# US 11,078,355 B2 · (Meth)acrylic copolymer, resin composition, molded body of same, and method for producing molded body

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- Number: US 11,078,355 B2
- Document ID: US11078355B2
- Status: Granted
- Kind: B2
- Application number: 16/334,197
- Filed: 2017-09-25
- Published: 2019-07-04
- Granted: 2021-08-03
- Earliest claimed: 2016-09-26
- Assignees: Mitsubishi Gas Chemical Company, Inc.
- Applicants: Mitsubishi Gas Chemical Company, Inc.
- Inventors: Kazuki Kouno; Hisayuki Kuwahara
- Web page: https://patentgrep.com/patent/US11078355B2

## CPC

- C08F 220/302: {and two or more oxygen atoms in the alcohol moiety}
- B29C 45/0001: {characterised by the choice of material}
- C08F 220/14: Methyl esters {, e.g. methyl (meth)acrylate}
- C08K 5/13: Phenols; Phenolates
- C08K 5/3475: condensed with carbocyclic rings
- C08K 5/3492: Triazines
- C08K 5/357: Six-membered rings
- C08K 5/524: Esters of phosphorous acids, e.g. of H3PO3
- C08L 33/04: Homopolymers or copolymers of esters {(C08L43/04 takes precedence)}
- C08L 33/066: {containing -OH groups}
- C08L 33/12: Homopolymers or copolymers of methyl methacrylate
- C08L 33/14: of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08L 69/00: Compositions of polycarbonates; Compositions of derivatives of polycarbonates
- B29K 2033/08: {Polymers of acrylic acid esters, e.g. PMA, i.e. polymethylacrylate}
- B29K 2033/12: {Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate}
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- 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)
- B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS

## Abstract

Provided is a resin composition which is capable of forming a molded body that has excellent surface hardness, transparency, hue and weather resistance, while exhibiting excellent wet heat resistance. A resin composition which contains a (meth)acrylic copolymer (A) and a polycarbonate-based resin (B), and wherein: the (meth)acrylic copolymer (A) contains an aromatic (meth)acrylate unit (a1), a methyl (meth)acrylate unit (a2) and a (meth)acrylate unit (a3) represented by formula (1); the mass ratio (a1)/(a2) is from 5/95 to 85/15; the content of the unit (a3) is 0.1-10 parts by mass relative to 100 parts by mass of the total of the units (a1) and (a2); and the unit (a1) is different from the unit (a3).

