymer having a weight average molecular weight of at least 100,000 Daltons and 2) 80 to 99 weight percent solvent monomers based on a total weight of the syrup. The solvent monomers comprise 1) an alkyl (meth)acylate and 2) an optional polar monomer. The polymerized product of the second polymerizable composition comprises the first polymer and a second polymer, wherein the second polymer or both the second polymer and the first polymer are crosslinked.

In a second aspect, an article is provided. The article includes a) a substate and b) an adhesive composition positioned adjacent to the substrate. The adhesive composition is the same as described above in the first aspect.

In a third aspect, a method of making an adhesive composition is provided. The method includes providing a first polymerizable composition that contains 1) an alkyl (meth)acrylate and 2) an optional polar monomer. The method further includes forming a syrup composition by partially polymerizing the first polymerizable composition, wherein the syrup composition comprises 1) 1 to 20 weight percent of solute polymer based on a total weight of the syrup composition, the solute polymer being a first polymer having a weight average molecular weight of at least 100,000 Daltons and 2) 80 to 99 weight percent of solvent monomers based on a total weight of the syrup, the solvent monomers comprising i) the alkyl (meth)acrylate and ii) the optional polar monomer. The method still further includes preparing a second polymerizable composition comprising 1) the syrup composition, 2) a polar monomer if the syrup composition is free of the optional polar monomer or if additional polar monomer is desired, 3) a polyether macromer of Formula (I) as described above in the first aspect, and 4) a crosslinking agent. The method yet further includes polymerizing the second polymerizable composition to form the adhesive composition comprising 1) the first polymer and 2) a second polymer, wherein the second polymer or both the second polymer and the first polymer are crosslinked.

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. These terms 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 the listed elements or a combination of any two or more of the listed elements.

The term “polymer” and “polymeric material” are used interchangeably to refer to homopolymers, copolymers, terpolymers, and the like.

The term “polymerizable component” refers to a compound that can undergo polymerization (i.e., the compound has a polymerizable group). The polymerizable component typically has an ethylenically unsaturated group such as a (meth)acryloyl-containing group or a vinyl group that is the polymerizable group. The polymerizable component can be referred to interchangeably as a “monomer”. The term “macromer” refers to a monomer having a polymeric group such as a polyether group (i.e., macromers are a subset of monomers). The term “polymerizable composition” refers to the reaction mixture that can be polymerized. It includes the polymerizable components (i.e., monomers including macromers) plus any other material such as a free radical initiator, chain transfer agent, antioxidant, solvent, and the like that may be included in the reaction mixture.

The term “monomeric unit” refers to the reaction product of a polymerizable component (i.e., a monomer (including a macromer)) within the polymeric material. As an example, the monomeric unit of acrylic acid (H ₂ C=CH-(C=0)-OH) is where the asterisks (*) indicate the attachment site to another group such as another monomeric unit in the polymer.

The term “(meth)acryloyl” refers to a group of formula CH ₂ =CR-(C=0)- where R is hydrogen (for an acryloyl group) or methyl (for a methacryloyl group).

The term “(meth)acrylate” refers to a methacrylate and/or acrylate. Likewise, the term (meth)acrylic acid” refers to methacrylic acid and/or acrylic acid and the term “(meth)acrylamide” refers to methacrylamide and/or acrylamide.

The term “polyether” refers to a polymeric group having at least 3 alkylene oxide groups. The alkylene oxide groups are often selected from ethylene oxide (-(C ₂ H ₄ O)-), propylene oxide (-(C ₃ H ₆ O)-), tetramethylene oxide (-(CTLO)-), or a mixture thereof. The terms “poly(tetramethylene oxide)” and “poly(tetrahydrofuran)” can be used interchangeably.

The terms “urea group” and “urea linkage” are used interchangeably to refer to a divalent group or linkage of formula -NH-(C=0)-NH-.

The terms “carbamate group” and “carbamate linkage” are used interchangeably to refer to a divalent group or linkage of formula -NH-(C=0)-0-

The term “vinyl” refers to a polymerizable component that has a group CH ₂ =CH- but that is not part of a (meth)acryloyl group.

The term “syrup” refers to a composition that contains both unreacted monomers and a polymerized product of monomers. The polymerized product can be referred to as a “solute polymer” and it is dissolved in the monomers. That is, the monomers function as a solvent for the polymerized product and can be referred to as “solvent monomers”. The syrup usually contains little or no other solvent such as a non-reactive organic solvent. The syrup is typically present as a homogeneous mixture with any liquids being miscible with each other.

Herein, the term “pressure-sensitive adhesive” or “PSA” is used in its conventional manner according to the Pressure-Sensitive Tape Council, which states that pressure -sensitive adhesives are known to possess properties including the following: (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., 23 °C). Central to all PSAs is a desired balance of adhesion and cohesion that is often achieved by optimizing the physical properties of the elastomer, such as glass transition temperature and modulus. For example, if the glass transition temperature (T _g ) or modulus of the elastomer is too high and above the Dahlquist criterion for tack (storage modulus of 3 x 10 ⁶ dynes/cm ² (100 kPa) at room temperature (e.g., 23 °C) and oscillation frequency of 1 Hz), the material will not be tacky and is less useful by itself as a PSA material.

Herein, the term “glass transition temperature” can be written interchangeably as “T _g ”.

The glass transition temperature for a polymeric material is typically measured by Dynamic Mechanical Analysis (DMA) as the maximum in tan delta (d). The glass transition temperature of a monomer (including the macromer) refers to the glass transition temperature of the homopolymer formed from the monomer, which can be a macromer.

As used herein, “flexible” refers to a substrate and/or article that can undergo roll up action with a bend radius of 200 mm or less, 100 mm or less, 50 mm or less, 20 mm or less, 10 mm or less, 5 mm or less, 4 mm or less, 3 mm or less, 2 mm or less, or 1 mm or less, without failure or visible defects, such as delamination, cracking, crazing, or haze.

As used herein, “foldable” refers to a substrate and/or article that can undergo repeated flexing or folding, such as up to 1,000 folds, up to 10,000 folds, up to 25,000 folds, up to 50,000 folds, up to 25,000 folds, up to 100,000 folds, or even up to 200,000 folds, without failure or visible defects such as delamination, cracking, crazing, or haze. In this context, a fold is formed in a substrate or article that is relatively flat when it is bent over (i.e., folded) on itself so that one part of it covers another part. The bend radius for folding is often 200 mm or less, 100 mm or less, 50 mm or less, 20 mm or less, 10 mm or less, 5 mm or less, 4 mm or less, 3 mm or less, 2 mm or less, or 1 mm or less.

The term “optically clear” refers to a material that has a haze value of less than about 1 percent as well as transmission and clarity values of 90 percent or more when measured as described in the Optical Durability test method in the Example section below.

Herein, 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 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.

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, 22 °C to 25 °C, or 23 °C.

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

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 ^x group is present in a formula, each R ^x group is independently selected.

Reference throughout this specification to “one embodiment,” “an embodiment,” “certain embodiments,” or “some embodiments,” etc., means that a specific 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 specific 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. These 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. Thus, the scope of the present disclosure should not be limited to the specific illustrative structures described herein, but rather extends at least to the structures described by the language of the claims, and the equivalents of those structures. 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.

Detailed Description

An adhesive composition containing the polymer derived from the polyether-containing monomer is provided. More specifically, the polyether-containing macromer has a urea (-NH- (C=0)-NH-) or carbamate (-NH-(C=0)-0-) linkage between the polyether group and a (meth)acryloyloxy group. The adhesive composition is typically a pressure-sensitive adhesive. Additionally, an article is provided that contains the adhesive composition positioned adjacent to a substrate. The articles can be, for example, an adhesive tape or can be part of another article such as, for example, an electronic device that is flexible and/or foldable. The adhesive compositions can be tolerant of high temperature and high humidity conditions (e.g., 65 degrees Celsius and 90 percent relative humidity for 14 days).

Overall, the adhesive composition contains polymeric material derived from a polymerizable composition containing polymerizable components that include a polyether- containing macromer that has a (meth)acrylolyoxy group plus a urea or carbamate linkage between the (meth)acrylolyoxy group and the polyether group. The polymerizable composition further includes an alkyl (meth)acrylate, an optional polar monomer, and a crosslinking agent. In many embodiments, the polymerizable composition includes the optional polar monomer.

The adhesive composition often contains at least two polymers (a first polymer and a second polymer) having different monomeric units and different molecular weights. The first polymer is typically derived from a first polymerizable composition that contains an alkyl (meth)acrylate and an optional polar monomer while the second polymer is derived from a second polymerizable composition that includes a polyether-containing macromer, an alkyl (meth)acrylate, an optional polar monomer, and a crosslinking agent. The second polymer is often prepared in the presence of the first polymer. Typically, at least the second polymer is crosslinked. In some embodiments, depending on the selected crosslinking agent, both the first polymer and the second polymer are crosslinked.

The adhesive composition can be used in the preparation of various articles. The adhesive composition desirably has good peel adhesive strength and remains adhered to a substrate even when the article is flexed, folded, impacted, or exposed to adverse environmental conditions. In some embodiments, the adhesive composition is used in an electronic device including those that are flexible and/or that can withstand an impact such as dropping. With proper selection of the polyether-containing macromer, the adhesive composition can have good resistance to hydrolysis when exposed to high temperature and high humidity conditions (e.g., 60 to 75 degrees Celsius and at least 90 percent relative humidity).

In some embodiments, the process of making the adhesive composition includes preparing the first polymer by partially polymerizing a first polymerizable composition to form a syrup composition. The syrup composition contains a solute polymer, which is the first polymer, dissolved in solvent monomers. The solvent monomers are the unreacted polymerizable components of the first polymerizable composition that includes (a) an alkyl (meth)acrylate and (b) an optional polar monomer. After formation of the first polymer, the following monomers are added to the syrup composition to form a second polymerizable composition: a polyether- containing macromer of Formula (I), a polar monomer if the syrup composition is free of the optional polar monomer (or if additional polar monomer is desired), and a crosslinking agent. That is, the second polymerizable composition contains the first polymer, an alkyl (meth)acrylate, a polar monomer, the polyether-containing macromer of Formula (I), and a crosslinking agent.

