US 11,951,720 B2
Thermoplastic resin laminate
Ken Taguwa, Kanagawa (JP); and Nobuyuki Koike, Tokyo (JP)
Assigned to MITSUBISHI GAS CHEMICAL COMPANY, INC., Tokyo (JP)
Appl. No. 17/286,970
Filed by MITSUBISHI GAS CHEMICAL COMPANY, INC., Tokyo (JP)
PCT Filed Oct. 21, 2019, PCT No. PCT/JP2019/041271
§ 371(c)(1), (2) Date Apr. 20, 2021,
PCT Pub. No. WO2020/085286, PCT Pub. Date Apr. 30, 2020.
Claims priority of application No. 2018-202085 (JP), filed on Oct. 26, 2018.
Prior Publication US 2021/0387445 A1, Dec. 16, 2021
Int. Cl. B32B 27/30 (2006.01); B32B 7/00 (2019.01); B32B 7/027 (2019.01); B32B 27/08 (2006.01); B32B 27/36 (2006.01); C08L 25/14 (2006.01); C08L 33/06 (2006.01); C08L 33/10 (2006.01); C08L 33/12 (2006.01); C08L 67/00 (2006.01)
CPC B32B 27/308 (2013.01) [B32B 27/36 (2013.01); B32B 7/00 (2013.01); B32B 7/027 (2019.01); B32B 27/08 (2013.01); B32B 27/30 (2013.01); B32B 27/302 (2013.01); B32B 2250/02 (2013.01); B32B 2250/24 (2013.01); B32B 2274/00 (2013.01); B32B 2307/30 (2013.01); B32B 2307/308 (2013.01); B32B 2307/702 (2013.01); B32B 2307/732 (2013.01); B32B 2333/12 (2013.01); B32B 2367/00 (2013.01); B32B 2451/00 (2013.01); B32B 2457/20 (2013.01); C08L 25/14 (2013.01); C08L 33/06 (2013.01); C08L 33/10 (2013.01); C08L 33/12 (2013.01); C08L 67/00 (2013.01); Y10T 428/31786 (2015.04); Y10T 428/31797 (2015.04)] 12 Claims
 
1. A thermoplastic resin laminate, which comprises a first layer mainly composed of an amorphous polyester resin (A) and a second layer mainly composed of a (meth)acrylic resin (B), the second layer being placed on the first layer; wherein
the content of the amorphous polyester resin (A) in the first layer is 80% by weight or more relative to the total weight of the first layer;
the content of the (meth)acrylic resin (B) in the second layer is 70% by weight or more relative to the total weight of the second layer;
the amorphous polyester resin (A) has a glass transition temperature of 110 to 135° C. and a weight average molecular weight of 30,000 to 50,000 and comprises a unit derived from 2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO) ata ratio of 25 to 40 mol % and a unit derived from 1,4-cyclohexanedimethanol (CHDM) at a ratio of 60 to 75 mol % relative to all diol units constituting the amorphous polyester resin (A) (100 mol %),
the (meth)acrylic resin (B) has a glass transition temperature of 110 to 135° C. and a weight average molecular weight of 100,000 to 150,000;
the absolute value of the difference between the glass transition temperature of the amorphous polyester resin (A) and the glass transition temperature of the (meth)acrylic resin (B) is 10° C. or less;
the (meth)acrylic resin (B) comprises:
a (meth)acrylic acid ester structural unit (a) represented by formula (1) below:

OG Complex Work Unit Chemistry
where R1 represents a hydrogen atom or a methyl group, and R2 represents a C1-C16 hydrocarbon group,
an aliphatic vinyl structural unit (b) represented by formula (2) below:

OG Complex Work Unit Chemistry
where R3 represents a hydrogen atom or a methyl group, and R4 is selected from among a cyclohexyl group, a cyclohexadiene group and a cyclohexene group, which are optionally substituted with a C1-C4 hydrocarbon group, and
optionally an aromatic vinyl structural unit (b′) represented by formula (3) below:

OG Complex Work Unit Chemistry
where R5 represents a hydrogen atom or a methyl group, and R6 represents a phenyl group which is optionally substituted with a C1-C4 hydrocarbon group;
the ratio of the sum of the (meth)acrylic acid ester structural unit (a), the aliphatic vinyl structural unit (b) and the aromatic vinyl structural unit (b′) is 90 to 100 mol % relative to the sum of all the structural units in the (meth)acrylic resin (B); and
the ratio of the (meth)acrylic acid ester structural unit (a) is 55 mol % to 85 mol % relative to the sum of the (meth)acrylic acid ester structural unit (a), the aliphatic vinyl structural unit (b) and the aromatic vinyl structural unit (b′).