JP2003128809A - Laminate film - Google Patents

Abstract

(57) [Summary] [Problem] To be excellent in weather resistance, moldability, flexibility, impact resistance, dust resistance, transparency, ethanol resistance, boiling water resistance, etc., and at the time of tension or bending (at the time of processing). To provide a laminate film for plastics, wood, metal, etc., which is unlikely to cause cloudiness or change in transparency. SOLUTION: Block (a) 4 of a methacrylic polymer
A block copolymer consisting of 0 to 75% by weight, preferably 45 to 70% by weight, and 60 to 25% by weight, preferably 55 to 30% by weight of the acrylic polymer block (b) is extruded or calendered. Laminated film obtained by molding. The block copolymer is obtained by atom transfer radical polymerization.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to weather resistance, moldability,
Flexibility, impact resistance, dust resistance, transparency, ethanol resistance,
The present invention relates to a laminated film which has excellent boiling water resistance and is less likely to cause cloudiness or a change in transparency during stretching or bending (processing).

[0002]

BACKGROUND OF THE INVENTION Methacrylic acid ester resins are used in various fields because they are particularly excellent in weather resistance and transparency among plastics. For example, they are molded into a sheet or a film, and various plastics, woods, metals, etc. It is widely used by laminating it on materials to prevent deterioration of the base material and to maintain its aesthetic appearance.

In order to improve the film moldability and impact resistance of a film formed from such a methacrylic acid ester resin, a rubber component is usually dispersed in the methacrylic acid ester resin or the graft copolymer itself. A method of using is devised. In particular, as the graft copolymer, it is generally said that a core-shell particle type graft copolymer obtained by graft-polymerizing an outer layer portion called a shell on an inner layer portion called a core is effective. Part), and a method of gradually changing the composition of the polymer other than the graft part (shell part) and the graft copolymer to obtain a gradient polymer (Japanese Patent Publication No. 47-13371). Japanese Patent Publication No. 509022). In addition, the glass transition temperature (Tg) of the core portion (inner layer portion) of the core-shell particle type graft copolymer is set to 1 for the purpose of suppressing cloudiness and change in transparency during deformation.
Techniques for raising the temperature above 0 ° C have also been proposed (Japanese Patent Publication No. 59-3).
6645, Japanese Patent Publication No. 59-36646). However, with these methods, the effect of improving impact resistance is insufficient, and when the film is laminated on a substrate and subjected to secondary processing or embossing, the film itself cracks, becomes cloudy in white, or the transparency decreases. The phenomenon of doing was recognized. Such a phenomenon is particularly remarkable at the time of pulling or bending (processing) at a low temperature. Further, if the amount of a flexible component is increased in order to solve these problems, there is a problem that moldability, transparency, dust resistance and ethanol resistance are impaired.

In recent years, acrylic block copolymers whose molecular weights, molecular weight distributions and structures have been controlled by various controlled polymerizations have been used as film materials or as impact modifiers for thermoplastic resins (Japanese Patent Application No. 2003-242242). Flat 11-2
60428, JP-A-10-179746). However, when these are used by adding them to a thermoplastic resin such as an acrylic resin, the effect of improving the impact resistance is small when added in a small amount, cracking or whitening occurs in the film, and when added in a large amount, mechanical strength is increased. There was a problem that the surface hardness was reduced. Similarly, even if an acrylic block copolymer is used alone as a laminate film material, there is a problem that the surface hardness is too low. If the surface hardness is low, scratches are likely to occur due to contact with objects or handling, and if the surface is embossed, the scratches are relatively inconspicuous, but it is used for smooth surfaces such as inner-layer construction In this case, even a small scratch will significantly impair the commercial value.

The present invention solves the above-mentioned problems of impact resistance and whitening resistance of the prior art, and is excellent in balance of mechanical strength, surface hardness, flexibility, etc. It is an object of the present invention to provide a laminated film which can be suitably and widely used in various fields such as interior / exterior materials, electric products, sundries and the like.

