LAMINATE FILM, MOLDED LAMINATE, AND METHOD FOR PRODUCING SAME

Abstract

Provided is a laminate film that exhibits an excellent appearance, chemical resistance, and weather resistance, and suppresses yellowing even after long-term heating. The laminate film is formed from a surface layer including a vinylidene fluoride resin (F) and an acrylic resin composition (Y) layer, the acrylic resin composition (Y) containing a hindered amine light stabilizer having a molecular weight of 1400 or more. Further provided is a molded laminate including a base material and the laminate film laminated to the base material. Further provided is a method for producing a molded laminate including a step for producing a preform body by vacuum forming or pressure forming the laminate film in a first die, and a step for integrating the preform body and the base material by injection molding the resin that is to be the base material in a second die.

Claims

1. A laminate film comprising: a surface layer comprising a vinylidene fluoride-based resin (F), and a layer comprising an acrylic resin composition (Y), wherein the acrylic resin composition (Y) comprises a hindered amine-based light stabilizer having a molecular weight of 1400 or more.

2. The laminate film according to claim 1, wherein the surface layer further comprises an acrylic resin (A.sub.F).

3. The laminate film according to claim 1, wherein: the surface layer further comprises an acrylic resin (A.sub.F), the vinylidene fluoride-based resin (F) is present in the surface layer in an amount of 62% by mass or more, based on a total mass of the vinylidene fluoride-based resin (F) and the acrylic resin (A.sub.F) in the surface layer and the acrylic resin (A.sub.F) is present in the surface layer in an amount of 38% by mass or less, based on the total mass of the vinylidene fluoride-based resin (F) and the acrylic resin (A.sub.F) in the surface layer.

4. The laminate film according to claim 1, wherein: the surface layer further comprises an acrylic resin (A.sub.F), the vinylidene fluoride-based resin (F) is present in the surface layer in an amount of 62% to 78% by mass, based on a total mass of the vinylidene fluoride-based resin (F) and the acrylic resin (A.sub.F) in the surface layer, and the acrylic resin (A.sub.F) is present in the surface layer in an amount of 22% to 38% by mass, based on a total mass of the vinylidene fluoride-based resin (F) and the acrylic resin (A.sub.F) in the surface layer.

5. The laminate film according to claim 1, wherein the hindered amine-based light stabilizer is present in the acrylic resin composition (Y) in an amount of 0.1 to 5 parts by mass relative to 100 parts by mass of a resin component in the acrylic resin composition (Y).

6. The laminate film according to claim 1, wherein the molecular weight of the hindered amine-based light stabilizer is 2000 or more.

7. The laminate film according to claim 1, wherein the molecular weight of the hindered amine-based light stabilizer is 2400 or more.

8. The laminate film according to claim 1, wherein a 10% mass reduction temperature of the hindered amine-based light stabilizer is 380° C. or higher based on thermogravimetric analysis.

9. The laminate film according to claim 1, wherein the hindered amine-based light stabilizer has, in its molecular structure, a piperidine skeleton and an amino group other than the piperidine skeleton.

10. The laminate film according to claim 9, wherein the amino group is an amino group derived from a tertiary amine.

11. The laminate film according to claim 1, wherein the hindered amine-based light stabilizer is a copolymer of a reactive hindered amine-based light stabilizer.

12. The laminate film according to claim 1, wherein the acrylic resin composition (Y) further comprises a hindered amine-based light stabilizer having a molecular weight of less than 1400, in an amount of 1 part by mass or less relative to 100 parts by mass of a resin component in the acrylic resin composition (Y).

13. The laminate film according to claim 1, wherein the surface layer further comprises a hindered amine-based light stabilizer, in an amount of 0.1 part by mass or less relative to 100 parts by mass of a resin component in the surface layer.

14. A molded laminate comprising: a base, and the laminate film according to claim 1, laminated on the base.

15. A method for producing a molded laminate, comprising: producing a preliminary molded article by vacuum molding or pressure molding the laminate film according to claim 1 in a first die; and integrating the preliminary molded article and a base by injection molding a resin that is to be the base in a second die.

16. A laminate film comprising: a surface layer comprising a vinylidene fluoride-based resin (F), and a layer comprising an acrylic resin composition (Y), wherein: an increase in an amount of yellowness (ΔYI) after heating for 500 hours in an atmosphere with a temperature of 100° C. is 3.0 or less when compared to before heating, and a light transmittance T.sub.1080 at a wavelength of 323 nm after having exposure to an integrated light amount of 1080 MJ/m.sup.2 by using an ultra accelerated weathering tester is 20% or less.