When polymerization is initiated, a second polymer is formed in the presence of the first polymer. During the second polymerization reaction, the first polymer typically does not undergo further polymerization except perhaps crosslinking depending on the selection of the crosslinking agent. The product is an adhesive composition that contains the first polymer and the second polymer. Either the second polymer or both the second polymer and the first polymer are crosslinked.

Polvether-containing macromer

The polymerizable components used to form the adhesive composition include a polyether-containing macromer that is of Formula (I).

CH ₂ =CHR ¹ -(C=0)-0-R ² -NH-(C=0)-X ¹ -Q ¹

(I) In Formula (I), the group R ¹ is hydrogen or methyl, the group R ² is an alkylene having 1 to 4 carbon atoms, the group X ¹ is -O- or -NH-, and Q ¹ is a polyether group. The polyether-containing macromer has a (meth)acrylolyoxy group plus a urea or carbamate linkage between the (meth)acryloyloxy group and the polyether group.

The group R ² is an alkylene having 1 to 4 carbon atoms. In many embodiments, R ² has either two or three carbon atoms.

The group Q ¹ is a polyether group of formula -(R ³ -0) _n -R ⁴ where each R ³ is independently an alkylene having 2 to 4 carbon atoms and R ⁴ is an alkyl having 1 to 4 carbon atoms. The variable n being in a range of 5 to 150. For example, the variable n is at least 5, at least 10, at least 20, at least 30, at least 40, or at last 50 and up to 150, up to 125, up to 100, up to 90, up to 80, up to 70, up to 60, up to 50, up to 40, or up to 30.

In some embodiments, Q ¹ is a poly(tetramethylene oxide) group, polypropylene oxide), polypropylene oxide)-co-poly(ethylene oxide), or polypthylene oxide). For some applications,

Q ¹ is a poly(tetramethylene oxide) group, a polypropylene oxide) group, or a polypropylene oxide)-co-poly(ethylene oxide). In some of these embodiments, Q ¹ is selected so that it is free of ethylene oxide or contains 0 to 30 mole percent ethylene oxide based on the total moles of alkylene oxide in the polyether group. For example, the polyether group is selected to contain no greater than 30 mole precent, no greater than 25 mole percent, no greater than 20 mole percent, no greater than 15 mole percent, no greater than 10 mole percent, or no greater than 5 mole percent ethylene oxide based on the total moles of alkylene oxide in the poly ether group. If the poly ether group contains ethylene oxide, it can contain at least 1 mole percent, at least 5 mole percent, or at least 10 mole percent ethylene oxide based on total moles of alkylene oxide in the polyether group. The group Q ¹ is often selected to be a polypropylene oxide) group or a polypropylene oxide)-co- polypthylene oxide) with 1 to 30 mole percent ethylene oxide based on the total moles of ethylene oxide and propylene oxide.

The polyether-containing monomer can be formed by reaction of an isocyanato-substituted alkyl (meth)acrylate of formula CFh=R ¹ -(C=0)-0-R ² -NCC) with a poly(alkylene oxide) amine or poly(alkylene oxide) alcohol of formula H-X'-Q ¹ as shown in Reaction Scheme A. The groups R ¹ , R ² , X ¹ , and Q ¹ are the same as described above for Formula (I).

Reaction Scheme A

CH ₂ =R ¹ -(C=0)-0-R ² -NC0 + H-XkQ ¹ CH ₂ =CHR ¹ -(C=0)-0-R ² -NH-(C=0)-X ¹ -Q ¹

The number average molecular weight of the polyether-containing macromer is often in a range of 400 to 6000 grams/mole. The number average molecular weight can be at least 400, at least 500, at least 600, at least 800, at least 1000, at least 1200, or at least 1500 grams/mole and up to 6000, up to 5500, up to 5000, up to 4500, up to 4000, up to 3500, up to 3000, up to 2500, up to 2000, up to 1500, or up to 1000 grams/mole. If the molecular weight is greater than 4000 grams/mole, the polyether-containing macromer may crystallize. If the weight is less than 500 grams/mole, the impact resistance of the adhesive composition tends to be compromised. The molecular weight can be determined using proton Nuclear Magnetic Resonance ('H-NMR).

The use of polyether-containing macromers, particularly those having a polyether group that is free of ethylene oxide or that contains 0 to 30 mole percent ethylene oxide based on total moles of alkylene oxide in the polyether group are often advantageous over many other known polyether-containing macromers that have been used in adhesive applications. The polyether- containing macromers of Formula (I) tend to be resistant to hydrolysis when exposed to high temperature and high humidity conditions (e.g., 60 to 75 degrees Celsius and at least 90 percent relative humidity). Thus, adhesive compositions derived from the polyether-containing macromers of Formula (I) rather than some other known polyether-containing macromers can have enhanced adhesion properties (e.g., peel strength) at elevated temperatures and/or under high humidity conditions. The adhesive compositions can have a combination of good impact resistance and good adhesion to high surface energy surfaces such as stainless steel at room temperature as well as after aging at elevated temperatures (e.g., 60 to 75 degrees Celsius) and under high humidity conditions (e.g., 90 percent relative humidity).

Adhesive composition

An adhesive composition is provided that comprises a polymeric material derived from a polymerizable composition comprising polymerizable components that include a) a polyether macromer of Formula (I) as described above, b) an alkyl (meth)acrylate, and c) an optional polar monomer, and d) a crosslinking agent.

The adhesive composition can be prepared by any suitable method. Often, a first polymer is formed by partially polymerizing a first polymerizable composition to form a syrup composition. The syrup composition contains a solute polymer, which is the first polymer, dissolved in solvent monomers. The solvent monomers are the unreacted polymerizable components of the first polymerizable composition that includes (a) an alkyl (meth)acrylate and (b) an optional polar monomer. After formation of the first polymer, the following monomers are added to the syrup composition to form a second polymerizable composition: a polyether- containing macromer of Formula (I) that has a (meth)acrylolyoxy group plus a urea or carbamate linkage between the (meth)acryloyloxy group and the polyether group, a polar monomer if the syrup composition is free of the optional polar monomer (or if additional polar monomer is desired), and a crosslinking agent. That is, the second polymerizable composition contains the first polymer, an alkyl (meth)acrylate, a polar monomer, a polyether-containing macromer, and a crosslinking agent. When polymerization is initiated, a second polymer is formed in the presence of the first polymer. The product is an adhesive composition that contains the first polymer and the second polymer. Either the second polymer or both the second polymer and the first polymer are crosslinked.

The first polymer is formed from a first polymerizable composition that includes an alkyl (meth)acrylate and an optional polar monomer. Other optional monomers can be included in the first polymerizable composition, but it typically does not contain a polyether-containing macromer such as those of Formula (I). The first polymerizable composition is usually only partially polymerized. Thus, the product of the first polymerizable composition is a syrup composition that contains (a) a syrup polymer that is a first polymer and (b) unreacted solute monomers.

Any suitable alkyl (meth)acrylate or mixture of alkyl (meth)acrylates can be used in the first polymerizable composition. The choice of the alkyl (meth)acrylate can influence the glass transition temperature of the final adhesive composition. Some alkyl (meth)acrylate monomers are classified as low T _g monomers based on the glass transition temperature of their corresponding homopolymers. The low T _g monomers, as measured from the corresponding homopolymers, often have a T _g no greater than 20 degrees Celsius, no greater than 10 degrees Celsius, no greater than 0 degrees Celsius, or no greater than -10 degrees Celsius. Other alkyl (meth)acrylates are classified as high T _g monomers based on the glass transition temperature of the corresponding homopolymers. The high T _g monomers, as measured from the corresponding homopolymers, often have a T _g greater than 30 °C, greater than 40 °C, or greater than 50 °C. The glass transition temperature if often measured using Dynamic Mechanical Analysis (DMA).

Suitable low T _g alkyl (meth)acrylate monomers include, but are not limited to, non-tertiary alkyl acrylates but can be an alkyl (meth)acrylate having a linear alkyl group with at least 4 carbon atoms. Specific examples of alkyl (meth)acrylates include, but are not limited to, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, sec-butyl acrylate, n-pentyl acrylate, 2-methylbutyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 4-methyl-2 -pentyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, 2-octyl acrylate, isooctyl acrylate, isononyl acrylate, isoamyl acrylate, n-decyl acrylate, isodecyl acrylate, n-decyl methacrylate, lauryl acrylate, isotridecyl acrylate, n-octadecyl acrylate, isostearyl acrylate, n-dodecyl methacrylate, and combinations thereof. The alkyl (meth)acrylate monomers are typically selected to include at least one low T _g monomer such as those that have a T _g no greater than -10 degrees Celsius when measured as a homopolymer. Such alkyl monomers include, but are not limited to, 2-ethylhexyl acrylate, isooctyl acrylate, n-butyl acrylate, 2-methylbutyl acrylate, iso-octyl acrylate, 2-octyl acrylate, and combinations thereof.

Some suitable high T _g alkyl (meth)acrylate monomers include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, isobomyl (meth)acrylate, stearyl (meth)acrylate, 3,3,5 trimethylcyclohexyl (meth)acrylate, and combinations thereof.

The total amount of the alkyl (meth)acrylate can be any amount up to 100 weight percent or up to 99 weight percent based on the total weight of monomers within the first polymerizable composition. The amount can be, for example, up to 98 weight percent, up to 97 weight percent, up to 95 weight percent, up to 92 weight percent, up to 90 weight percent, up to 85 weight percent, or up to 80 weight percent. The lower amount is often at least 50 weight percent but can be lower if optional monomers are included in the first polymerizable composition. The amount is often least 55 weight percent, at least 60 weight percent, at least 65 weight percent, at least 70 weight percent, at least 75 weight percent, at least 80 weight percent, at least 85 weight percent, or at least 90 weight percent.

In addition to the alkyl (meth)acrylate, the first polymerizable composition optionally (but usually) contains a polar monomer. The polar monomer contains an ethylenically unsaturated group plus a polar group. The ethylenically unsaturated group is either a vinyl or (meth)acryloyl group. Suitable polar groups can be an acidic group, a hydroxyl group, an ether (or polyether) group, or a nitrogen-containing group. The nitrogen-containing group is typically a primary amido group, secondary amido group, tertiary amido group, or amino group. A polar monomer with an acidic group can be referred to as an “acidic polar monomer” while those with a hydroxyl group, ether group, or nitrogen-containing group can be referred to as a “non-acidic polar monomer”.