[0006]

The object of the present invention is to provide excellent weather resistance, moldability, flexibility, impact resistance, dust resistance, transparency, ethanol resistance, boiling water resistance, and the like, and when it is pulled or bent. It is to provide a laminated film in which white turbidity and change in transparency do not easily occur at the time of processing (processing).

[0007]

Means for Solving the Problems The present inventors have proposed a laminate film comprising a block copolymer containing a methacrylic polymer block and an acrylic polymer block,
Weather resistance, moldability, flexibility, impact resistance, dust resistance, transparency,
The inventors have found that it is excellent in ethanol resistance, boiling water resistance, and the like, and that white turbidity and change in transparency do not easily occur at the time of pulling or bending (during processing), and completed the present invention.

That is, the present invention comprises molding a block copolymer (A) comprising 40 to 75% by weight of a methacrylic polymer block (a) and 60 to 25% by weight of an acrylic polymer block (b). A laminate film (claim 1), wherein the block copolymer (A) comprises 45 to 70% by weight of a methacrylic polymer block (a) and 55 to 30% by weight of an acrylic polymer block (b). The laminated film according to claim 1 (claim 2), the methacrylic polymer block (a) is 50 to 100% by weight of methyl methacrylate, and another methacrylic acid ester copolymerizable therewith and / or The acrylic polymer block (b) is composed of 0 to 50% by weight of another vinyl monomer, and the acrylic polymer block (b) is 50 to 100% by weight of butyl acrylate and co-polymerized therewith. A laminated film (claim 3) or a block copolymer (A) according to claim 1 or 2, comprising a polymer block composed of 0 to 50% by weight of other possible acrylic acid ester and / or vinyl monomer. Is produced by atom transfer radical polymerization, the laminate film according to claim 1, 2 or 3 (claim 4), wherein the methacrylic polymer block (a) comprises methyl methacrylate, The laminate film (claim 5) according to claim 1, 2, 3 or 4, wherein the polymer block (b) is a polymer block consisting of butyl acrylate, and the block copolymer (A) is a triblock copolymer. Claims 1 and 2 which are united,
The laminated film according to claim 3, 4 or 5 (claim 6) and the thermoplastic resin composition comprising the block copolymer (A) according to claim 1, 2, 3, 4, 5 or 6 and a thermoplastic resin (B). Laminated film formed by molding a material (claim 7)
Regarding

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The block copolymer (A) containing a methacrylic polymer block and an acrylic polymer block which can be used in the present invention is an ab type diblock copolymer, a- b-a type triblock copolymer, b-
It is at least one type of block copolymer selected from an ab type triblock copolymer and an (ab) n type multiblock copolymer. Among these, ab-a type triblock copolymers (ab) from the viewpoints of film formability, impact resistance, flexibility and dust resistance of the formed film.
An n-type multiblock copolymer or a mixture thereof is preferable, and an aba type triblock copolymer is more preferable.

The structure of the block copolymer (A) is a linear block copolymer or a branched (star) block copolymer, and may be a mixture thereof. The structure of such a block copolymer is properly used according to the required properties such as film formability, processing properties and mechanical properties.

The number average molecular weight of the block copolymer (A) is not particularly limited, but is preferably 30,000 to 500,000, and more preferably 50,000 to 400,000. If the number average molecular weight is small, the viscosity is low, and if the number average molecular weight is large, the viscosity tends to be high, and therefore the viscosity is set according to the required processing characteristics. The molecular weight is measured in terms of polystyrene by gel permeation chromatography (GPC) using a polystyrene gel column with chloroform as the mobile phase.

Weight average molecular weight (Mw) and number average molecular weight (Mn) of the block copolymer (A) measured by GPC.
The ratio (Mw / Mn) is also not particularly limited, but is preferably 1.8 or less. When Mw / Mn exceeds 1.8, the homogeneity of the block copolymer is deteriorated, and the impact resistance of the formed film and the whitening resistance during bending or stretching (during processing) tend to be deteriorated.

