# US 10,870,779 B2 · Removable water-based pressure-sensitive adhesive composition and removable pressure-sensitive adhesive sheet

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- Number: US 10,870,779 B2
- Document ID: US10870779B2
- Status: Granted
- Kind: B2
- Application number: 16/094,724
- Filed: 2017-11-06
- Published: 2019-04-25
- Granted: 2020-12-22
- Earliest claimed: 2016-11-07
- Assignees: Saiden Chemical Industry Co., Ltd.
- Applicants: Saiden Chemical Industry Co., Ltd.
- Inventors: Kentaro Miyazawa; Shuji Kawamura; Hirokazu Umemiya
- Web page: https://patentgrep.com/patent/US10870779B2

## CPC

- C09J 7/385: {Acrylic polymers}
- C08F 220/06: Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
- C08F 220/10: Esters
- C08F 220/1802: {C2-(meth)acrylate, e.g. ethyl (meth)acrylate}
- C08F 220/56: Acrylamide; Methacrylamide
- C08K 5/0025: {Crosslinking or vulcanising agents; including accelerators}
- C08K 5/11: of acyclic polycarboxylic acids
- C08K 5/28: Azides
- C08K 5/353: Five-membered rings
- C09J 11/06: organic
- C09J 11/08: Macromolecular additives
- C09J 133/02: Homopolymers or copolymers of acids; Metal or ammonium salts thereof
- C09J 133/04: Homopolymers or copolymers of esters {(C09J143/04 takes precedence)}
- C09J 133/06: of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J 133/08: Homopolymers or copolymers of acrylic acid esters
- C09J 133/10: Homopolymers or copolymers of methacrylic acid esters
- C09J 133/24: Homopolymers or copolymers of amides or imides
- C09J 133/26: Homopolymers or copolymers of acrylamide or methacrylamide
- C08F 220/1808: {C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate}
- C08L 33/06: of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- 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)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

The present application provides a re-releasable aqueous pressure-sensitive adhesive composition containing: as a main component, an emulsion [A] of a (meth)acrylic acid-based ester copolymer, an emulsion [B] of a (meth)acrylic acid-based ester copolymer, and a crosslinker [C]. The emulsion [A] contains a constituent unit that has a carboxy group or a hydroxy group and reacts with a crosslinker. The emulsion [B] is included in the composition in an amount of 0.6 parts by mass or more in terms of a solid content based on 100 parts by mass of a solid content of the emulsion [A] and functions as a crosslinking assistant. The emulsion [B] has a peculiar structure dissolving in water upon neutralization and is unmeasurable in a particle diameter distribution analysis at pH from 6.5 to 7.5. The crosslinker [C] is a hydrazide-based compound that is soluble or dispersible in water.

## Claims

### Claim 1

A re-releasable aqueous pressure-sensitive adhesive composition comprising: as a main component, an emulsion [A] of a first (meth)acrylic acid-based ester copolymer, the emulsion [A] having a constituent unit that reacts with a crosslinker [C]; an emulsion [B] of a second (meth)acrylic acid-based ester copolymer, in an amount of 0.6 parts by mass or more in terms of a solid content based on 100 parts by mass of a solid content of the emulsion [A], wherein the emulsion [B] functions as a crosslinking assistant; and further, the crosslinker [C] together with the emulsion [A] and the emulsion [B], wherein the crosslinker [C] comprises a hydrazide-based compound that is soluble or dispersible in water, the emulsion [A] of the first (meth)acrylic acid-based copolymer comprises: as a main component, a constituent unit (a1) derived from a first (meth)acrylate-based monomer; a constituent unit (a2) in an amount of 0.5 to 3.0% by mass, the constituent unit (a2) being derived from a first unsaturated monomer containing a functional group, wherein the first unsaturated monomer is at least one monomer selected from a group consisting of an unsaturated monomer having a carboxyl group and an unsaturated monomer having a hydroxy group; and a constituent unit (a3) in an amount of 0.1 to 1.0% by mass, wherein the constituent unit (a3) is derived from a first ethylenically unsaturated monomer and has reactivity with the hydrazide-based compound that is contained in the crosslinker [C] and that is soluble or dispersible in water, the emulsion [B] of the second (meth)acrylic acid-based ester copolymer comprises: a constituent unit (b1) derived from a second (meth)acrylate-based monomer in an amount of 15 to 60% by mass; a constituent unit (b2) derived from a second unsaturated monomer having a carboxy group in an amount of 20 to 50% by mass; and a constituent unit (b3) in an amount of 20 to 45% by mass, wherein the constituent unit (b3) is derived from a second ethylenically unsaturated monomer and has reactivity with the hydrazide-based compound that is contained in the crosslinker [C] and that is soluble or dispersible in water, the emulsion [B] is an emulsion that dissolves in water upon neutralization and is unmeasurable in a particle diameter analysis at a pH in a range from 6.5 to 7.5 and the crosslinker [C] is crosslinkable with at least the constituent unit (a3) of the emulsion [A] and the constituent unit (b3) of the emulsion [B].

### Claim 2 (depends on 1)

The re-releasable aqueous pressure-sensitive adhesive composition according to claim 1, wherein the crosslinker [C] is contained in the composition in an amount of 0.05 to 0.5 parts by mass based on 100 parts by mass of the solid content of the emulsion [A].

### Claim 3 (depends on 1)

The re-releasable aqueous pressure-sensitive adhesive composition according to claim 1, wherein each of the first ethylenically unsaturated monomer that forms the constituent unit (a3) derived therefrom and the second ethylenically unsaturated monomer that forms the constituent unit (b3) derived therefrom comprises at least one compound selected the group consisting of diacetone (meth)acrylamide, (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, and N,N-dimethyl(meth)acrylamide.

### Claim 4 (depends on 1)

The re-releasable aqueous pressure-sensitive adhesive composition according to claim 1, further comprising a crosslinker [C′] crosslinkable with the constituent unit (a2) and the constituent unit (b2),
wherein the crosslinker [C′] is at least one compound selected from the group consisting of an oxazoline-based compound and a metal chelate compound, the oxazoline-based compound having within a molecule thereof, two or more oxazoline groups.

### Claim 5 (depends on 1)

The re-releasable aqueous pressure-sensitive adhesive composition according to claim 1, further comprising a non-phthalic acid-based plasticizer [D] in an amount of 0.5 to 5 parts by mass based on 100 parts by mass of the solid content of the emulsion [A].

### Claim 6 (depends on 5)

The re-releasable aqueous pressure-sensitive adhesive composition according to claim 5, wherein the non-phthalic acid-based plasticizer [D] comprises dibutoxyethoxyethyl adipate.

### Claim 7 (depends on 1)

The re-releasable aqueous pressure-sensitive adhesive composition according to claim 1, wherein both the emulsion [A] and the emulsion [B] have an average particle diameter in a range from 100 to 900 nm.

### Claim 8 (depends on 1)

A re-releasable pressure-sensitive adhesive sheet comprising: a pressure-sensitive adhesive layer; and a base material sheet, wherein the pressure-sensitive adhesive layer is formed on at least one face of the base material sheet, and the pressure-sensitive adhesive layer comprising the re-releasable aqueous pressure-sensitive adhesive composition of claim 1.