Multilayer structure polymer and resin composition together with acrylic resin film material, acrylic resin laminate film, photocurable acrylic resin film or sheet, laminate film or sheet and laminate molding obtained by laminating thereof

• US 20060110617A1
• Filed: 12/26/2003
• Published: 05/25/2006
• Est. Priority Date: 01/10/2003
• Status: Active Grant

• Current Assignee: Mitsubishi Chemical Corporation (Mitsubishi Chemical Group Corp.)
• Original Assignee: Mitsubishi Rayon Company Limited (Mitsubishi Chemical Holdings Corporation)
• Inventors: Abe, Junichi, Abe, Yoshinori, Fujii, Hideyuki, Kitaike, Yukio, Kitashima, Koichiro, Okazaki, Shogo
• Granted Patent: US 7,781,062 B2
• Time in Patent Office: Days
• US Class Current: 428/522
• CPC Class Codes: B29C 45/14811 Multilayered articles B29C45/14827 takes precedence
• CPC Class Codes: B29K 2633/08 Polymers of acrylic acid esters, e.g. PMA, i.e. polymethylacrylate
• CPC Class Codes: B29L 2031/3005 Body finishings
• CPC Class Codes: B29L 2031/3044 Bumpers
• CPC Class Codes: B29L 2031/3047 Steering wheels
• CPC Class Codes: B32B 2605/003 Interior finishings
• CPC Class Codes: B32B 27/08 of synthetic resin
• CPC Class Codes: B32B 27/18 characterised by the use of special additives
• CPC Class Codes: B32B 27/30 comprising vinyl (co)polymers; comprising acrylic (co)polymers
• CPC Class Codes: B32B 27/308 comprising acrylic (co)polymers
• CPC Class Codes: C08F 265/06 Polymerisation of acrylate or methacrylate esters on to polymers thereof
• CPC Class Codes: C08F 285/00 Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
• CPC Class Codes: C08J 2333/06 of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
• CPC Class Codes: C08J 5/18 Manufacture of films or sheets
• CPC Class Codes: Y10T 428/254 Polymeric or resinous material
• CPC Class Codes: Y10T 428/2998 including synthetic resin or polymer
• CPC Class Codes: Y10T 428/3154 Of fluorinated addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31544 Addition polymer is perhalogenated
• CPC Class Codes: Y10T 428/31928 Ester, halide or nitrile of addition polymer
• CPC Class Codes: Y10T 428/31935 Ester, halide or nitrile of addition polymer

Abstract

An acrylic resin film material comprising at least a multilayer structure polymer with a particular structure prevent a molded item from being whitened during insert- or in-mold molding and meet the requirement for surface hardness, heat resistance, and transparency or matting performance for vehicle applications. It is also possible to use an acrylic resin film material exhibiting a difference of 30% or less between haze values as determined in accordance with the testing method of JIS K7136 (haze measurement method) after and before a tensile test where a test piece with a width of 20 mm is pulled under the conditions of an initial inter-chuck distance of 25 mm, a rate of 50 mm/min and a temperature of 23° C. until an end-point inter-chuck distance becomes 33 mm as well as having a pencil hardness of 2 B or higher as determined in accordance with JIS K5400.

Claims

1. :

A multilayer structure polymer (I) comprising

(1) an innermost layer polymer (I-A),

(2) an intermediate layer polymer (I-B) with a glass-transition temperature of 25 to 100°

C. comprising a composition different from that of the innermost layer polymer (I-A), and

(3) an outermost layer polymer (I-C), wherein the innermost layer polymer comprises

(I-A1) an alkyl acrylate in 50 to 99.9 wt %,

(I-A2) an alkyl methacrylate in 0 to 49.9 wt %,

(I-A3) another monomer fog comprising a copolymerizable double bond in 0 to 20 wt %,

(I-A4) a multifunctional monomer in 0 to 10 wt %, and

(I-A5) a graft crosslinker in 0.1 to 10 wt %;

wherein the intermediate layer polymer (I-B) comprises

(I-B1) an alkyl acrylate in 9.9 to 90 wt %,

(I-B2) an alkyl methacrylate in 9.9 to 90 wt %,

(I-B3) another monomer comprising a copolymerizable double bond in 0 to 20 wt %,

(I-B4) a multifunctional monomer in 0 to 10 wt %, and

(I-B5) a graft crosslinker 0.1 to 10 wt %; and

wherein the outermost layer polymer (I-C) comprises

(I-C1) an alkyl methacrylate in 80 to 100 wt %,

(I-C2) an alkyl acrylate in 0 to 20 wt %, and

(I-C3) another monomer comprising a copolymerizable double bond in 0 to 20 wt %.

2. :

A resin composition (III) comprising

the multilayer structure polymer (I) as claimed in claim 1 and a thermoplastic polymer (II) comprising an alkyl methacrylate.

