# US 9,518,200 B2 · Curable resin composition, adhesive composition, cured object or composite

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- Number: US 9,518,200 B2
- Document ID: US9518200B2
- Status: Granted
- Kind: B2
- Application number: 13/318,057
- Filed: 2010-04-30
- Published: 2012-03-22
- Granted: 2016-12-13
- Earliest claimed: 2009-04-30
- Assignees: Denka Company Limited
- Applicants: Hayato Miyazaki; Jun Watanabe; Hiroshi Suto
- Inventors: Hayato Miyazaki; Jun Watanabe; Hiroshi Suto
- Web page: https://patentgrep.com/patent/US9518200B2

## CPC

- C09J 133/08: Homopolymers or copolymers of acrylic acid esters
- C08F 287/00: Macromolecular compounds obtained by polymerising monomers on to block polymers
- C09J 133/10: Homopolymers or copolymers of methacrylic acid esters
- C09J 153/00: Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- Y10T 428/2891: including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof
- 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
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

A curable resin composition that is adhesive and transparent. The curable resin composition comprises (1) a polymerizable vinyl monomer, (2) a curing agent, (3) a reducing agent, and (4) an acrylic block copolymer having a structure represented by formula (1): [a1]-[b]-[a2] (1) wherein [a1] and [a2] each independently represents a polymer block which consists mainly of structural units derived from an alkyl acrylate and/or an alkyl methacrylate and has a glass transition temperature of 90° C. or higher, and [b] represents a polymer block which consists mainly of structural units derived from an alkyl acrylate and/or an alkyl methacrylate and has a glass transition temperature of −10° C. or lower, the copolymer satisfying the relationship (total mass of [a1] and [a2]/(mass of [b])=5/95 to 80/20.

## Claims

### Claim 1

A curable resin composition, comprising:
a polymerizable vinyl monomer,
a curing agent comprising an organic peroxide,
a paraffin,
a (meth)acrylic acid,
a reducing agent, and
an acrylic block copolymer having a structure of formula (II):
[a1]-[b]-[a2] (II)
wherein
[a1] is a polymer block consisting of polymethylmethacrylate, and having a glass transition temperature of from 100 to 120° C.;
[a2] is a polymer block consisting of polymethylmethacrylate, and having a glass transition temperature of from 100 to 120° C.;
[b] is a polymer block consisting of poly-n-butylacrylate, and having a glass transition temperature of from −50 to −45° C.;
a ratio of a total mass of [a1] and [a2] to a mass of [b] is from 40/60 to 55/45;
the polymerizable vinyl monomer comprises from 30 to 80 parts by mass of (A) a methylmethacrylate monomer, from 10 to 50 parts by mass of (B) a phenoxyethylmethacrylate monomer and/or a 2-hexylethylmethacrylate monomer, and from 1 to 20 parts by mass of (C) a 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane monomer and/or an ethylene oxide-modified bisphenol A dimethacrylate monomer;
the curable resin composition, when cured, has a haze of from 3% to 10%, expressed as a ratio of diffuse transmittance over luminous transmittance;
wherein a total content of the polymerizable vinyl monomer, the curing agent, the paraffin, the (meth)acrylic acid, the reducing agent, and the acrylic block copolymer having a structure of formula (II) is at least 90 mass %; and
a content of the acrylic block copolymer is from 40 to 70 parts by mass per 100 parts by mass of the polymerizable vinyl monomer.

### Claim 2 (depends on 1)

The composition of claim 1,
wherein a content of the organic peroxide is from 0.1 to 20 parts by mass per 100 parts by mass of the polymerizable vinyl monomer,
a content of the paraffin is from 0.01 to 2.5 parts by mass per 100 parts by mass of the polymerizable vinyl monomer,
a content of the reducing agent is from 0.05 to 15 parts by mass per 100 parts by mass of the polymerizable vinyl monomer, and
a content of the (meth)acrylic acid is from 0.1 to 20 parts by mass per 100 parts by mass of the polymerizable vinyl monomer.