Although acidic polar monomers can have any suitable acidic group such as a sulfonic acid group, phosphonic acid group, or carboxylic acid group, the acidic group is often a carboxylic acid group. Exemplary polar monomers with a carboxylic acid group include those selected from (meth)acrylic acid, b-carboxyethyl (meth)acrylate, 2-(meth)acryloyloxyethyl phthalic acid, 2- (meth)acryloyloxy succinic acid, and combinations thereof. In many embodiments, the polar monomer with an acidic group is (meth)acrylic acid and is often acrylic acid. Depending on the pH, the acidic polar monomers can be in the form of a salt.

For some electronic devices, acidic monomers may be absent or present in a minimal amount so that its presence does not result in the corrosion or dissolution of metal -containing components that are included in such devices. In some embodiments, the polymerizable components are free or substantially free (e.g., less than 0.5 weight percent, less than 0.1 weight percent, less than 0.05 weight percent, or less than 0.01 weight percent based on a total weight of polymerizable components) of acid polar monomers.

Exemplary polar monomers with a hydroxyl group include, but are not limited to, hydroxyalkyl (meth)acrylates (e.g., 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate), hydroxyalkyl (meth)acrylamides (e.g., 2-hydroxyethyl (meth)acrylamide and 3-hydroxypropyl (meth)acrylamide), ethoxylated hydroxyethyl (meth)acrylate, aryloxy substituted hydroxyalkyl (meth)acrylates (e.g., 2-hydroxy-2-phenoxypropyl (meth)acrylate), and hydroxy-propyl-carbamate acrylate.

Exemplary ether-containing polar monomers include those selected from 2- ethoxyethoxyethyl (meth)acrylate, 2-methoxyethoxyethyl (meth)acrylate, di(ethylene glycol)-2- ethylhexyl-ether acrylate, ethylene glycol-methyl ether acrylate, and combinations thereof.

Suitable ether-containing (meth)acrylate monomers usually have a number average molecular weight less than 300 Daltons, less than 275 Daltons, or less than 250 Daltons.

Exemplary polar monomers with a primary amido group include (meth)acrylamide. Exemplary polar monomers with secondary amido groups include, but are not limited to, N-alkyl (meth)acrylamides and N-alkoxyalkyl (meth)acrylamides such as N-methyl (meth)acrylamide, N- ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, and N-octyl (meth)acrylamide, N-(3- methoxypropyl)acrylamide, and N-(isobutoxymethyl)acrylamide. Exemplary polar monomers with a tertiary amido group include, but are not limited to, N-vinyl carbazole, N-vinyl caprolactam, N- vinyl-2-pyrrolidone, N-vinyl azlactone, 4-(meth)acryloylmorpholine, N-vinylimidazole, ureido (meth)acrylate, and N,N-dialkyl (meth)acrylamides such as N,N-dimethyl (meth)acrylamide, N,N- diethyl (meth)acrylamide, N,N-dipropyl (meth)acrylamide, and N,N-dibutyl (meth)acrylamide.

Polar monomers with an amino group include various N,N-dialkylaminoalkyl (meth)acrylates and N,N-dialkylaminoalkyl (meth)acrylamides. Examples include, but are not limited to, N,N-dimethyl aminoethyl (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.

The first polymerizable composition can include 0 to 50 weight percent polar monomer. This amount is often no greater than 50 weight percent, no greater than 45 weight percent, no greater than 40 weight percent, no greater than 35 weight percent, no greater than 30 weight percent, no greater than 25 weight percent, no greater than 20 weight percent, no greater than 15 weight percent, no greater than 10 weight percent, or no greater than 5 weight percent based on a total weight of polymerizable components. If present, the amount of the polar monomer or mixtures thereof is often at least 0.1 weight percent, at least 0.5 weight percent, at least 1 weight percent, at least 2 weight percent, at least 5 weight percent, at least 10 weight percent, at least 15 weight percent, or at least 20 weight percent based on a total weight of monomers in the first polymerizable composition.

In some embodiments, the polar monomer can be an acidic polar monomer, a non-acidic polar monomer, or a combination thereof. If the first polymerizable composition includes acidic polar monomer, the amount of the acidic polar monomer is usually present in an amount no great than 30 weight percent based on a total weight of monomers in the first polymerizable composition. Typically, if more than 30 weight percent of the acidic polar monomer is used, the resultant adhesive composition may be too stiff. The amount is often no greater than 25 weight percent, no greater than 20 weight percent, no greater than 15 weight percent, 12 weight percent, no greater than 10 weight percent, no greater than 8 weight percent, no greater than 6 weight percent, no greater than 5 weight percent, no greater than 4 weight percent, no greater than 3 weight percent, or no greater than 2 weight percent and at least 0.5 weight percent, at least 1 weight percent, at least 2 weight percent, at least 3 weight percent, or at least 5 weight percent based on the total weight of monomers in the first polymerizable composition. The amount of any non-acidic polar monomers combined with the acidic polar monomer can be any amount such that the sum of all the polar monomers is no greater than 50 weight percent, no greater than 45 weight percent, no greater than 40 weight percent, no greater than 35 weight percent, no greater than 30 weight percent, no greater than 25 weight percent, no greater than 20 weight percent, no greater than 15 weight percent, no greater than 10 weight percent, or no greater than 5 weight percent based on a total weight of monomers in the first polymerizable composition.

In some embodiments, first polymerizable composition often includes both an acidic polar monomer and a nitrogen-containing polar monomer (e.g., a polar monomer with a primary amido group, a secondary amido group, a tertiary amido group, or an amino group). This combination of polar monomers can provide an adhesive composition that has excellent high impact resistance, and/or drop resistance properties, and excellent bond making ability (i.e., good tack, instant bond formation). These performance criteria are often highly desirable for applications within e- bonding and industrial market segments.

In other embodiments, however, the first polymerizable composition little or no acidic polar monomers. That is, the first polymerizable composition is free of acidic polar monomers or contains less than 1 weight percent, no greater than 0.5 weight percent, no greater than 0.2 weight percent, no greater than 0.1 weight percent, no greater than 0.05 weight percent, no greater than 0.02 weight percent, or no greater than 0.01 weight percent based on the total weight of the first polymerizable composition. The amount of any non-acidic polar monomers in such fist polymerizable compositions is usually no greater than 50 weight percent, no greater than 45 weight percent, no greater than 40 weight percent, no greater than 35 weight percent, no greater than 30 weight percent, no greater than 25 weight percent, no greater than 20 weight percent, no greater than 15 weight percent, no greater than 10 weight percent, or no greater than 5 weight percent based on a total weight of monomers in the first polymerizable composition.

The first polymerizable composition often contains 50 to 100 weight percent alkyl (meth)acrylate and 0 to 50 weight percent polar monomer based on a total weight of polymerizable components in the first polymerizable composition. In many embodiments, the first polymerizable composition contains 50 to 99 weight percent alkyl (meth)acrylate and 1 to 50 weight percent polar monomer, 60 to 99 weight percent alkyl (meth)acrylate and 1 to 40 weight percent polar monomer or 70 to 99 weight percent alkyl (meth)acrylate and 1 to 30 weight percent polar monomer. For example, the first polymerizable composition can include 70 to 95 weight percent alkyl (meth)acrylate and 5 to 30 weight percent polar monomer, 80 to 99 weight percent alkyl (meth)acrylate and 1 to 20 weight percent polar monomer, 80 to 95 weight percent alkyl (meth)acylate and 5 to 20 weight percent polar monomer, 85 to 95 weight percent alkyl (meth)acrylate and 1 to 15 weight percent polar monomer, 85 to 95 weight percent alkyl (meth)acylate and 5 to 15 weight percent polar monomer, or 80 to 90 weight percent alkyl (meth)acylate and 10 to 20 weight percent polar monomer. If the polar monomer includes an acidic monomer, the amount of the acidic monomer can be 0.5 to 30 weight percent, 0.5 to 20 weight percent, or 0.5 to 15 weight percent with any remainder polar monomer being a non-acidic polar monomer.

Other optional monomers can be included in the first polymerizable composition. The optional monomers typically do not include a macromer or a crosslinking agent. In many embodiments, the first polymerizable composition is free or substantially free of vinyl acetate and non-polar vinyl monomers. As used herein to describe vinyl acetate and non-polar vinyl monomers, the term “substantially free” means that the first polymerizable composition contain no greater than 1 weight percent, no greater than 0.5 weight percent, no greater than 0.2 weight percent, no greater than 0.1 weight percent, no greater than 0.05 weight percent, or no greater than 0.01 weight percent of these monomers based on the total weight of monomers.

In addition to the monomers (e.g., an alkyl (meth)acylate and an optional polar monomer), the first polymerizable composition typically includes a free-radical initiator. The initiator can be a thermal initiator or a photoinitiator. Multiple thermal initiators or photoinitiators can be used. The amount of the free radical initiator can influence the molecular weight of the first polymer, with larger amounts of the free radical initiator typically producing lower molecular weight polymers. The amount of the initiator is often in a range of 0.01 to 5 weight percent based on the total weight of polymerizable components in first polymerizable composition. The amount can be at least 0.01 weight percent, at least 0.05 weight percent, at least 0.1 weight percent, at least 0.2 weight percent, at least 0.5 weight percent, or at least 1 weight percent and up to 5 weight percent, up to 4 weight percent, up to 3 weight percent, up to 2 weight percent, up to 1 weight percent, or up to 0.5 weight percent.

Exemplary thermal initiators include various azo compound such as those commercially available under the trade designation VAZO from Chemours Co. (Wilmington, DE, USA) including VAZO 67, which is 2,2’-azobis(2-methylbutane nitrile), VAZO 64, which is 2,2’- azobis(isobutyronitrile), VAZO 52, which is (2,2’-azobis(2,4-dimethylpentanenitrile), and VAZO 88, which is l,r-azobis(cyclohexanecarbonitrile); various peroxides such as benzoyl peroxide, cyclohexane peroxide, lauroyl peroxide, di-tert-amyl peroxide, tert-butyl peroxy benzoate, di- cumyl peroxide, and peroxides commercially available from Atofina Chemical, Inc. (Philadelphia, PA, USA) underthe trade designation LUPERSOL (e.g., LUPERSOL 101, which is 2,5-bis(tert- butylperoxy)-2,5-dimethylhexane, and LUPERSOL 130, which is 2,5-dimethyl-2,5-di-(tert- butylperoxy)-3-hexyne); various hydroperoxides such as tert-amyl hydroperoxide and tert-butyl hydroperoxide; and mixtures thereof.