Description

EXAMPLES

[0195] The invention is further explained in view of the following Examples and Comparative Examples. Before those examples, each preparation example and various evaluation methods of a polymer blend of the rubber-containing polymer (G.sub.Y), the acrylic resin composition (Y), the vinylidene fluoride-based resin (F), and the acrylic resin (A.sub.F) are explained. Incidentally, in Examples and Comparative Examples, and Table 1, the description “parts” means “parts by mass”, unless specifically described otherwise.

Preparation Examples 1 to 4

Preparation Example 1

Preparation of the Rubber-Containing Polymer (G.SUB.Y.-1)

[0196] After adding 10.8 parts of deionized water to a vessel equipped with a stirrer, the monomer mixture (c-1) consisting of 0.3 part of MMA (methyl methacrylate), 4.5 parts of n-BA (n-butyl acrylate), 0.2 part of BDMA (1,3-butylene glycol dimethacrylate), and 0.05 part of AMA (allyl methacrylate) and 0.025 part of CHP (cumene hydroperoxide) were added followed by mixing under stirring at room temperature. Subsequently, under stirring, 1.3 parts of an emulsifying agent (trade name “PHOSPHANOL RS610NA”, manufactured by TOHO Chemical Industry Co., Ltd.) was added to the vessel, and by continuing the stirring for 20 minutes, an emulsion was prepared. Incidentally, the polymer obtained by polymerizing the above monomer mixture (c-1) only has Tg of −48° C.

[0197] Next, to a vessel equipped with a condenser, 139.2 parts of deionized water was added, and the liquid temperature was raised to 75° C. Furthermore, a mixture prepared by adding 0.20 part of sodium formaldehyde sulfoxylate, 0.0001 part of ferrous sulfate, and 0.0003 part of EDTA (ethylene diamine tetraacetic acid) to 5 parts of deionized water was added all at once to the above polymerization vessel. Subsequently, under stirring the liquid in the reaction vessel under nitrogen atmosphere, the above emulsion was added dropwise over 8 minutes to the polymerization vessel, and the reaction was allowed to occur for 15 minutes to complete the first-stage polymerization of the monomer mixture (c).

[0198] Subsequently, the monomer mixture (c-2) consisting of 9.6 parts of MMA, 14.4 parts of n-BA, 1.0 part of BDMA 1.0 part, and 0.25 part of AMA 0.25 was added dropwise over 90 minutes to the polymerization vessel together with 0.016 part of CHP. The reaction was allowed to occur for 60 minutes to complete the second-stage polymerization of the monomer mixture (c). Accordingly, the polymer (P1-1) was obtained. Incidentally, the polymer obtained by polymerizing the above monomer mixture (c-2) only has Tg of −10° C.

[0199] Subsequently, the monomer mixture (i-1) consisting of 6 parts of MMA, 4 parts of MA (methyl acrylate), and 0.075 part of AMA was added dropwise to the above polymerization vessel over 45 minutes together with 0.0125 part of CHP. The reaction was allowed to occur for 60 minutes. Accordingly, the polymer (P2-1) was obtained. Incidentally, the polymer obtained by polymerizing the above monomer mixture (i-1) only has Tg of 60° C.

[0200] Subsequently, the monomer mixture (g-1) consisting of 57 parts of MMA, 3 parts of MA, and 0.264 part of n-OM (n-octyl mercaptan) was added dropwise to the above polymerization vessel over 140 minutes together with 0.075 part of t-BH (tertiary butyl hydroperoxide). The reaction was allowed to occur for 60 minutes. Accordingly, the monomer mixture (g-1) was graft-polymerized to the above polymer to obtain a latex of the rubber-containing polymer (G.sub.Y-1). Incidentally, the polymer obtained by polymerizing the above monomer mixture (g-1) only has Tg of 99° C.

[0201] The obtained latex of the rubber-containing polymer (G.sub.Y-1) was filtered by using a vibration type filtering device equipped with a mesh (average pore size: 62μm) made of SUS (stainless steel) as a filtering material. Subsequently, the filtrate was precipitated in an aqueous solution containing 3.5 parts of calcium acetate followed by washing and collecting. The collected hydrous product was dried to obtain the rubber-containing polymer (G.sub.Y-1) in powder form. Gel content ratio of the rubber-containing polymer (G.sub.Y-1) was 70% by mass, and the mass average particle diameter was 0.11 μm.