## Claims

### Claim 1

A (meth)acrylic copolymer, which contains an aromatic (meth)acrylate unit (a1), a methyl (meth)acrylate unit (a2) and a (meth)acrylate unit (a3) represented by formula (1) below; wherein: the mass ratio (a1)/(a2) is from 5/95 to 99/1; and the unit (a1) is different from the unit (a3):
wherein:
X represents a halogen atom or a C1-10 alkyl group;
R1 represents a C1-10 alkyl group;
R2 represents a single bond, a C1-10 alkylene group, a C1-10 oxyalkylene group or a C1-10 hydroxyoxyalkylene group;
R3 represents a hydrogen atom or a methyl group;
a represents an integer of 0 to 3;
b represents an integer of 0 to 4; and
wherein the content of the unit (a3) is 0.1 to 4 parts by mass relative to 100 parts by mass of the total of the units (a1) and (a2);
wherein the unit (a1) contains a structural unit represented by any one of formula (3) to formula (5):
wherein in formula (3) to formula (5):
Y represents a single bond, or a divalent group selected from the group consisting of —C(R15)(R16)—, —C(═O)—, —O—, —OC(═O)—, —OC(═O)O—, —S—, —SO—, —SO2— and any combination thereof;
R4 and R5 each independently represent a C1-10 linear alkyl group, a C3-10 branched alkyl group, a C3-10 cyclic alkyl group, a C1-10 linear alkoxy group, a C3-10 branched alkoxy group, a C3-10 cyclic alkoxy group, a halogen atom, a phenyl group or a phenylphenyl group;
R6 represents a branched or unbranched C2-6 alkylene group, a C6-10 cycloalkylene group or a C6-10 arylene group;
R7 represents a hydrogen atom or a methyl group;
R8 represents a C1-10 linear alkyl group, a C3-10 branched alkyl group, a C3-10 cyclic alkyl group, a C1-10 linear alkoxy group, a C3-10 branched alkoxy group, a C3-10 cyclic alkoxy group or a halogen atom;
R9 represents a branched or unbranched C2-6 alkylene group, a C6-10 cycloalkylene group or a C6-10 arylene group;
R10 represents a hydrogen atom or a methyl group;
R11 and R12 each independently represent a C1-10 linear alkyl group, a C3-10 branched alkyl group, a C3-10 cyclic alkyl group, a C1-10 linear alkoxy group, a C3-10 branched alkoxy group, a C3-10 cyclic alkoxy group, a halogen atom, a phenyl group or a phenylphenyl group;
R13 represents a branched or unbranched C2-6 alkylene group, a C6-10 cycloalkylene group or a C6-10 arylene group;
R14 represents a hydrogen atom or a methyl group;
R15 and R16 each independently represent a hydrogen atom, a C1-10 linear alkyl group, a C3-10 branched alkyl group, a C3-10 cyclic alkyl group, a C1-10 linear alkoxy group, a C3-10 branched alkoxy group, a C3-10 cyclic alkoxy group, a phenyl group or a phenylphenyl group, or R15 and R16 may be bonded to each other to form a C3-10 cyclic alkyl group together with a carbon atom to which they are attached;
m represents an integer of 0 to 10;
n represents an integer of 1 or 2;
k represents an integer of 1 to 3;
l represents an integer of 0 to 2;
i represents an integer of 1 to 3;
j represents an integer of 0 to 2;
p represents an integer of 0 to 4;
q represents an integer of 0 to 5;
r represents an integer of 0;
s represents an integer of 0; and
t represents an integer of 0.

### Claim 2 (depends on 1)

The (meth)acrylic copolymer according to claim 1, wherein the unit (a1) contains a structural unit represented by formula (3):

### Claim 3 (depends on 1)

A resin composition which contains the (meth)acrylic copolymer according to claim 1.

### Claim 4 (depends on 1)

The (meth)acrylic copolymer according to claim 1, wherein the unit (a3) contains a structural unit represented by formula (2):

### Claim 5 (depends on 1)

The (meth)acrylic copolymer according to claim 1, wherein the (meth)acrylic copolymer has a mass-average molecular weight of 3,000 to 1,000,000.

### Claim 6 (depends on 1)

The (meth)acrylic copolymer according to claim 1, wherein the unit (a1) is represented by the formula (3); and in the formula (3), m represents an integer of 1 to 3.

### Claim 7 (depends on 1)

The (meth)acrylic copolymer according to claim 1, wherein the unit (a1) is represented by the formula (3); and in the formula (3), Y represents a single bond, —C(R15)(R16)—, —C(═O)—, —O—, —SO— or —SO2—.

### Claim 8 (depends on 1)

The (meth)acrylic copolymer according to claim 1, wherein the unit (a1) is represented by the formula (3); and in the formula (3), both p and q are 0.

### Claim 9 (depends on 1)

The (meth)acrylic copolymer according to claim 1, wherein the unit (a1) is represented by the formula (4); and in the formula (4), k represents an integer of 1 to 3, and r is 0.

### Claim 10 (depends on 1)

The (meth)acrylic copolymer according to claim 1, wherein the unit (a1) is represented by the formula (5); and in the formula (5), i represents an integer of 1 to 3, and both s and t are 0.

### Claim 11 (depends on 1)

The (meth)acrylic copolymer according to claim 1, wherein the mass ratio (a1)/(a2) is from 5/95 to 85/15.

### Claim 12 (depends on 1)

The (meth)acrylic copolymer according to claim 1, wherein the mass ratio (a1)/(a2) is from 5/95 to 40/60.