In many embodiments, a photoinitiator is used to form the first polymer. Some exemplary photoinitiators are benzoin ethers (e.g., benzoin methyl ether or benzoin isopropyl ether) or substituted benzoin ethers (e.g., anisoin methyl ether). Other exemplary photoinitiators are substituted acetophenones such as 2,2-diethoxyacetophenone or 2,2-dimethoxy-2- phenylacetophenone (commercially available under the trade designation IRGACURE 651 from BASF Corp. (Florham Park, NJ, USA) or under the trade designation ESACURE KB-1 from Sartomer (Exton, PA, USA)). Still other exemplary photoinitiators are substituted alpha-ketols such as 2-methyl-2-hydroxypropiophenone, aromatic sulfonyl chlorides such as 2- naphthalenesulfonyl chloride, and photoactive oximes such as 1 -phenyl- l,2-propanedione-2-(0- ethoxycarbonyl)oxime. Other suitable photoinitiators include, for example, 1 -hydroxy cyclohexyl phenyl ketone (commercially available underthe trade designation IRGACURE 184), bis(2,4,6- trimethylbenzoyl)phenyl phosphine oxide (commercially available under the trade designation IRGACURE 819), 1 - [4-(2-hydroxyethoxy)phenyl] -2 -hydroxy-2 -methyl- 1 -propane- 1 -one (commercially available underthe trade designation IRGACURE 2959), 2 -benzyl-2 - dimethylamino-l-(4-morpholinophenyl)butanone (commercially available underthe trade designation IRGACURE 369), 2 -methyl- l-[4-(methylthio)phenyl]-2-morpholinopropan-l -one (commercially available underthe trade designation IRGACURE 907), and 2-hydroxy-2 -methyl- 1- phenyl propan- 1 -one (commercially available underthe trade designation DAROCUR 1173 from Ciba Specialty Chemicals Corp. (Tarrytown, NY, USA)).

Chain-transfer agents optionally can be included in the first polymerizable composition to control the molecular weight of the first polymer. Suitable chain-transfer agents include, but are not l im ited to, those selected from the group of carbon tetrabromide, hexabromoethane, bromotrichloromethane, 2-mercaptoethanol, tert-dodecylmercaptan, isooctylthiogiycoate, 3- mercapto-1, 2-propanediol, cumene, pentaerythritol tetrakis(3-mercapto butyrate) (available under the trade name KARENZ MX PEI from Showa Denko), ethylene glycol bisthioglycolate, and mixtures thereof. Depending on the reactivity of the chain-transfer agent sel ected, the amount of chain transfer agent is often in a range of 0 to 5 weight percent based on the total weight of monomers in the first polymerizable composition. In some embodiments, the amount of the chain transfer agent is at least 0.05 weight percent, at least 0.1 weight percent, at least 0.2 weight percent, at least 0.3 weight percent, or at least 0.5 weight percent and can be up to 5 weight percent, up to 4.5 weight percent, up to 4 weight percent, up to 3.5 weight percent, up to 3 weight percent, up to 2.5 weight percent, up to 2 weight percent, up to 1.5 weight percent, or up to 1 weight percent. The weight percent values are based on the total weight of the polymerizabl e components in the first polymerizable composition to form the first polymer.

Polymerization of the first polymerizable composition to form the first polymer can occur in the presence or absence of an optional non-reactive organic solvent. If a non-reactive organic solvent is included in the first polymerizable composition, the amount is often selected to provide the desired viscosity. Examples of suitable non-reactive organic solvents include, but are not limited to, methanol, tetrahydrofuran, ethanol, isopropanol, pentane, hexane, heptane, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, toluene, xylene, and ethylene glycol alkyl ether. Those organic solvents can be used alone or as mixtures thereof. If used, the amount of the non reactive organic solvent is often no greater than 10 weight percent, no greater than 5 weight percent, no greater than 4 weight percent, no greater than 3 weight percent, no greater than 2 weight percent, or no greater than 1 weight percent based on a total weight of the first polymerizable composition. In some embodiments, no non-reactive organic solvent is purposely added but may be a component (eg., contaminant or diluent) of another constituent of the first polymerizable composition. In many embodiments, the first polymerizable composition is free or substantially free of non-reactive organic solvents. As used herein with reference to the non reactive organic solvent, “substantially free” means that the first polymerizable composition contains less than 1 weight percent, less than 0.5 weight percent, less than 0.1 weight percent, less than 0.05 weight percent, or less than 0.01 weight percent non-reactive organic solvent.

The first polymerizable composition is typically partially polymerized to form a syrup composition that contains a solute polymer dissolved in solute monomers. The polymerization process typically occurs by exposure of the first polymerizable composition to actinic radiation, which is often ultraviolet radiation, or to heat (e ., 40 to 100 degrees Celsius). The solute polymer is the first polymer and the solute monomers are the unreacted monomers. The polymerization time is typically selected so that no greater than 20 weight percent of the monomers in the first polymerizable composition are polymerized. That is, the syrup composition usually contains 1 to 20 weight percent solute polymer (i.e., the first polymer) and 80 to 99 weight percent solvent monomers based on a total weight of the syrup composition. The amount of the solute polymer can be at least 1 weight percent, at least 2 weight percent, at least 3 weight percent, at least 5 weight percent, or at least 10 weight percent and up to 20 weight percent, up to 15 weight percent, up to 10 weight percent, or up to 5 weight percent based on the total weight of monomers in the first polymerizable composition. The remainder of the syrup composition is typically predominately the solvent monomers (e ., there can be small amounts of other components added to the first polymerizable composition such as the initiator and/or chain transfer agent and/or non reactive organic solvent).

In some examples, the syrup composition contains 1 to 15 weight percent first polymer and 85 to 99 weight percent solvent monomers, 1 to 10 weight percent first polymer and 90 to 99 weight percent solvent monomers, 5 to 20 weight percent first polymer and 80 to 95 weight percent solvent monomers, or 5 to 15 weight percent first polymer and 85 to 95 weight percent solvent monomers. The solvent monomers include both the alkyl (meth)acrylate and the optional polar monomer. The amounts are based on the total weight of the syrup composition.

In some more specific examples, the syrup composition contains 1 to 20 weight percent first polymer, 0 to 50 weight percent polar monomers, and 50 to 99 weight percent alkyl (meth)acrylate monomers or 1 to 20 weight percent first polymer, 1 to 50 weight percent polar monomers, and 50 to 98 weight percent alkyl (meth)acrylate monomers. For example, the syrup composition can contain 1 to 20 weight percent first polymer, 0 to 40 weight percent polar monomers, and 50 to 99 weight percent alkyl (meth)acrylate monomers or 1 to 20 weight percent first polymer, 1 to 40 weight percent polar monomers, and 50 to 98 weight percent alkyl(meth)acrylate monomers. In some examples, the syrup compositions contain 1 to 20 weight percent first polymer, 1 to 30 weight percent polar monomers, and 50 to 98 weight percent alkyl (meth)acrylate monomers or 1 to 20 weight percent first polymer, 1 to 15 weight percent polar monomers, and 65 to 98 weight percent alkyl (meth)acrylate monomers. In other examples, the syrup composition contains 5 to 20 weight percent first polymer, 1 to 25 weight percent polar monomers, and 55 to 94 weight percent alkyl (meth)acrylates or 5 to 20 weight percent first polymer, 1 to 15 weight percent polar monomers, and 65 to 94 weight percent alkyl (meth)acrylates. In still other examples, the syrup composition contains 1 to 15 weight percent first polymer, 1 to 30 weight percent polar monomers, and 55 to 98 weight percent alkyl (meth)acrylate or 1 to 15 weight percent first polymer, 1 to 20 weight percent polar monomers, and 65 to 98 weight percent alkyl (meth)acrylate. In yet another example, the syrup composition contains 1 to 10 weight percent first polymer, 1 to 30 weight percent polar monomers, and 60 to 98 weight percent alkyl (meth)acrylate or 1 to 10 weight percent first polymer, 1 to 15 weight percent polar monomers, and 75 to 98 weight percent alkyl (meth)acrylate.

The first polymer (i.e., solute polymer) typically has a weight average molecular weight of at least 100,000 Daltons. For example, the weight average molecular weight can be at least 200,000 Daltons, at least 300,00 Daltons, at least 400,000 Daltons, at least 500,000 Daltons, or at least 600,000 Daltons and up to 1,000,000 Daltons, up to 2,000,000 Daltons, or up to 3,000,000 Daltons or even higher. The weight average molecular weight can be determined using size exclusion chromatography (SEC) with polystyrene standards. The first polymer is usually not crosslinked but can be crosslinked depending on the selection of the crosslinking agent included in the second polymerizable composition.

The second polymer is formed from a second polymerizable composition that includes (a) an alkyl (meth)acrylate, (b) a polar monomer, (c) a polyether-containing macromer of Formula (I), and (d) a crosslinking agent. The second polymer, which is crosslinked, can be formed in the presence or absence of the first polymer.

In some embodiments, the second polymer can be formed in the presence of the first polymer. That is, the second polymerizable composition can further include the first polymer. If the first polymer is present, it is typically part of a syrup composition formed from the first polymerizable composition. Alternatively, in other embodiments, the second polymerizable composition can be prepared that does not include either a syrup composition or the first polymer.

Typically, the second polymerizable composition contains (a) a syrup composition formed from a first polymerizable composition comprising (i) an alkyl (meth)acrylate and (ii) an optional polar monomer, (b) a polar monomer if the syrup composition is free of the optional polar monomer (or if additional polar monomer is desired), (c) a polyether-containing macromer, and (d) a crosslinking agent having a plurality of (meth)acryloyl groups. The syrup composition contains (a) 1 to 20 weight percent solute polymer having a weight average molecular weight of at least 100,000 Daltons and that is the first polymer and (b) 80 to 99 weight percent solvent monomers. The polymerized product of the second polymerizable composition contains the first polymer plus a second polymer that is crosslinked. Because the first polymer is not a living polymer, it does not polymerize further during the polymerization of the second polymerizable composition to form the second polymer (although, depending on the crosslinking agent in the second polymerizable composition, the first polymer may undergo crosslinking). Thus, the polymerized product of the second polymerizable composition is a polymeric blend of the first and second polymers.