Preparation Example 2

Preparation of the Acrylic Resin Composition (Y-1)

[0202] 75 parts of the rubber-containing polymer (G.sub.Y-1), 25 parts of MMA/MA copolymer (MMA/MA=99/1 (mass ratio), mass average molecular weight of Mw: 100,000, Tg glass transition temperature: 105° C., reduction viscosity: 0.059 L/g) as the thermoplastic polymer (B.sub.Y), 1.4 parts of a ultraviolet absorbing agent (manufactured by BASF Japan, trade name “TINUVIN 234”), 0.3 part of a hindered amine-based light stabilizer (manufactured by BASF Japan, trade name “CHIMASSORB 2020 FDL”, molecular weight of 2600 to 3400), and 0.1 part of a phenol-based anti-oxidant (manufactured by BASF Japan, trade name “IRGANOX 1076”) were admixed with one another by using a Henschel mixer. The obtained mixture was supplied to a bent type twin screw extruder (manufactured by TOSHIBA MACHINE CO LTD., trade name “TEM-35B”) which has been heated to 200 to 240° C. followed by kneading to obtain pellets of the acrylic resin composition (Y-1). Gel content ratio of the acrylic resin composition (Y-1) was 55% by mass.

Preparation Example 3

Preparation of Raw Material for Surface Layer

[0203] 68 parts of “KF Polymer T#850” (trade name, ratio of heterogeneous bond: 8.3%, crystal melting point of 173° C.) manufactured by KUREHA CORPORATION as the vinylidene fluoride-based resin (F), 32 parts of MMA/MA copolymer (MMA/MA=99/1 (mass ratio), mass average molecular weight of Mw: 100,000, Tg glass transition temperature: 105° C.) as the acrylic resin (A.sub.F), and 0.1 part of “ADEKASTAB AO-60” (trade name, manufactured by ADEKA CORPORATION) as an anti-oxidant were admixed with one another by using a Henschel mixer. The obtained mixture was supplied to a bent type twin screw extruder (manufactured by TOSHIBA MACHINE CO., LTD., trade name “TEM-35B”) which has been heated to 180 to 220° C. followed by kneading to obtain pellets of a raw material for surface layer (i.e., resin composition for forming a surface layer).

Preparation Example 4

Preparation of Reactive HALS Copolymer

[0204] To a polymerization vessel equipped with a condenser, a mixture containing 92 parts of MMA, 3 parts of MA, 5 parts of ADEKASTAB LA-82, 0.4 part of n-OM, 0.12 part of AMBN (2,2′-azobis (2-methylbutyronitrile)), 0.02 part of MMA/methacrylate salt/methacrylic acid ethyl sulfonate salt copolymer (mass composition ratio=30/10/69), 0.01 part of sodium sulfate, and 127 parts of deionized water was added. The atmosphere inside the polymerization vessel was sufficiently substituted with nitrogen gas, and after that the liquid inside the polymerization vessel was heated to 75° C. under stirring, the polymerization reaction was allowed to occur under nitrogen gas atmosphere. 2 hours later, the liquid inside the polymerization vessel was heated to 95° C., and by maintaining it for 60 minutes, the polymerization was completed. The obtained polymer beads were dehydrated and dried to obtain a reactive HALS copolymer which has mass average molecular weight of 16100.

[0205] <Evaluation Method>

[0206] Methods for evaluating the yellowness, weather resistance, appearance, and chemical resistance of a laminate film are as described below.

[0207] (1) Yellowness of Laminate Film

[0208] For the laminate film, yellowness YI.sub.0 was measured according to the method described in JIS K7105, 6. 3 by using a spectrophotometric colorimeter (manufactured by NIHON DENKI KOGYO Co., Ltd., trade name: SE2000). Furthermore, for the laminate film which has been kept for 500 hours in an atmosphere with temperature of 100° C., yellowness YI.sub.500 was also measured in the same manner as above.

[0209] (2) Weather Resistance of Laminate Film

[0210] The laminate film was measured, as a UV cutting property, for the light transmittance T.sub.0 (%) at wavelength of 323 nm using a UV-Visible—near IR spectrophotometer (manufactured by JASCO Corporation, model V-630). Furthermore, the laminate film was exposed to light till to have integrated light amount of 1080 MJ/m.sup.2 by using an ultra accelerated weathering tester (manufactured by Iwasaki Electric Co., Ltd., product name: SUV-F1), and the light transmittance T.sub.1080 (%) was measured for the laminate film in the same manner as above.

[0211] (3) Appearance of Laminate Film

[0212] Appearance of the laminate film was observed with a naked eye, and 4-step evaluation was made based on the following criteria. [0213] ++: Thermally degraded product and bleed out were not observed. [0214] +: Only the bleed out was observed. [0215] −: Only the thermally degraded product was observed. [0216] −−: Both the thermally degraded product and bleed out were observed.