### Claim 13

A (meth)acrylic copolymer, which contains an aromatic (meth)acrylate unit (a1), a methyl (meth)acrylate unit (a2) and a (meth)acrylate unit (a3) represented by formula (1) below, wherein: the mass ratio (a1)/(a2) is from 5/95 to 99/1; the content of the unit (a3) is 0.1 to 10 parts by mass relative to 100 parts by mass of the total of the units (a1) and (a2); and the unit (a1) is different from the unit (a3):
wherein:
X represents a halogen atom or a C1-10 alkyl group;
R1 represents a C1-10 alkyl group;
R2 represents a single bond, a C1-10 alkylene group, a C1-10 oxyalkylene group or a C1-10 hydroxyoxyalkylene group;
R3 represents a hydrogen atom or a methyl group;
a represents an integer of 0 to 3;
b represents an integer of 0 to 4;
wherein the unit (a1) contains a structural unit represented by formula (5):
wherein in formula (5):
R11 and R12 each independently represent a C1-10 linear alkyl group, a C3-10 branched alkyl group, a C3-10 cyclic alkyl group, a C1-10 linear alkoxy group, a C3-10 branched alkoxy group, a C3-10 cyclic alkoxy group, a halogen atom, a phenyl group or a phenylphenyl group;
R13 represents a branched or unbranched C2-6 alkylene group, a C6-10 cycloalkylene group or a C6-10 arylene group;
R14 represents a hydrogen atom or a methyl group;
i represents an integer of 1 to 3;
j represents an integer of 0 to 2; and
both s and t are 0.

### Claim 14

A resin composition which contains a (meth)acrylic copolymer (A) and a polycarbonate-based resin (B), wherein:
the (meth)acrylic copolymer (A) contains an aromatic (meth)acrylate unit (a1), a methyl (meth)acrylate unit (a2) and a (meth)acrylate unit (a3) represented by formula (1) below; the mass ratio (a1)/(a2) is from 5/95 to 99/1; and the unit (a1) is different from the unit (a3):
wherein:
X represents a halogen atom or a C1-10 alkyl group;
R1 represents a C1-10 alkyl group;
R2 represents a single bond, a C1-10 alkylene group, a C1-10 oxyalkylene group or a C1-10 hydroxyoxyalkylene group;
R3 represents a hydrogen atom or a methyl group;
a represents an integer of 0 to 3; and
b represents an integer of 0 to 4; and
wherein the content of the unit (a3) is 0.1 to 4 parts by mass relative to 100 parts by mass of the total of the units (a1) and (a2);
wherein the unit (a1) contains a structural unit represented by any one of formula (3) to formula (5):
wherein in formula (3) to formula (5):
Y represents a single bond, or a divalent group selected from the group consisting of —C(R15)(R16)—, —C(═O)—, —O—, —OC(═O)—, —OC(═O)O—, —S—, —SO—, —SO2— and any combination thereof;
R4 and R5 each independently represent a C1-10 linear alkyl group, a C3-10 branched alkyl group, a C3-10 cyclic alkyl group, a C1-10 linear alkoxy group, a C3-10 branched alkoxy group, a C3-10 cyclic alkoxy group, a halogen atom, a phenyl group or a phenylphenyl group;
R6 represents a branched or unbranched C2-6 alkylene group, a C6-10 cycloalkylene group or a C6-10 arylene group;
R7 represents a hydrogen atom or a methyl group;
R8 represents a C1-10 linear alkyl group, a C3-10 branched alkyl group, a C3-10 cyclic alkyl group, a C1-10 linear alkoxy group, a C3-10 branched alkoxy group, a C3-10 cyclic alkoxy group or a halogen atom;
R9 represents a branched or unbranched C2-6 alkylene group, a C6-10 cycloalkylene group or a C6-10 arylene group;
R10 represents a hydrogen atom or a methyl group;
R11 and R12 each independently represent a C1-10 linear alkyl group, a C3-10 branched alkyl group, a C3-10 cyclic alkyl group, a C1-10 linear alkoxy group, a C3-10 branched alkoxy group, a C3-10 cyclic alkoxy group, a halogen atom, a phenyl group or a phenylphenyl group;
R13 represents a branched or unbranched C2-6 alkylene group, a C6-10 cycloalkylene group or a C6-10 arylene group;
R14 represents a hydrogen atom or a methyl group;
R15 and R16 each independently represent a hydrogen atom, a C1-10 linear alkyl group, a C3-10 branched alkyl group, a C3-10 cyclic alkyl group, a C1-10 linear alkoxy group, a C3-10 branched alkoxy group, a C3-10 cyclic alkoxy group, a phenyl group or a phenylphenyl group, or R15 and R16 may be bonded to each other to form a C3-10 cyclic alkyl group together with a carbon atom to which they are attached;
m represents an integer of 0 to 10;
n represents an integer of 1 or 2;
k represents an integer of 1 to 3;
l represents an integer of 0 to 2;
i represents an integer of 1 to 3;
j represents an integer of 0 to 2;
p represents an integer of 0 to 4;
q represents an integer of 0 to 5;
r represents an integer of 0;
s represents an integer of 0; and
t represents an integer of 0.