The alkyl (meth)acrylate monomers that can be used for preparation of the second polymer can be the same as those described for use in the preparation of the first polymer. In some embodiments, at least some of the alkyl (meth)acrylate monomers included in the second polymerizable composition are the unreacted solvent monomers in the syrup composition formed by partial polymerization of the first polymerizable composition. Additional amounts of the alkyl (meth)acrylate monomers used to form the first polymer or other types of these monomers can be added to the second polymerizable composition, if desired.

The second polymerizable composition typically include 25 to 95 weight percent alkyl (meth)acrylate monomers based on a total weight of polymerizable components in the second polymerizable composition. The amount of the alkyl (meth)acrylate can be at least 25 weight percent, at least 30 weight percent, at least 35 weight percent, at least 40 weight percent, at least 45 weight percent, at least 50 weight percent, at least 55 weight percent, at least 60 weight percent, at least 65 weight percent, or at least 70 weight percent and up to 95 weight percent, up to 90 weight percent, up to 85 weight percent, up to 80 weight percent, up to 75 weight percent, up to 70 weight percent, up to 65 weight percent, or up to 60 weight percent. The amount is based on the total weight of polymerizable components in the second polymerizable composition.

The polar monomers that can be used for the preparation of the second polymer can be the same as those described as optional polar monomers for use in the preparation of the first polymer. In some embodiments, at least some of the polar monomers included in the second polymerizable composition are the unreacted polar monomers in the syrup composition formed by partial polymerization of the first polymerizable composition. That is, the first polymerizable composition contained polar monomers. If polar monomers were included in the first polymerizable composition, additional polar monomers can be added to the second polymerizable monomer, if desired. These additional polar monomers can be the same or different than those included in the first polymerizable composition. If polar monomers were not included in the first polymerizable composition, they are typically included in the second polymerizable composition.

The second polymerizable composition typically includes 0.5 to 40 weight percent polar monomer based on a total weight of polymerizable components in the second polymerizable composition. The amount of the polar monomer can be at least 0.5 weight percent, at least 1 weight percent, at least 2 weight percent, at least 3 weight percent, at least 5 weight percent, or at least 10 weight percent and up to 40 weight percent, up to 35 weight percent, up to 30 weight percent, up to 25 weight percent, up to 20 weight percent, up to 15 weight percent, up to 10 weight percent, or up to 5 weight percent. The polar monomer can be an acidic monomer, a non-acidic monomer, or a combination thereof. As in the first polymerizable composition, the amount of a polar monomer having an acidic group is usually no greater than 30 weight percent, no greater than 25 weight percent, no greater than 20 weight percent, no greater than 15 weight percent, no greater than 10 weight percent, or no greater than 5 weight percent based on the total weight of polymerizable components in the second polymerizable composition.

In addition to the alkyl (meth)acrylate and the polar monomer, the second polymerizable composition includes a polyether-containing macromer of Formula (I). The polyether can contain alkylene oxide groups selected from ethylene oxide, propylene oxide, and tetramethylene oxide. The polyether typically contains 0 to 30 mole percent ethylene oxide. In many embodiments, the polyether is poly(tetramethylene oxide), polypropylene oxide), or polyethylene oxide)-co- poly(propylene oxide) containing no greater than 30 mole percent ethylene oxide based on the total moles of propylene oxide and ethylene oxide.

The polyether-containing macromer often has a glass transition temperature (as measured using a homopolymer of the macromer) that is no greater than -10 °C. For example, the glass transition temperature can be no greater than -20 °C, no greater than -30 °C, no greater than -40 °C, no greater than -50 °C, or no greater than -60 °C. Such a low macromer glass transition temperature imparts compliance and flexibility to the adhesive composition containing the first and second polymers. The polyether-containing macromer can be crystalline or non-crystalline provided that the adhesive composition is not crystalline.

The second polymerizable composition typically include 2 to 50 weight percent polyether- containing macromer based on a total weight of polymerizable components in the second polymerizable composition. The amount can be at least 2 weight percent, at least 3 weight percent, at least 5 weight percent, at least 10 weight percent, at least 15 weight percent, or at least 20 weight percent and up to 50 weight percent, up to 45 weight percent, up to 40 weight percent, up to 35 weight percent, up to 30 weight percent, up to 25 weight percent, up to 20 weight percent, up to 15 weight percent, or up to 10 weight percent. The amount is based on the total weight of polymerizable components in the second polymerizable composition.

The second polymerizable composition further includes a crosslinking agent. That is, the second polymer is crosslinked. Typically, such crosslinking improves durability and cohesion properties of the adhesive composition. Depending on the choice of the crosslinking agent and whether the second polymer is formed in the presence of the first polymer, the crosslinking agent included in the second polymerizable composition may result in crosslinking of only the second polymer or crosslinking of both the first and the second polymers.

Suitable crosslinking agents for use in the second polymerizable composition include, but are not limited to, multifunctional (meth)acrylate monomers or multifunctional (meth)acrylamide monomers, aziridine crosslinkers, and various thermal or photoactive crosslinkers. Examples of aziridine crosslinkers include, but are not limited to, l,r-isophthaloyl-bis(2-methylaziridine) and trimethylolpropane tris(2 -methyl- 1 -aziridine propionate).

Examples of suitable thermal and photoactive crosslinkers include, but are not limited to, organic peroxides, benzophenone derivatives such as 4-benzoylphenyl acrylate, azide-containing compounds such as 2,6-bis(4-azidobenzylidene)cyclohexanone, and bis-diazirines. The use of aziridine crosslinkers and the thermal or photoactive crosslinkers can result in crosslinking of both the first and second polymers. Use of the multifunctional (meth)acrylate or multifunctional (meth)acrylamide crosslinkers typically results in the crosslinking of the second polymer but not the first polymer.

In many embodiments, the crosslinking agent is a multifunctional (meth)acrylate monomer. Such crosslinking agents have a plurality of (meth)acryloyl groups (e.g., 2, 3, or 4 (meth)acryloyl groups). The number of (meth)acryloyl groups is typically 2, 3, or 4. Examples of multifunctional (meth)acrylate monomer crosslinking agents include, but are not limited to, 1,3- butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, ethoxylated bisphenol A diacrylate, tetraethylene glycol diacrylate, and trimethyloyl propane triacrylate. The polymerizable components of the second polymerizable composition often contain 0.01 to 5 weight percent of the crosslinking agent. The amount can be at least 0.01 weight percent, at least 0.05 weight percent, at least 0.1 weight percent, at least 0.2 weight percent, at least 0.3 weight percent, at least 0.5 weight percent, or at least 1 weight percent and up to 5 weight percent, up to 4 weight percent, up to 3 weight percent, up to 2 weight percent, or up to 1 weight percent based on the total weight of polymerizable components in the second polymerizable composition. The amount of the crosslinking agent included depends on well-understood factors such as the desired degree of crosslinking and/or the relative effectiveness of the crosslinking agent in the specific system, as measured by well-known tests such as shear adhesion.

The second polymerizable composition is usually free of a multivalent salt that can function as a crosslinking agent. Using a crosslinking agent that can form covalent bonds (rather than ionic bonds) with the second polymer tends to result in the formation of adhesive compositions with improved shear strength, especially at elevated temperatures.

Other components can be added to the second reaction polymerizable composition such as any of the initiators, chain transfer agents, and non-reactive organic solvents described above for use in the first polymerizable composition. The amount of these components is comparable to that described for use in the first polymerizable composition.

Considering only the polymerizable components, which excludes the first polymer either because it does not undergo further polymerization or because it is absent, the second polymerizable composition typically contains 0.5 to 40 weight percent polar monomers, 25 to 95 weight percent alkyl (meth)acrylate monomers, 2 to 50 weight percent polyether-containing macromer, and 0.01 to 5 weight percent crosslinking agent based on the total weight of polymerizable components in the second polymerizable composition. For example, the second polymerizable composition can contain 1 to 30 weight percent polar monomers, 30 to 95 weight percent alkyl (meth)acrylate monomers, 4 to 40 weight percent polyether-containing macromer, and 0.01 to 5 (or 0.01 to 1) weight percent crosslinking agent. In another example, the second polymerizable composition can contain 1 to 20 weight percent polar monomers, 40 to 90 weight percent alkyl (meth)acrylate monomers, 4 to 40 weight percent polyether-containing macromer, and 0.01 to 5 (or 0.01 to 1) weight percent crosslinking agent. In yet another example, the second polymerizable composition can contain 1 to 15 weight percent polar monomers, 55 to 90 weight percent alkyl (meth)acrylate monomers, 5 to 30 weight percent poly ether-containing macromer, and 0.01 to 5 (or 0.01 to 1) weight percent crosslinking agent. The amounts are based on the total weight of polymerizable components in the second polymerizable composition.

If the second polymerizable composition includes a syrup composition containing the first polymer as the solute polymer and unreacted syrup monomers, the second polymerizable composition usually contains 50 to 98 weight percent syrup composition, 2 to 50 weight percent polyether-containing macromer, and 0.01 to 5 weight percent crosslinking agent. If the syrup composition is free of polar monomer, 0.5 to 40 weight percent polar monomers is added. Considering the content of the syrup composition, the second polymerizable composition typically contains 0.5 to 20 weight percent first polymer (i.e., the solute polymer in the syrup composition), 0.5 to 40 weight percent polar monomers, 25 to 95 weight percent alkyl (meth)acrylate monomers, 2 to 50 weight percent polyether-containing macromer, and 0.01 to 5 weight percent crosslinking agent. The amounts are based on the total weight of the second polymerizable composition.

