Thermoplastic polymer composition, sheet or film, and multi-layered film

Patent metadata

Field	Value
Publication number	US-9567459-B2
Application number	US-201414765893-A
Country	US
Kind code	B2
Filing date	Mar 4, 2014
Priority date	Mar 7, 2013
Publication date	Feb 14, 2017
Grant date	Feb 14, 2017

Abstract

Provided are a thermoplastic polymer composition having good mold processability, flexibility, rubber elasticity, scratch resistance, abrasion resistance, transparency, ease of coating, and mechanical properties when formed into a sheet or film, a sheet or film produced using the thermoplastic polymer composition, and a multi-layered film. The thermoplastic polymer composition includes (I) a block copolymer having a number average molecular weight of 30,000 to 200,000, or a hydrogenated product thereof, which has a polymer block (A) mainly composed of α-methylstyrene units and a polymer block (B) mainly composed of conjugated diene compound units or isobutylene units, (II) an acryl-based polymer, and (III) a softening agent at a ratio satisfying the formulae (1) and (2) as described in claim 1 , and has a sea-island structure in which the components (II) are dispersed in the form of particles in a continuous phase including the component (I), in which the average dispersed particle diameter of the dispersed particles of the components (II) is 200 nm or less, and 35% by mass or more of the dispersed particles have dispersed particle diameters of less than 60 nm.

First claim

The invention claimed is:

1. A thermoplastic polymer composition, comprising:
(I) a block copolymer having a number average molecular weight of 30,000 to 200,000, or a hydrogenated product thereof;
(II) an acryl-based polymer; and
(III) a softening agent;
wherein:
the block copolymer comprises a polymer block (A) and a polymer block (B);
the polymer block (A) comprises a-methylstyrene units in an amount of 50% by mass or more based on a total mass of the polymer block (A);
the polymer block (B) comprises conjugated diene compound units or isobutylene units in an amount of 50% by mass or more based on a total mass of the polymer block (B);
component (I), component (II), and component (III) are present in a ratio satisfying formulae (1) and (2):
0.05≦ W ( II )/ W ( I )≦2  (1)

0≦ W ( III )/( W ( I )+ W ( II )+ W ( III ))≦0.5  (2)

where W(I), W(II), and W(III) represent a content by mass of component (I), component (II), and component respectively, in the thermoplastic polymer composition;
the thermoplastic polymer composition has a sea-island structure in which component (II) is dispersed in the form of particles in a continuous phase including component (I);
an average dispersed particle diameter of the dispersed particles of component (II) is 200 nm or less; and
35% or more of the dispersed particles of component (II) have a dispersed particle diameter of 40 nm or more and less than 60 nm.

2. The thermoplastic polymer composition according to claim 1 , wherein a haze value measured in accordance with JIS K 7105, using a specimen of the thermoplastic polymer composition having a thickness of 200 μm, is 1.4 or less.

3. The thermoplastic polymer composition according to claim 1 , wherein, when a needle having a diameter of 1 mm and a tip radius of 0.5 mm is thrust into a specimen of the thermoplastic polymer composition molded to have a thickness of 200 μm at a speed of 50 mm/min in accordance with JIS Z 1707, a thrust strength at a time of needle penetration is 19 N or more.

4. The thermoplastic polymer composition according to claim 1 , wherein, in component (I):
a number average molecular weight of the polymer block (A) is 2,000 to 20,000;
the polymer block (B) comprises a block (b1) and a block (b2);
the block (b1) has a content of 1,4-bond structural units of the conjugated diene compound units of less than 30% by mole;
the block (b2) has a number average molecular weight of 3,500 to 65,000; and
the block (b2) has a content of 1,4-bond structural units of the conjugated diene compound units of 30% by mole or more.

5. The thermoplastic polymer composition according to claim 1 , wherein a specific gravity of thermoplastic polymer composition, measured by an immersion method in accordance with ISO 1183, is 0.9 g/cm 3 to 1.08 g/cm 3 .

6. The thermoplastic polymer composition according to claim 1 , wherein 40% to 60% of the dispersed particles of component (II) have a dispersed particle diameter of 40 nm or more and less than 60 nm.

7. A sheet or film produced using the thermoplastic polymer composition according to claim 1 .

8. The sheet or film according to claim 7 , wherein the haze value measured using a specimen having a thickness of 200 μm in accordance with HS K 7105 is 1.4 or less, and
when a needle having a diameter of 1 mm and a tip radius of 0.5 mm is thrust into a specimen having a thickness of 200 μm at a speed of 50 mm/min, the thrust strength at a time of needle penetration is 19 N or more in accordance with JIS Z 1707.

9. A multi-layered film comprising a layer containing the thermoplastic polymer composition according to claim 1 .

10. A method for producing the sheet or film according to claim 7 , comprising a step of performing molding by using a film molding device including a static mixer.

11. The thermoplastic polymer composition according to claim 1 , wherein component (I) comprises a (poly(α-methyl styrene)-polybutadiene-poly(a-methylstyrene) triblock copolymer, or a hydrogenated product thereof.

12. The thermoplastic polymer composition according to claim 4 , wherein component (I) comprises a (poly(α-methyl styrene)-polybutadiene-poly(a-methylstyrene) triblock copolymer having the structure A-b1-b2-X-b2-b1-A where X is a residue of a coupling agent, or a hydrogenated product thereof.

13. The thermoplastic polymer composition according to claim 1 , wherein component (II) comprises polymethyl methacrylate.

14. The thermoplastic polymer composition according to claim 1 , wherein component (II) comprises polymethyl methacrylate and at least one of an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, and an ethylene-butyl acrylate copolymer.

15. The thermoplastic polymer composition according to claim 1 , wherein component (II) comprises polymethyl methacrylate and an ethylene-methyl acrylate copolymer.

16. The thermoplastic polymer composition according to claim 1 , wherein component (III) comprises at least one of a paraffin-based oil and an ethylene-α-olefin copolymerization oligomer.

17. The thermoplastic polymer composition according to claim 1 , wherein component (III) comprises a paraffin-based oil.

18. The thermoplastic polymer composition according to claim 4 , wherein:
component (I) comprises a (poly(α-methyl styrene)-polybutadiene-poly(α-methylstyrene) triblock copolymer having the structure A-b1-b2-X-b2-b1-A where X is a residue of a coupling agent, or a hydrogenated product thereof;
component (II) comprises polymethyl methacrylate; and
component (III) comprises a paraffin-based oil.

19. The thermoplastic polymer composition according to claim 1 , wherein:
0.6≦ W ( II )/ W ( I )≦1.3.

20. The thermoplastic polymer composition according to claim 1 , wherein:
0.03≦ W ( III )/( W ( I )+ W ( II )+ W ( III ))≦0.3.

Assignees

• Kuraray Co

Inventors

• Akahori Yosuke
• Konishi Daisuke
• Nakata Hiromichi

Classifications

• C08J2425/10

  with conjugated dienes · CPC title

• B32B27/20

  using fillers, pigments, thixotroping agents · CPC title

• B32B2307/554

  Wear resistance · CPC title

• B32B2307/412

  Transparent · CPC title

• C08K5/0016

  Plasticisers · CPC title