### Claim 15 (depends on 14)

The resin composition according to claim 14, wherein the unit (a3) contains a structural unit represented by formula (2):

### Claim 16 (depends on 14)

The resin composition according to claim 14, wherein the (meth)acrylic copolymer (A) has a mass-average molecular weight of 3,000 to 1,000,000.

### Claim 17 (depends on 14)

The resin composition according to claim 14, which contains an ultraviolet absorber (C) in an amount of 0 to 0.5 parts by mass relative to 100 parts by mass of a resin component that contains the (meth)acrylic copolymer (A) and the polycarbonate-based resin (B).

### Claim 18 (depends on 17)

The resin composition according to claim 17, wherein the ultraviolet absorber (C) comprises at least one of a benzotriazole-based compound, a triazine-based compound and a benzoxazinone-based compound.

### Claim 19 (depends on 14)

The resin composition according to claim 14, which contains an antioxidant (D) in an amount of 0.05 to 1.0 parts by mass relative to 100 parts by mass of the resin component that contains the (meth)acrylic copolymer (A) and the polycarbonate-based resin (B).

### Claim 20 (depends on 19)

The resin composition according to claim 19, wherein the antioxidant (D) comprises a phenol-based antioxidant or a phosphite-based antioxidant.

### Claim 21 (depends on 14)

The resin composition according to claim 14, wherein the unit (a1) is represented by the formula (3).

### Claim 22 (depends on 14)

The resin composition according to claim 14, wherein in the resin component, the content of the (meth)acrylic copolymer (A) is 5 to 60% by mass, and the content of the polycarbonate-based resin (B) is 40 to 95% by mass.

### Claim 23 (depends on 14)

The resin composition according to claim 14, wherein the mass ratio (a1)/(a2) is from 5/95 to 85/15.

### Claim 24 (depends on 14)

The resin composition according to claim 14, which further contains a (meth)acrylic copolymer (E) that is different from the (meth)acrylic copolymer (A) wherein in the resin component, the content of the (meth)acrylic copolymer (A) is 5 to 40% by mass, the content of the polycarbonate-based resin (B) is 40 to 95% by mass and the content of the (meth)acrylic copolymer (E) is 0 to 30% by mass.

### Claim 25 (depends on 24)

The resin composition according to claim 24, wherein the (meth)acrylic copolymer (E) contains 10 to 85% by mass of a (meth)acrylate unit (e1) represented by general formula (6) below and 15 to 90% by mass of a methyl (meth)acrylate unit (e2):
wherein:
R17 each independently represents a C1-10 linear alkyl group, a C3-10 branched alkyl group, a C3-10 cyclic alkyl group, a C1-10 linear alkoxy group, a C3-10 branched alkoxy group, a C3-10 cyclic alkoxy group, a halogen atom, a substituted or unsubstituted phenyl group or a substituted or unsubstituted phenylphenyl group;
R18 represents a hydrogen atom or a methyl group; and
u represents an integer of 0 to 5.

### Claim 26 (depends on 14)

A molded body formed by using the resin composition according to claim 14.

### Claim 27 (depends on 14)

A method for producing a molded body, wherein the resin composition according to claim 14 is injection-molded.

### Claim 28 (depends on 14)

The resin composition according to claim 14, wherein
(i) the unit (a1) is represented by the formula (3); and in the formula (3), m represents an integer of 1 to 3, Y represents a single bond, —C(R15)(R16)—, —C(═O)—, —O—, —SO— or —SO2—, and both p and q are 0;
(ii) the unit (a1) is represented by the formula (4); or
(iii) the unit (a1) is represented by the formula (5).