[0217] (4) Chemical Resistance of Laminate Film

[0218] On top of a laminate film, an aqueous solution of lactic acid with concentration of 10% by mass was added dropwise. After allowing it to stand for 24 hours at a temperature of 80° C., the appearance of the laminate film was observed with a naked eye, and the chemical resistance of the laminate film was evaluated according to the following criteria. [0219] +: Dissolution and swelling were not observed. [0220] −: One or both of dissolution and welling was observed.

[0221] (5) Sticking to roll during production of laminate film

[0222] Compared to the production of a laminate film in which the layer (Y) contains no hindered amine-based light stabilizer in Comparative Example 2, the state of sticking to a roll was evaluated. [0223] +: Sticking to roll was equivalent to the case of Comparative Example 2. [0224] −: Sticking to roll was more significant than Comparative Example 2.

Example 1

[0225] A multi-manifold die was installed on a tip part of a single screw extruder 1 and a single screw extruder 2. The pellets of the acrylic resin composition (Y-1) which have been obtained from Preparation Example 2 were supplied to a single screw extruder 1 which has cylinder temperature of 230 to 240° C. and a cylinder diameter of 40 mm followed by melt plasticization. Furthermore, the pellets for a surface layer which have been obtained from Preparation Example 3 were supplied to a single screw extruder 2 which has cylinder temperature of 200 to 230° C. and a cylinder diameter of 30 mm followed by melt plasticization. In addition, both melt plasticized products were supplied to a multi-manifold die which has been heated to 250° C. to obtain a laminate film. Incidentally, by having the temperature of a cooling roll at 90° C. and preparing the acrylic resin composition (Y-1) to be contact with a cooling roll at that time, a laminate film was obtained. Results of evaluating the yellowness, weather resistance, appearance, and chemical resistance of a laminate film are shown in Table 1. The laminate film has surface layer thickness of 12.5 μm and the acrylic resin composition (Y-1) layer thickness of 112.5 μm.

Examples 2 to 17 and Comparative Examples 1 and 2

[0226] A laminate film was obtained in the same manner as Example 1 except that the composition of a layer including the vinylidene fluoride-based resin (F) and the composition of the layer of the acrylic resin composition (Y) are modified to those described in Table 1 or Table 2. The evaluation results are described in Table 1 or Table 2. Incidentally, conditions for producing the laminate film of Comparative Example 1 are different in that the layer (Y) does not contain a hindered amine-based light stabilizer with molecular weight of 1400 or more, but contains a hindered amine-based light stabilizer with molecular weight of less than 1400. Conditions for producing the laminate film of Comparative Example 2 are different in that the layer (Y) does not contain any hindered amine-based light stabilizer.

Comparative Example 3

[0227] Without using pellets for a surface layer, a single screw extruder 2, and a multi-manifold die, a T die was installed on top of the tip of a single screw extruder 1. Other than that, a monolayer film consisting only of the layer of the acrylic resin composition (Y) was obtained in the same manner as Comparative Example 1. The evaluation results are shown in Table 2.

[0228] [Discussions]

[0229] The laminate film of Comparative Example 1 was insufficient in terms of the yellowness after heating. The laminate film of Comparative Example 2 had high light transmittance at wavelength of 323 nm and an insufficient UV cutting property after the weather resistance test. The monolayer film of Comparative Example 3 has no layer including the vinylidene fluoride-based resin (F), and thus, even in a case in which the acrylic resin composition (Y) includes a hindered amine-based light stabilizer with molecular weight of less than 1400, the chemical resistance was insufficient although coloration derived from de-fluorination reaction of a vinylidene fluoride-based resin did not occur.