In some examples, the second polymerizable composition contains 1 to 20 weight percent first polymer (i.e., the solute polymer in the syrup composition), 1 to 40 weight percent polar monomers, 25 to 95 weight percent alkyl (meth)acrylate monomers, 4 to 40 weight percent polyether-containing macromer, and 0.01 to 5 (or 0.01 to 1) weight percent crosslinking agent. In still other examples, the second polymerizable composition contains 5 to 20 weight percent first polymer (i.e., the solute polymer in the syrup composition), 1 to 30 weight percent polar monomers, 40 to 90 weight percent alkyl (meth)acrylate monomers, 4 to 40 weight percent polyether-containing macromer, and 0.01 to 5 (or 0.01 to 1) weight percent crosslinking agent. In yet further examples, the second polymerizable composition contains 5 to 15 weight percent first polymer (i.e., the solute polymer in the syrup composition), 1 to 20 weight percent polar monomers, 50 to 90 weight percent alkyl (meth)acrylate monomers, 5 to 30 weight percent polyether-containing macromer, and 0.01 to 5 (or 0.01 to 1) weight percent crosslinking agent.

The amounts are based on the total weight of the second polymerizable composition.

Like the first polymerizable composition, the second polymerizable composition can be polymerized by exposure of the second polymerizable composition to actinic radiation, which is often ultraviolet radiation, or to heat (e.g., 40 to 100 degrees Celsius).

The adhesive composition typically includes both a first polymer plus a second polymer. The adhesive composition contains 0.5 to 20 weight percent of the first polymer and 80 to 99.5 weight percent of the second polymer based on a total weight of polymeric material in the adhesive composition. The first polymer has a weight average molecular weight of at least 100,000 Daltons and is a polymerized product of a first polymerizable composition comprising (a) an alkyl (meth)acrylate and (b) an optional polar monomer. The second polymer is a polymerized product of a second polymerizable composition comprising (a) an alkyl (meth)acrylate, (b) a polar monomer, (c) a polyether-containing macromer, and (d) a crosslinking agent. The second polymer is crosslinked, but the first polymer can be either crosslinked or not crosslinked.

Any method of making the adhesive composition can be used. In many embodiments, the method includes polymerizing the second polymer in the presence of the first polymer. More specifically, the method includes providing a first polymerizable composition that comprises (a) an alkyl (meth)acrylate and (b) an optional polar monomer. The method further includes forming a syrup composition by partially polymerizing the first polymerizable composition. The syrup composition contains (a) 1 to 20 weight percent solute polymer and (b) 80 to 99 weight percent solvent monomers based on a total weight of the syrup composition. The solute polymer has a weight average molecular weight of at least 100,000 Daltons and is a first polymer. The method yet further includes preparing a second polymerizable composition comprising (a) the syrup composition, (b) a polar monomer if the syrup composition is free of the optional polar monomer or if additional polar monomer is desired, (c) a polyether-containing macromer, and (d) a crosslinking agent. The method still further includes polymerizing the second polymerizable composition to form an adhesive composition comprising the first polymer plus a second polymer. The second polymer is crosslinked, but the first polymer can be either crosslinked or not crosslinked depending on the selection of the crosslinking agent. The adhesive composition is typically a pressure-sensitive adhesive.

In some embodiments, the second polymerizable composition is coated on a substrate and then cured on the substrate. The substrate can be in the form of a moving web that is passed through an oven (e.g., 40 to 100 degrees Celsius) or under ultraviolet radiation for polymerization (i.e., curing) of the second polymerizable composition.

The adhesive composition typically contains 0.5 to 20 weight percent of the first polymer and 80 to 99.5 weight percent of the second polymer based on a total weight of polymeric material in the adhesive composition. For example, the adhesive composition can include 1 to 20 weight percent first polymer and 80 to 99 weight percent second polymer, 2 to 20 weight percent first polymer and 80 to 98 weight percent second polymer, 5 to 20 weight percent first polymer and 80 to 95 weight percent second polymer, or 5 to 15 weight percent first polymer and 85 to 95 weight percent second polymer based on the total weight of polymeric material in the adhesive composition.

The adhesive composition can contain other optional components in addition to the first and second polymers. The combination of the first and second polymers may have adhesive properties suitable for performing as a pressure-sensitive adhesive. Alternatively, optional additives such as atackifier and/or plasticizer may be combined with the first and second polymers to provide a composition with suitable adhesive properties. Useful tackifiers include, for example, rosin ester resins, terpene phenol resins, and hydrogenated C5-C9 hydrocarbon resins. The amount of the optional tackifier is often in a range of 0 to 25 weight percent, 0 to 20 weight percent, 0 to 15 weight percent, 0 to 10 weight percent, or 0 to 5 weight percent based on the total weight of the first and second polymers (or their polymerizable components).

Optional antioxidants and/or stabilizers such as those available under the trade designation IRGANQX 1010 (pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)) from BASF Corp. (Florham Park, NJ, USA) can be added to increase the temperature stability of the first and/or second polymers. If used, the antioxidant and/or stabilizer is typically added in a range of 0.01 weight percent to 1.0 weight percent on the total weight of the first and second polymers (or their polymerizable components).

Various other optional components can be added to the adhesive composition such as, for example, adhesion promoters (e.g., (3-glycidyloxypropyl)trimethoxysilane or (3- glycidyloxypropyl)triethoxysilane), colorants (e.g., titania or carbon black), dyes, corrosion inhibiters (e.g., benzotriazole), antistatic agents, plasticizers, thickeners, thixotropic agents, processing aides, nanoparticles, fibers, fillers, and combinations thereof. Generally, the amounts of each additive would depend on the use of the adhesive composition.

The adhesive composition typically has a glass transition temperature no greater than 25 °C or 20 °C as determined by Dynamic Mechanical Analysis. For example, the glass transition temperature can be no greater than -20 °C, no greater than -25 °C, no greater than -30 °C, no greater than -35 °C, or no greater than -40 °C. The glass transition temperature is often greater than -50 °C, greater than -40 °C, or greater than -30 °C. In some embodiments, the glass transition temperature is in a range of -30 °C to 0 °C. The glass transition temperature can be measured using Dynamic Mechanical Analysis. The DMA scan often contains a single peak.

Articles

Articles are provided that include the adhesive composition and a substrate. Any suitable substrate can be used. In many embodiments, a layer of the adhesive composition is positioned adjacent to the substrate. The adhesive composition may directly contact the substrate or may be separated from the substrate by one of more layers such as a primer layer.

Any suitable substrate can be used. In some articles, the substrate is flexible. Examples of flexible substrate materials include, but are not limited to, polymeric films, woven or nonwoven fabrics; metal foils, foams (e.g., polyacrylic, polyethylene, polyurethane), and combinations thereof (e.g., metalized polymeric film). Polymeric films include, for example, polypropylene (e.g., biaxially oriented), polyethylene (e.g., high density or low density), polyvinyl chloride, polyurethane (e.g., thermoplastic polyurethanes), polyester (e.g., polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polylactic acid copolymer), polycarbonate, polyacrylate, polymethyl(meth)acrylate (PMMA), polyvinylbutyral, polyimide, polyamide, fluoropolymer, cellulose acetate, triacetyl cellulose (TAC), ethyl cellulose, and polycyclic olefin polymers (COP). The woven or nonwoven fabric may include fibers or filaments of synthetic or natural materials, such as cellulose, cotton, nylon, rayon, glass, ceramic materials, and the like.

In some embodiments, the article is or contains an adhesive tape. Examples of such adhesive tapes include transfer tapes, one-sided adhesive tapes, two-sided tapes (i.e., a core substrate with an adhesive layer on each side of the substrate, or die-cut adhesive articles (e.g. the article has an adhesive layer positioned adjacent to one release liner or positioned between two release liners). Such adhesive tapes may include a wide variety of substrates for use as a backing or release liner. Examples include woven and nonwoven materials, plastic fdms, metal foils, and the like.

Adhesive tapes are often prepared by coating the second polymerizable composition upon a variety of flexible or inflexible backing materials and/or release liners using conventional coating techniques to produce a one-sided tape or a two-sided tape. The second polymerizable composition is often cured while on backing material and/or release liner to form the adhesive composition. In the case of a one-sided adhesive tape, the second polymerizable composition can be coated on a layer of backing material and the side of the backing material opposite that where the adhesive is disposed can be coated with a suitable release material (e.g., a release layer or release liner). Release materials are known and include materials such as, for example, silicone, polyethylene, polycarbamate, polyacrylics, and the like. For two-sided adhesive tape, a first adhesive composition layer is on a first major surface of a backing material and a second layer of adhesive composition is on the opposing major surface of the backing material. The second layer may include the adhesive compositions as described herein or a different adhesive composition.

For a die-cut adhesive article or for a transfer tape, the adhesive composition is typically positioned between two release liners.

The adhesive articles can be part of another article. For example, the adhesive composition can bind two parts of an article together. In some such articles, the adhesive is positioned adjacent to a substrate that is flexible and/or foldable and is used within another article that is flexible and/or foldable such as within an electronic device that is flexible and/or foldable.

In some embodiments, the article containing the adhesive composition is part of an electronic device. In such devices, the adhesive composition typically forms a layer between two substrates for binding of the two substrates together. Examples of suitable substrates include materials such as polyacrylate, polymethyl methacrylate, polycarbonate, polyamide, polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycyclic olefin polymers (COP), thermoplastic polyurethane, triacetyl cellulose (TAC), and metal foil.

A common application of adhesives in the electronics industry is in the manufacturing of various displays such as computer monitors, TVs, cell phones, small displays (in cars, appliances, wearables, electronic equipment, etc.). Flexible electronic displays, where the display can be bent freely without cracking or breaking, is a rapidly emerging technology area for making electronic devices using, for example, flexible plastic substrates. This technology allows integration of electronic functionality into non-planar objects, conformity to desired design, and flexibility during use that can give rise to a multitude of new applications. Thus, in some embodiments, the electronic device includes a flexible display. With the emergence of flexible electronic displays, there is an increasing demand for adhesives, and particularly for optically clear adhesives (OCA), to serve as an assembly layer or gap fdling layer between an outer cover lens or sheet (based on glass, polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), polyimide, polyethylene naphthalate (PEN), cyclic olefin copolymer, etc.) and an underlying display module of electronic display assemblies. The presence of the OCA improves the performance of the display by increasing brightness and contrast, while also providing structural support to the assembly. In a flexible assembly, the OCA will also serve as the assembly layer, which in addition to the typical OCA functions, may also absorb most of the folding induced stress to prevent damage to the fragile components of the display panel and protect the electronic components from breaking under the stress of folding. The OCA layer may also be used to position and retain the neutral bending axis at or at least near the fragile components of the display, such as for example the barrier layers, the driving electrodes, or the thin film transistors of an organic light emitting display (OLED). The adhesive compositions described herein can be prepared to be an OCA.