### Claim 3

A curable resin composition, consisting essentially of:
a polymerizable vinyl monomer,
from 0.1 to 20 parts by mass of an organic peroxide as a curing agent, per 100 parts by mass of the polymerizable vinyl monomer,
from 0.01 to 2.5 parts by mass of a paraffin, per 100 parts by mass of the polymerizable vinyl monomer,
from 0.1 to 20 parts by mass of a (meth)acrylic acid, per 100 parts by mass of the polymerizable vinyl monomer,
from 0.05 to 15 parts by mass of a reducing agent, per 100 parts by mass of the polymerizable vinyl monomer, and
from 40 to 70 parts by mass of an acrylic block copolymer, per 100 parts by mass of the polymerizable vinyl monomer,
wherein the acrylic block copolymer has a structure of formula (II):
[a1]-[b]-[a2] (II)
wherein
[a1] is a polymer block consisting of polymethylmethacrylate, and having a glass transition temperature of from 100 to 120° C.;
[a2] is a polymer block consisting of polymethylmethacrylate, and having a glass transition temperature of from 100 to 120° C.;
[b] is a polymer block consisting of poly-n-butylacrylate, and having a glass transition temperature of from −50 to −45° C.;
a ratio of a total mass of [a1] and [a2] to a mass of [b] is 1/1;
the polymerizable vinyl monomer consists essentially of from 30 to 80 parts by mass of (A) a methylmethacrylate monomer, from 10 to 50 parts by mass of (B) a phenoxyethylmethacrylate monomer and/or a 2-hexylethylmethacrylate monomer, and from 1 to 20 parts by mass of (C) a 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane monomer and/or an ethylene oxide-modified bisphenol A dimethacrylate monomer; and
the curable resin composition, when cured, has a haze of from 3% to 10%, expressed as a ratio of diffuse transmittance over luminous transmittance.

### Claim 4 (depends on 3)

The curable resin composition of claim 3, wherein a weight-average molecular weight of the acrylic block copolymer is from 5,000 to 4,000,000.

### Claim 5 (depends on 3)

The curable resin composition of claim 3, wherein a molecular weight distribution of the acrylic block copolymer is from 0.5 to 1.5.

### Claim 6 (depends on 3)

The curable resin composition of claim 3, wherein the reducing agent is at least one thiourea derivative selected from the group consisting of acetyl-2-thiourea, benzoylthiourea, N,N-diphenyithiourea, N,N-diethylthiourea, N,N-dibutylthiourea, and tetramethylthiourea.

### Claim 7 (depends on 3)

The curable resin composition of claim 3, wherein a molecular weight distribution of the acrylic block copolymer is from 1.0 to 1.2.

### Claim 8 (depends on 3)

The curable resin composition of claim 3, wherein the reducing agent is at least one thiourea derivative selected from the group consisting of acetyl-2-thiourea, benzoylthiourea, N,N-diphenylthiourea, and N,N-diethylthiourea.

### Claim 9 (depends on 3)

The curable resin composition of claim 3, wherein the reducing agent is acetyl-2-thiourea.

### Claim 10 (depends on 3)

The curable resin composition of claim 3, wherein the curing agent is at least one selected from the group consisting of cumene hydroperoxide, paramenthane hydroperoxide, tertiary butyl hydroperoxide, diisopropylbenzene dihydroperoxide, methylethylketone peroxide, benzoyl peroxide, and tertiary butyl peroxybenzoate.

### Claim 11 (depends on 3)

The curable resin composition of claim 3, wherein the curing agent is cumene hydroperoxide.

### Claim 12 (depends on 3)

The curable resin composition of claim 3, wherein the polymerizable vinyl monomer consists essentially of from 40 to 70 parts by mass of the monomer (A), from 20 to 40 parts by mass of the monomer (B), and from 5 to 15 parts by mass of the monomer (C).

### Claim 13 (depends on 3)

The curable resin composition of claim 3,
wherein the composition is a two-component curable resin composition,
the curing agent is in a first component of the two-component curable resin composition, and
the reducing agent is in a second component of the two-component curable resin composition.

### Claim 14 (depends on 3)

An adhesive composition comprising the curable resin composition of claim 3.

### Claim 15 (depends on 14)

A cured object comprising the adhesive composition of claim 14.

### Claim 16 (depends on 15)

A composite, comprising an adhered object coated or bonded by the cured object of claim 15.

### Claim 17 (depends on 16)

The composite of claim 16, wherein the adhered object is a transparent resin, and
wherein a haze of the adhesive composition in cured form is from 3% to 10%, expressed as a ratio of diffuse transmittance over luminous transmittance.