# US 8,785,517 B2 · Pressure-sensitive adhesives with onium-epdxy crosslinking system

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- Number: US 8,785,517 B2
- Document ID: US8785517B2
- Status: Granted
- Kind: B2
- Application number: 13/155,935
- Filed: 2011-06-08
- Published: 2012-11-29
- Granted: 2014-07-22
- Earliest claimed: 2011-05-25
- Assignees: 3M Innovative Properties Company
- Applicants: Arlin L. Weikel; Larry R. Krepski; Jason D. Clapper; Wayne S. Mahoney; Babu N. Gaddam
- Inventors: Arlin L. Weikel; Larry R. Krepski; Jason D. Clapper; Wayne S. Mahoney; Babu N. Gaddam
- Web page: https://patentgrep.com/patent/US8785517B2

## CPC

- C08L 63/10: Epoxy resins modified by unsaturated compounds
- C08F 224/00: Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen (cyclic esters of polyfunctional acids C08F218/00; cyclic anhydrides of unsaturated acids C08F220/00, C08F222/00)
- C09D 4/06: {Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond} in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
- C09J 7/38: Pressure-sensitive adhesives [PSA]
- C09J 133/062: {Copolymers with monomers not covered by C09J133/06}
- C09J 133/10: Homopolymers or copolymers of methacrylic acid esters
- C08F 220/325: {containing glycidyl radical, e.g. glycidyl (meth)acrylate}
- Y10T 428/2809: including irradiated or wave energy treated component
- Y10T 428/2852: Adhesive compositions
- Y10T 428/287: including epoxy group or epoxy polymer
- Y10T 428/2891: including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H)
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

A pre-adhesive composition is described comprising an acid- and epoxy-functional (meth)acryloyl copolymer, which when crosslinked using an ionic photoacid generator (PAG) provides a pressure-sensitive adhesive and pressure-sensitive adhesive articles having desirable properties.

## Claims

### Claim 1

A crosslinkable composition comprising:
a) an epoxy-functional (meth)acrylic copolymer comprising interpolymerized monomers comprising:
i) an alkyl (meth)acrylate monomer;
ii) an epoxy-functional (meth)acryloyl monomer;
iii) an acid-functional ethylenically unsaturated monomer in amounts of 1 to 15 parts by weight of the 100 parts of the total monomer;
iv) an optional non-acid functional polar monomer;
v) an optional vinyl monomer, and
vi) an optional multifunctional (meth)acrylate crosslinker; and
b) an ionic photoacid generator.

### Claim 2 (depends on 1)

The crosslinkable composition of claim 1 wherein the epoxy-functional (meth)acryloyl monomer is used in an amount of no greater than 20 parts by weight, and the ionic photoacid generator is used in an amount of no greater than 1 part by weight, relative to 100 parts by weight of the total monomer.

### Claim 3 (depends on 1)

The crosslinkable composition of claim 1 wherein the ionic photoacid generator is used in an amount of 0.01 to 1 part by weight.

### Claim 4 (depends on 1)

The crosslinkable composition of claim 1 wherein the epoxy-functional (meth)acryloyl monomer is used in an amount of 1 to 20 parts by weight.

### Claim 5 (depends on 1)

The crosslinkable composition of claim 1 wherein the epoxy-functional (meth)acrylic copolymer comprises interpolymerized monomers comprising:
i) 85 to 99 parts by weight of a (meth)acrylic acid ester of a non-tertiary alcohol;
ii) 1 to 20 parts by weight of an epoxy-functional (meth)acryloyl monomer; and
iii) 1 to 15 parts by weight of an acid-functional ethylenically unsaturated monomer;
based on 100 parts of the total monomer content.

### Claim 6 (depends on 1)

The crosslinkable composition of claim 1 wherein the epoxy-functional (meth)acryloyl monomer is used in an amount of 1 to 10 parts by weight based on 100 parts total monomer.

### Claim 7 (depends on 1)

The crosslinkable composition of claim 1 wherein the (meth)acrylic copolymer further comprises interpolymerized monomers comprising a non-acid-functional polar monomer and a vinyl monomer.

### Claim 8 (depends on 1)

The crosslinkable composition of claim 1 further comprising a multifunctional (meth)acrylate monomer.

### Claim 9 (depends on 1)

The crosslinkable composition of claim 1 wherein the ionic photoacid generator is selected from iodonium salts; sulfonium salts, sulfoxonium salts, selenonium salts, sulfoxonium salts, phosphonium salts, and arsonium salts.

### Claim 10 (depends on 9)

The crosslinkable composition of claim 9 wherein the salts are selected from SbF6−, AsF6−, PF6−, and BF4− salts.

### Claim 11 (depends on 1)

The crosslinkable composition of claim 1 wherein the epoxy-functional (meth)acryloyl monomer is of the formula:
wherein:
R7 is —H or C1-C4 alkyl;
X1 is —O— or —NR9—;
R8 is an epoxy-substituted hydrocarbyl group; and
R9 is —H or a C1-C4 alkyl.

### Claim 12 (depends on 11)

The crosslinkable composition of claim 11 wherein R8 is
where R4 is a C1-C6 alkylene.