In some embodiments, the electronic device includes a photovoltaic device. Photovoltaic devices are rapidly advancing in performance and device construction. The ability to roll or fold portable arrays is an attractive design for off grid uses such as remote area travel or living, camping, and mobile applications. As the photovoltaic (PV) components become more efficient, the number of modules needed to produce enough power decreases, reducing both size and weight. Integrating organic PV cells or inorganic PV cells onto or into a flexible format offer advantageous designs.

Other flexible articles that can include the adhesive composition described herein include, for example, reliable keyboards, electronic games, sensors, light-emitting elements, and articles of clothing.

The article is often formed by positioning an adhesive layer adjacent to a substrate. The adhesive composition is often formed from the second polymerizable composition that is coated on a substrate (e.g., a backing or a release liner) using conventional coating techniques and then cured. For example, the second polymerizable composition can be applied by methods such as roller coating, flow coating, dip coating, spin coating, spray coating, and die coating. The adhesive composition that is coated may have any desirable weight percent solids but is often in a range of 10 to 100 weight percent solids based on the total weight of the adhesive composition.

The desired solids content may be achieved by further dilution of the coating composition, or by partial drying. The second polymerizable composition is usually cured by actinic radiation (e.g., radiation in the UV and/or visible region of the electromagnetic spectrum) or by application of heat. The thickness of the adhesive layer composition is often in a range of 10 to 1000 micrometers. The thickness can be at least 10, at least 20, at least 30, at least 50, at least 75, at least 100, at least 200, at least 300, at least 400, at least 500, at least 600, or at least 700 micrometers and up to 1000, up to 900, up to 800, up to 700, up to 600, up to 500, up to 400, up to 300, up to 200, or up to 100 micrometers.

Advantageously, the articles with the adhesive layer compositions described herein containing a polymer derived from the polyether-containing macromer having a urea or carbamate linkage between the polyether group and the (meth)acryloyl group tend to have improved impact resistance compared to articles with adhesive layers that do contain such a polymer. The impact resistance is determined by the total energy in the tensile impact test described below in the Examples section. This characteristic is particularly useful for electronic devices. Moreover, compared to polymers derived from polyether-containing macromers lacking a urea or carbamate linkage (e.g., methoxy poly(ethylene glycol) (meth)acrylate, the adhesive strength is more stable during extended aging under high temperature/high humidity conditions, which is often required in electronics bonding applications.

Further, the adhesive layer compositions can be selected to be clear (such as optically clear) based on the optical clarity test described below in the Example section. That is, both before and after aging at 65 °C and 90 percent relative humidity for 500 hours, the adhesive compositions preferably have haze values of less than about 1 percent as well as transmission and clarity values of 90 percent or more.

In many embodiments, the adhesive layer compositions can be both optically clear and foldable. Foldable adhesive compositions often need to have a low shear modulus over a broad temperature range. For example, the shear modulus is preferably less than 550 or 500 kiloPascals at -20 degrees Celsius and less than 50 kiloPascals at 25 degrees Celsius using the rheology test method described in the Example section below. The adhesive compositions with a polymer derived from a polyether-containing macromer having a urea or carbamate linkage between the polyether group and the (meth)acryloyl group can have the desired low shear modulus while maintaining good peel adhesion. It has been challenging to obtain the combination of good peel strength adhesion, low shear modulus, and optical clarity in adhesive compositions.

Further, the adhesive layer compositions preferably pass the creep compliance test described in the Example section. To pass the creep compliance test, the adhesive composition had a maximum percent strain greater than 200 percent and had greater than 90 percent elastic recovery after 60 seconds.

The peel adhesion is typically reduced by less than 50 percent after being stored for two weeks at 65 °C and 90 percent relative humidity compared to being stored for one day at 21 °C and 50 percent relative humidity. For example, the reduction can be less than 40 percent, less than 35 percent, less than 30 percent, less than 25 percent, less than 20 percent, less than 15 percent, or less than 10 percent.

Examples Unless otherwise noted or readily apparent from the context, all parts, percentages, ratios, etc. in the Examples and the rest of the specification are by weight.

Table 1. Materials Used in the Examples

Test Methods

Peel Adhesion Testing at 12”/min or 2.4”/min

For all peel adhesion testing, the easy side, RF02N release liner (SKC Haas Display Films LLC, Seoul KR) was removed, and the exposed side of the tacky adhesive transfer tape was rolled by hand lamination (using a 6 inch (15 cm) rubberized hand roller, Polymag Tek, NY) onto a 6 inch (15 cm) wide primed polyester film backing (3M, 2-mil (50-pm) biaxially oriented PET film with plasma treatment conditions described in U.S. Pat. No. 10,134,566 (David et al.)) ensuring no air bubbles were trapped between the adhesive and the primed polyester film. Peel adhesion was measured at an angle of 180 degrees. For peel adhesion testing to annealed 18 gauge, 304 stainless steel (SS), polycarbonate (PC) and polypropylene (PP), (all from Chem. Instruments, Fairfield, OH), and glass, float glass, air side (3M Glass Laboratory), the RF12N release liner (SKC Haas Display Films LLC, Seoul KR) was removed from the tapes on PET backings and the adhesives were laminated directly to the 2- inch x 6-inch (5.08 cm x 15.24 cm) substrate using a weighted rubberized (4.5 lb, 2.04 kg) hand roller with 4 repetitions of 3 second roll downs. This method followed ASTM D3330, test method E, liner side. All samples and substrates were conditioned in a controlled temperature and humidity (CTH) room (set at 23°C, 50% RH (relative humidity)) prior to peel testing. SS and Glass test panels (not PP or PC) were cleaned with methyl ethyl ketone (MEK) before and after testing. Peel testing was done using an SP-2100 iMass (iMass Inc., Accord, MA USA) at a rate of 12 inches/min (0.3 m/min) for SS and PP, and 2.4”/min (0.06 m/min) for Glass and PC. Each sample was peeled at least three times from the same substrate and averages of all three measurements are reported. Peel testing done on SS and PP at 12 inches/min is reported in N/mm. Peel testing done on Glass and PC at 2.4 inches/min is reported in Kgf/in. Note: 1 N/mm = 2.59 Kgf/in.

For peel testing after extended aging on SS, samples on SS were placed in an oven set at 65 °C/90% RH for 14 days. The samples were then removed and placed in a CTH room for 1 hour prior to testing immediately at CTH conditions. Failure modes: adh = adhesive (clean separation between the adhesive tape and the substrate with no internal failure of the adhesive), coh = cohesive (internal failure of the adhesive leaving adhesive on the substrate and the backing), #2B = 2 bond failure (separation of the adhesive from the backing and transfer of the adhesive onto the substrate), Gel = edge of the adhesive tape was gelled up with the chemical. Tensile Impact Testing

A test tape sample with PET release liners on both surfaces was cut in a circular ring geometry with a 3.11 cm outer diameter, 2.61 cm inner diameter (2.5 mm bond width). The RF02N liner (SKC Haas Display Films LLC, Seoul KR) was removed exposing the adhesive surface and the tape was adhered to the surface of a SS test frame (4.07 x 4.07 x 0.3 cm) with a circular hole (2.4 cm diameter) cut in the middle; wherein the tape is centered over the hole. The RF12N liner (SKC Haas Display Films FFC, Seoul KR) was then removed from the test tape and a stainless steel circular puck (3.3 cm diameter x 0.3 cm thick) was centered over the test tape and adhered to the stainless frame surface using a 4 kg weight which was placed on the bonded SS puck, tape, SS frame article for 30 seconds. The weight was removed, and the testing fixture was allowed to dwell for 48 hours at CTH. The samples were tested at a drop height of 205 mm with a 3 kg mass using an Instron CEAST 9340 Drop Tower (Norwood, MA), wherein the impact was through the hole in the stationary frame such that the puck was separated from the frame. The total energy and failure mode were recorded, and at-least five replicates were completed for each sample.

Rheology and Glass Transition Temperature.

Rheological testing was performed on an TA Instruments discovery hybrid rheometer (DHR-3), (New Castle, DE). All data was collected by heating / cooling at a rate of 3 °C/min at oscillatory frequencies of 1 Hz with strain values in the linear viscoelastic regime (typically < 5%). The glass transition temperature (at 1 Hz) was determined as the peak of the tan(5) curve from the rheology plot of G’ and G” (y axis -1) vs. temperature (°C), (x axis) and tan(5) (y axis-2). The peak (i.e. highest value) in tan(5) was selected from y axis-2, and the corresponding temperature on the x axis was selected as the glass transition temperature. Tan(5) is an abbreviation for the tangent of the phase angle between the stress and strain oscillation waves in the shear rheology oscillation. Samples that passed the rheology requirements in Table 9 had a shear modulus (G’) of less than 550 kPa at -20 °C and a shear modulus at 25 °C of less than 50 kPa. Samples that did not satisfy both requirements failed the rheology test, with the results shown in Table 9.

Creep Compliance by Dynamic Mechanical Analysis (DMA) Testing

The adhesives were evaluated for creep compliance using a TA Instruments discovery hybrid rheometer (DHR-3), (New Castle, DE) equipped with a Peltier stage and fitted with an 8- mm parallel plate geometry. The sample temperature was maintained at 25 °C with the Peltier stage, while a stress of 40 kPa was applied to the sample for a period of 5 seconds. After 5 seconds of applying the stress, the maximum strain (or max. % strain) is achieved (highest % strain on y axis), and the applied stress was returned to 0 kPa. The max. % strain was recorded (i.e. the peak in the % strain data) to provide a measure of extensibility of the adhesive. The sample was allowed to recover elastically from the maximum strain % for at least 60 sec after the removal of the stress. The % elastic recovery after 60 sec was determined by the following equation: % elastic recovery after 60 sec = (((Max. % strain) - (residual % strain at 60 sec))/(Max. % strain)) xlOO. Samples passed the creep compliance test requirements if they had a “Maximum (Max.) % strain” of greater than 200%, as well as having greater than 90% elastic recovery after 60 sec. Samples that did not satisfy both of these requirements failed the creep compliance test.