TABLE-US-00001 TABLE 1 Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Unit ple 1 ple 2 ple 3 ple 4 ple 5 ple 6 ple 7 ple 8 ple 9 ple 10 Layer Resin (F) KF polymer parts 68 including T#850 (F) Acrylic BR-80 parts 32 resin (A.sub.F) Anti- ADEKASTAB parts 0.1 oxidant AO-60 Layer Rubber-containing parts 75 (Y) polymer (G.sub.y) Thermoplastic parts 25 polymer (B.sub.y) UV TINUVIN 234 parts 1.4 absorbing agent Light CHIMASSORB parts 0.3 0 0 0 0 0 0 0.1 0.2 1 stabilizer 2020 FDL (Molecular weight 2600 to 3400) Uvinul 5050 H parts 0 0.3 0 0 0 0 0 0 0 0 (Molecular weight 3000 to 4000) CYASORB UV- parts 0 0 0.3 0 0 0 0 0 0 0 3346 (Molecular weight 1600 + 10%) CYASORB UV- parts 0 0 0 0.3 0 0 0 0 0 0 3529 (Molecular weight 1700 + 10%) TINUVIN NCR parts 0 0 0 0 0.3 0 0 0 0 0 371 FF (Molecular weight 2800 to 4000) CHIMASSORB parts 0 0 0 0 0 0.3 0 0 0 0 944 FDL (Molecular weight 2000 to 3100) FLAMESTAB parts 0 0 0 0 0 0 0.3 0 0 0 NOR 116 FF (Molecular weight 2261) ADEKASTAB parts 0 0 0 0 0 0 0 0 0 0 LA-57 (Molecular weight 791) Reactive HALS parts 0 0 0 0 0 0 0 0 0 0 copolymer (Molecular weight 16100) Anti- Irganox 1076 parts 0.1 oxidant Yellow- YI.sub.0 — 1.2 1.1 1.3 1.2 1.2 1.5 1.2 1.0 1.1 1.4 ness YI.sub.500 — 1.9 2.2 2.4 2.3 2.3 2.9 3.3 1.4 1.5 2.3 ΔYI = YI.sub.500 − YI.sub.0 — 0.7 1.1 1.1 1.1 1.1 1.4 2.1 0.4 0.4 0.9 Light T.sub.0 % <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 transmit- T.sub.1080 % 0.2 0.4 0.3 0.3 0.5 0.4 0.3 2.3 0.9 0.3 tance Film appearance — ++ +− ++ ++ ++ ++ ++ ++ ++ ++ Chemical resistance — + + + + + + + + + + Sticking to roll — + + − − + + + + + +

TABLE-US-00002 TABLE 2 Com- Com- Ccm- par- par- par- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ative ative ative ple ple ple ple ple ple ple Exam- Exam- Exam- Unit 11 12 13 14 15 16 17 ple 1 ple 2 ple 3 Layer Resin KF polymer parts 68 78 62 68 — includ- (F) T#850 ing Acrylic BR-80 parts 32 22 38 32 — (F) resin (A.sub.F) Anti- ADEKASTAB parts 0.1 — oxidant AO-60 Layer Rubber-containing parts 75 (Y) polymer (G.sub.y) Thermoplastic parts 25 polymer (B.sub.y) UV TINUVIN parts 1.4 absorbing 234 agent Light CHIMASSORB parts 0 0 0 10 0   0.3   0.3 0 0 0 stabilizer 2020 FDL (Molecular weight 2600 to 3400) Uvinul 5050 E parts   0.1   0.2 1 0 0 0 0 0 0 0 (Molecular weight 3000 to 4000) CYASORB parts 0 0 0 0 0 0 0 0 0 0 UV-3346 (Molecular weight 1600 + 10%) CYASORB parts 0 0 0 0 0 0 0 0 0 0 UV-3529 (Molecular weight 1700 + 10%) TINUVIN parts 0 0 0 0 0 0 0 0 0 0 NCR 371 FF (Molecular weight 2800 to 4000) CHIMASSORB parts 0 0 0 0 0 0 0 0 0 0 944 FDL (Molecular weight 2000 to 3100) FLAMESTAB parts 0 0 0 0 0 0 0 0 0 0 NOR 116 FF (Molecular weight 2261) ADEKASTAB parts 0 0 0 0 0 0 0   0.3 0 0.3 LA-57 (Molecular weight 791) Reactive parts 0 0 0 0 0 0 0 0 0 0 HALS copolymer (Molecular weight 16100) Anti- Irganox 1076 parts 0.1 oxidant Yellow- YI.sub.0 — 1.1 1.1 1.4 5.0 1.1 2.2 1.1 1.2 1.1 1.0 ness YI.sub.500 — 1.6 1.8 2.8 6.8 1.9 3.0 1.8 5.0 1.6 1.1 ΔYI = YI.sub.500 YI.sub.0 — 0.5 0.7 1.4 1.8 0.8 0.8 0.7 3.8 0.5 0.1 Light T.sub.0 % <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 transmit- T.sub.1080 % 4.6 2.8 0.3 0.1 1.2 0.2 0.2 0.7 25.3 0.6 tance Film appearance — ++ ++ ++ + ++ ++ ++ ++ ++ ++ Chemical resistance — + + + + + + + + + − Sticking to roll — + + + + + + + + + +