### Claim 13 (depends on 1)

The crosslinkable composition of claim 1 wherein the epoxy-functional (meth)acryloyl monomer is of the formula:
wherein:
R10 is a (hetero)hydrocarbyl group;
R11 is —H or —H or C1-C4 alkyl;
X2 is —NR12— or —O—; and
R12 is —H or a C1-C4 alkyl.

### Claim 14 (depends on 1)

A crosslinkable composition of claim 1 comprising:
a) an epoxy-functional (meth)acrylic copolymer that comprises interpolymerized monomers comprising:
i) 85 to 99 parts by weight of a (meth)acrylic acid ester monomer;
ii) 1 to 20 parts by weight of an epoxy-functional (meth)acryloyl monomer;
iii) 1 to 15 parts by weight of an acid-functional ethylenically unsaturated monomer;
iv) 0 to 10 parts by weight of a non-acid-functional polar monomer;
v) 0 to 5 parts by weight of a vinyl monomer;
vi) 0 to 5 parts of a multifunctional (meth)acrylate crosslinker; and
b) 0.01 to 1 parts by weight of an ionic photoacid generator based on 100 parts by weight total monomer i) to yl).

### Claim 15 (depends on 14)

The crosslinkable composition of claim 14 further comprising a tackifier.

### Claim 16 (depends on 1)

The crosslinkable composition of claim 1 wherein the epoxy-functional (meth)acryloyl monomer is of the formula:
where R4 is C1-C4 alkylene.

### Claim 17 (depends on 1)

A crosslinkable syrup composition comprising:
the solute (meth)acryloyl copolymer of claim 1 comprising a plurality of interpolymerized monomers comprising pendant epoxy units;
a component comprising at least one free-radically polymerizable solvent monomer; and
an ionic photoacid generator.

### Claim 18 (depends on 17)

The crosslinkable syrup composition of claim 17 where the solute (meth)acryloyl copolymer comprises:
i) 85 to 99 parts by weight of a (meth)acrylic acid ester monomer;
ii) 1 to 20 parts by weight of an epoxy-functional (meth)acryloyl monomer;
iii) 1 to 15 parts by weight of an acid-functional ethylenically unsaturated monomer;
iv) 0 to 10 parts by weight of a non-acid-functional polar monomer;
v) 0 to 5 parts by weight of a vinyl monomer;
based on 100 parts by weight total monomer.

### Claim 19 (depends on 17)

The crosslinkable syrup composition of claim 17 where the solvent monomer comprises:
(meth)acrylic acid ester monomer;
epoxy-functional (meth)acryloyl monomer;
optional acid-functional ethylenically unsaturated monomer;
optional non-acid-functional polar monomer;
optional vinyl monomer;
optional multifunctional (meth)acrylate crosslinker.

### Claim 20 (depends on 17)

The crosslinkable syrup composition of claim 17 wherein the interpolymerized monomers comprise an epoxy-functional (meth)acryloyl monomer is of the formula:
wherein:
R7 is —H or C1-C4 alkyl;
X1 is —O— or —NR—;
R8 is an epoxy-substituted hydrocarbyl group; and
R9 is —H or a C1-C4 alkyl.

### Claim 21 (depends on 17)

The crosslinkable syrup composition of claim 17 wherein the interpolymerized monomers comprise an epoxy-functional (meth)acryloyl monomer of the formula:
wherein:
R10 is a (hetero)hydrocarbyl group (preferably, hydrocarbyl);
R11 is —H or C1-C4 alkyl;
X2 is —NR12— or —O—; and
R12 is —H or a C1-C4 alkyl.

### Claim 22 (depends on 17)

The crosslinkable syrup composition of claim 17 wherein the ionic photoacid generator is selected from iodonium salts; sulfonium salts, selenonium salts sulfoxonium salts, phosphonium salts and arsonium salts.

### Claim 23 (depends on 17)

The crosslinkable syrup composition of claim 17 wherein the ionic photoacid generator is used in an amount of 0.01 to 1 part by weight, relative to 100 parts by weight of solute copolymer and solvent monomer(s).

### Claim 24 (depends on 17)

A pressure-sensitive adhesive composition prepared from a crosslinkable composition of the crosslinkable syrup composition of claim 17.

### Claim 25 (depends on 24)

A pressure-sensitive adhesive article comprising a coating of the adhesive of claim 24 on a backing.

### Claim 26

A method of preparing a pressure-sensitive adhesive comprising the steps of
a) providing a syrup copolymer composition comprising solvent monomer(s) and a solute copolymer of interpolymerized monomer units of:
i) an alkyl (meth)acrylate monomer;
ii) an epoxy-functional (meth)acryloyl monomer;
iii) an acid-functional ethylenically unsaturated monomer in amounts of 1 to 15 parts by weight of the 100 parts of the total monomer;
iv) an optional non-acid functional polar monomer;
v) an optional vinyl monomer; and
b) combining the syrup copolymer composition with an ionic photoacid generator, optional multifunctional (meth)acrylate and optional photoinitiator, and
c) irradiating with UV radiation.