Optical Durability Testing

Transmission/haze/clarity (“THC”) measurements were performed using a BYK-Chemie (Wesel, Germany) Haze-gard i, which uses a single LED light source. Transmission refers to the total percentage of light transmitted through the sample (or the ratio of the transmitted light to the incident light). Haze equals the percentage of transmitted light that is diffracted at an angle greater than 2.5 degrees from the path of the incident light. Increased haze reduces contrast and results in a milky or cloudy appearance. Clarity (or small/narrow angle scattering) equals the percentage of transmitted light that is diffracted at an angle of less than 2.5 degrees from the path of the incident light. Reduced clarity means contours of an image can seem distorted and less distinct.

The adhesive transfer tape (50 pm liner, 50 pm adhesive, 50 pm liner assembly), ATT, was cut to approximately 5 cm width by 10 cm length. The RF02N liner was removed, and the 50 micron thick adhesive with the second liner was laminated to an optically clear piece of 1 mm thick glass (Eagle Glass, Coming Glass, Coming, NY). The second liner, RF12N was then removed and a 2 mil (50 pm) thick layer of optically clear polyethylene terephthalate (PET, Skyrol SH-81 from SKC Haas, Seoul, Korea) was laminated onto the assembly layer. The laminated sample was placed in the Haze-gard i to measure THC through the PET/PSA/glass assembly. It should be noted that the THC values for the PET alone were 95.10%T, 0.95%H, and 99.9%C while the THC values for the glass alone were 93.8%T, 0.11%H, and 100%C.

Samples were then aged in an oven chamber set to 65 °C and 90% relative humidity for 500 hours. After samples were removed from the heat/humidity chamber and allowed to equilibrate in conditions of 50% relative humidity (RH) and 23 °C for at least 1 h, haze measurements were re-measured. Typically, samples acceptable for optically clear adhesive (OCA) applications will retain haze values of less than about 1% and transmission and clarity of 90% or more, before and after aging.

Number Average Molecular Weight by ¾-NMR

Nuclear Magnetic Resonance Spectroscopy was performed on a Bruker 500 MHz instrument. 'H-NMR was in CDCL (residual solvent referenced to 7.26 ppm). The number average molecular weight was calculated by setting the terminal PO unit -CH3 signal at 1.0 ppm to 3.0. Molecular Weight by Size Exclusion Chromatography (SEC)

The molecular weight (both number average and weight average) were measured using a SEC method. A Waters ACQUITY instrument using a THF mobile phase at flow rate of lml/min was used. Separation was conducted on sequential Styragel Guard pre-column (20 pm, 4.6 mm X 30 mm) and two separation columns Styragel, HR 5E, mixed bed (5pm, 7.8 mm X 300 mm, 2K - 4M) columns. Molecular weight data are reported relative to polystryrene standards.

Preparatory Examples

Synthesis of urea acrylate polyether macromers using JEFFAMINES

Reaction Scheme 1

The following procedure is for converting M600 into M600-UREA acrylate, but is representative for all JEFFAMINE starting materials (i.e. M600, M1000, M2005, M2070, M3085, and XTJ436). For A-D4000-A, 2 molar equivalents of 2-isocyanoethyl acrylate were used per 1 molar equivalent of D4000.

A dry round bottom flask was charged with dry dichloromethane (140 g) and M600 (20.0 g, 33.3 mmol, 1 eq.). The solution was cooled down to 0 °C. Then, 2-isocyanoethyl acrylate (5.18 g, 36.6 mmol, 1.1 eq) was added dropwise over the course of 15 min. The reaction was allowed to warm to room temperature and was stirred for an additional 20 hrs. The solvent was removed by rotary evaporation. Residual 2-isocyanoethyl acrylate monomer and solvent was removed by sparging with air at 40 °C for at least 24 hrs or until residual 2-isocyanoethyl acrylate could not be detected by 'H-NMR spectroscopy. 'H-NMR spectra confirmed all product structures.

Synthesis of PTHF-NH ₂

Reaction Scheme 2

Synthesis of PTHF-NH2 was accomplished by following modified procedures presented in US 4,833,213 (Leir et al.). More specifically, methyl trifluoromethane sulfonate (4.8 mF, 6.96 g, 0.043 moles) was added to a flask containing dry tetrahydrofuran (THF, 585 g, 8.1 moles). The reaction was stirred at room temperature for 7 minutes then FHMDS (90 mF of a 1.0 M solution in THF, 0.09 moles) was added. The reaction was stirred at room temperature overnight to quench. The excess THF was removed by rotatory evaporation. The polymer was then dissolved in 500 mL DCM, washed three times with 150 mL water, and the organic layer dried over MgSCL. The dried organic layer was gravity fdtered and the solvent removed by rotatory evaporation to yield the crude polymer. The crude polymer was dissolved in 300 mL toluene in a 1 liter round bottom flask and 100 mL methanol was added. The methanol was distilled off under ambient pressure, additional methanol (100 mL) was added and distilled off. A crude sample was taken for ¹ H-NMR analysis, which revealed the reaction was incomplete. To the round bottom comprising the polymer in toluene, an additional 300 mL methanol was added. The reaction mixture was refluxed for 24 hours, cooled to room temperature, fdtered through celite to remove salts, and the solvent removed by rotatory evaporation to yield PTHF-NH ₂ . Product was confirmed by ¹ H-NMR spectroscopy and found to have a M _n = 1.1 kg/mol.

Synthesis of PTHF-UREA

Reaction Scheme 3

A dry round bottom flask was charged with dry dichloromethane (85 g) and PTHF-NH ₂ (12.8 g, 10.7 mmol, 1 eq.). The solution was cooled to 0 °C and 2-isocyanoethyl acrylate (1.88 g, 13.3 mmol, 1.2 eq) was added dropwise over the course of 15 min. The reaction was allowed to warm to room temperature and was stirred for an additional 22 hrs. The solvent was removed by rotatory evaporation. Residual 2-isocyanoethyl acrylate monomer and solvent was removed by sparging with air at 40 °C for at least 24 hrs or until residual 2-isocyanoethyl acrylate could not be detected by ¹ H-NMR. Product was confirmed by ¹ H-NMR spectroscopy.

General Synthesis of PTHF-OH

Reaction Scheme 5

PTHF-OH (1 kDa): A flame-dried round bottom flask was charged with 590 g of dry tetrahydrofuran (THF), and a Teflon-coated stir bar, and capped with a rubber septum. 5.0 mL of freshly distilled methyl trifluoromethane sulfonate was then added. The reaction was stirred at ambient temperature for 7 minutes before 100 mL of aq. NaOH (2% by weight) was added. The residual THF monomer was removed by rotary evaporation. The PTHF was next diluted with 500 mL of DCM and subsequently washed with DI water (3x 150 mL). The DCM layer was dried over MgSO ₄ and fdtered. PTHF-OH was isolated by removing the DCM by rotary evaporation and drying under high vacuum. THF conversion= 7.3%. M _n,(NMR) = 1024 g/mol.

PTHF-OH (3 kDa): The same procedure for PTHF-OH (1 kDa) was used except the reaction was quenched at 18 min. crude conversion = 30%, M _n,(NMR) =3500 g/mol

General Carbamate Synthesis

Reaction Scheme 6

PPG-CARB: A dry round bottom flask was charged with poly(propylene glycol) monobutyl ether (Mn ~ 1000 g/mol, 20 g, 20 mmol, 1 eq.), dibutyl tin dilaurate (8 mg), and a Teflon coated stir bar. Then, 2-isocyanoethyl acrylate (2.85 mL, 20.2 mmol, 1.01 eq.) was added dropwise. The reaction was stirred for 48 hrs at room temperature. Then, the solution was heated to 40 °C and sparged with air for 24 hrs to yield a colorless liquid. Product confirmed by 'H-NMR spectroscopy. PEG-CARB: The same procedure was used as PPG-CARB except using PEG-OH. PTHF-CARB1: The same procedure was used as PPG-CARB except using PTHF-OH (1 kDa). PTHF-CARB3: The same procedure was used as PPG-CARB except using PTHF-OH (3 kDa).

Examples: Preparation and Characterization of Adhesive Compositions and Adhesive Tapes Monomers were combined in the appropriate wt-% ratios to target the desired final copolymer composition, with a total wt-% of 100%. All other components added were based on the weight of the first monomer composition and are reported as parts per hundred resin (phr).

The syrups were prepared according to the compositions in Table 2. To each monomer mixture was added IRGACURE 651 at 0.02 phr (with respect to the total mass of 100 wt-% of the monomers). The mixture of monomers and initiator was degassed with nitrogen for 10 min, and then exposed to low intensity (0.3 mW/cm2) UV-A radiation from a 360 nm UV-LED light source, while stirring until a syrup composition having a viscosity of approximately 1000-2000 cP was obtained. The molecular weight of each syrup polymer in Table 3 was measured by the SEC method with polystyrene standards.

IRGACURE 651 (0.2 phr), HDDA, macromonomer, GPTMS and additional additives were added to each syrup composition according to Table 4 and Table 8, and the resulting solutions were visibly well mixed. The solution was coated between PET release liners (Tight side: RF12N and easy side: RF02N; all available from SKC Haas, Seoul, Korea, 2 mil) at an adhesive thickness of 8 mils (0.2 mm). The coated solutions were cured with 2 J/cm ² of total UV-A 365 nm UV-LED irradiation to produce tacky adhesive films.

Table 2. Monomer compositions used in making syrup polymers in wt %

Table 3. Molecular weight data of resulting syrup polymers from Table 2

Table 4. Example compositions made using specified base syrup polymer

The rheological properties of the adhesive compositions are shown in Table 5. Table 5. Rheological properties of the adhesive compositions

Table 6. 180 degree peel adhesion data of the tapes from stainless steel Table 7. Tensile impact data

Table 8. Example compositions made using specified base syrup polymer

EX -29 was coated at a thickness of 200 microns.

Table 9. Rheology and creep compliance results

Table 10. Peel adhesion test results

Table 11. Optical durability testing results