3. :

An acrylic resin film material (A) comprising the multilayer structure polymer (I) as claimed in claim.

4. :

The acrylic resin film material (A) of claim 3, further comprising a thermoplastic polymer (II) comprising an alkyl methacrylate.

5. :

The acrylic resin film material (A) as claimed in claim 3, further comprising a matting agent.

6. :

The acrylic resin film material (A) as claimed in claim 3, wherein at least one side has a 60°

surface glossiness of 100% or less.

7. :

The acrylic resin film material (A) as claimed in claim 3, wherein a heat distortion temperature as determined in accordance with ASTM D648 is 80°

C. or higher.

8. :

The acrylic resin film material (A) as claimed in claim 3, further comprising at least one decorative layer in at least one side.

9. :

An acrylic resin laminate film comprising the acrylic resin film material (A) as claimed in claim 3 and another acrylic resin film material (A′

).

11. :

A photocurable acrylic resin film or sheet comprising

the acrylic resin film material (A) as claimed in claim 3 and

a photocurable resin composition (Z) layer comprising

a thermoplastic resin comprising

a radical polymerizable unsaturated side chain group (z-1) and a photoinitiator (z-2).

13. :

A laminate film or sheet comprising of the acrylic resin film material (A) as claimed in claim 3, and a thermoplastic resin layer (C).

16. :

A laminate molded item comprising the acrylic resin film material (A) as claimed in claim 3 laminated on a base E.

17. :

The laminate molded item as claimed in claim 16 prepared by vacuum- or press molding the acrylic resin film material (A) in an injection mold, and then injection-molding a resin to be the base (E) in the injection mold.

18. :

The laminate molded item as claimed in claim 16 prepared by vacuum- or press molding the acrylic resin film material (A), and then placing the molding in an injection mold, and injection-molding a resin to be the base (E) in the injection mold.

19. :

An acrylic resin laminate film comprising the acrylic resin film material (A) as claimed in claim 3 and another fluororesin film material (A″

).

31. :

A process for preparing the laminate molded item of claim 16 comprising

vacuum- or press molding the multilayer structure polymer (I), and

injection-molding the vacuum- or press molded multilayer structure to form the laminate molded item.

32. :

The laminated molded item as claimed in claim 16 prepared by vacuum- or press molding the acrylic resin film material (A), and then placing the molding in an injection mold, and injection-molding a resin to be the base (E) in the injection mold.

10. (canceled)

12. (canceled)

14-15. -15. (canceled)

20. :

An acrylic resin film material (A) exhibiting a difference of 30% or less between haze values as determined in accordance with the testing method of JIS K7136 (haze measurement method) after and before a tensile test where a test piece with a width of 20 mm is pulled under the conditions of an initial inter-chuck distance of 25 mm, a rate of 50 mm/min and a temperature of 23°

C. until an end-point inter-chuck distance becomes 33 mm as well as having a pencil hardness of 2 B or higher as determined in accordance with JIS K5400.

21. :

The acrylic resin film material (A) as claimed in claim 20, wherein at least one side has a 600 surface glossiness of 100% or less.

22. :

The acrylic resin film material (A) as claimed in claim 20, wherein a heat-distortion point as determined in accordance with ASTM D648 is 80°

C. or higher.

23. :

The acrylic resin film material (A) as claimed in claim 20, further comprising at least one decorative layer.

24. :

An acrylic resin laminate film comprising the acrylic resin film material (A) of claim 20 and another acrylic resin material (A′

).

25. :

An acrylic resin laminate film comprising the acrylic resin film material (A) of claim 20 and a fluororesin film material (A″

).

26. :

A photocurable acrylic resin film or sheet comprising the acrylic resin film material (A) of claim 20 and a photocurable resin composition (Z) layer comprising a thermoplastic resin comprising a radical polymerizable unsaturated side chain group (z-l) and a photoinitiator (z-2).

27. :

A laminate film or sheet comprising the acrylic resin film material (A) of claim 20 and a thermoplastic resin layer (C).

28. :

A laminate molded item comprising the acrylic resin film material (A) of claim 20 laminated on a base (E).

29. :

A method for preparing the laminate molded item of claim 28 comprising;

vacuum or press molding the acrylic resin film material (A) and

injection-molding the vacuum or press molded acrylic resin film material (A) and a resin to form the laminate molded item.

30. :

The laminate molded item as claimed in claim 28 prepared by vacuum- or press molding the acrylic resin film material (A) in an injection mold, and then injection-molding a resin to be the base (E) in the injection mold.

33. :

The laminate molded item as claimed in claim 28 prepared by vacuum- or press molding the acrylic resin film material (A), and then placing the molding in an injection mold, and injection-molding a resin to be the base (E) in the injection mold.