The methacrylic polymer block (a) constituting the block copolymer (A) comprises 50 to 100% by weight of a methacrylic acid ester and 0 to 50% by weight of a vinyl type monomer copolymerizable therewith. Consists of. Examples of the methacrylic acid ester constituting (a) include methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate. , Methacrylic acid-tert-butyl, methacrylic acid-n-pentyl, methacrylic acid-n-hexyl, methacrylic acid cyclohexyl, methacrylic acid-n-heptyl, methacrylic acid-n-octyl, methacrylic acid- 2-Ethylhexyl, Nonyl Methacrylate, Decyl Methacrylate, Dodecyl Methacrylate, Phenyl Methacrylate, Toluyl Methacrylate, Benzyl Methacrylate, Isobornyl Methacrylate, 2-Methoxyethyl Methacrylate, Methacrylic Acid-3-methoxybutyl, methacrylic acid-2-hi Droxyethyl, 2-hydroxypropyl methacrylate, stearyl methacrylate, glycidyl methacrylate, 2-aminoethyl methacrylate, γ-
(Methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of methacrylic acid, trifluoromethylmethyl methacrylate, methacrylic acid-2-trifluoromethylethyl, methacrylic acid Acid-2-perfluoroethylethyl, methacrylic acid-
2-perfluoroethyl-2-perfluorobutylethyl, methacrylic acid-2-perfluoroethyl, methacrylic acid perfluoromethyl, methacrylic acid diperfluoromethylmethyl, methacrylic acid-2-perfluoromethyl-2 -Perfluoroethylmethyl, methacrylic acid-
2-perfluorohexylethyl, methacrylic acid-2-
Examples thereof include perfluorodecylethyl and methacrylic acid-2-perfluorohexadecylethyl. These may be used alone or in combinations of two or more. Among these, methyl methacrylate is preferable in terms of availability.

Examples of the vinyl monomer copolymerizable with the methacrylic acid ester which constitutes (a) include methyl acrylate, ethyl acrylate, -n-propyl acrylate, isopropyl acrylate, acrylate- n-butyl, isobutyl acrylate, t-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-heptyl acrylate, n-octyl acrylate, acrylate- 2-ethylhexyl,
Nonyl acrylate, decyl acrylate, dodecyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, acrylic acid
-2-methoxyethyl, acrylic acid-3-methoxybutyl,
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, stearyl acrylate, glycidyl acrylate, 2-aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxy Methylsilane, ethylene oxide adduct of acrylic acid, trifluoromethylmethyl acrylate, 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl acrylate, 2-perfluoroethyl-2-perfluorobutyl acrylate Ethyl, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl acrylate, Ak Le acid 2 perfluorodecyl ethyl, acrylate esters such as acrylic acid-2-perfluoroalkyl-hexadecyl ethyl; styrene, alpha-
Aromatic alkenyl compounds such as methylstyrene, p-methylstyrene and p-methoxystyrene; Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile;
Conjugated diene compounds such as butadiene and isoprene; halogen-containing unsaturated compounds such as vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene and vinylidene fluoride; silicon-containing unsaturated compounds such as vinyltrimethoxysilane and vinyltriethoxysilane Compound;
Unsaturated dicarboxylic acid compounds such as maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid, fumaric acid, monoalkyl and dialkyl esters of fumaric acid; vinyl acetate, vinyl propionate, vinyl pivalate, benzoic acid Vinyl ester compounds such as vinyl and vinyl cinnamate; various maleimide compounds such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide and cyclohexylmaleimide. Examples include vinyl monomers. These may be used alone or in combinations of two or more. As these vinyl-based monomers, preferred ones can be selected according to the moldability of the film, the secondary processability of the molded film, and the required mechanical properties.

The glass transition temperature of (a) is 25 ° C. or higher, preferably 40 ° C. or higher, and more preferably 50 ° C. or higher. When the glass transition temperature is lower than 25 ° C, the film moldability and heat resistance tend to be low.

The acrylic polymer block (b) constituting the block copolymer (A) comprises 50 to 100% by weight of an acrylic ester and 0 to 50% by weight of a vinyl monomer copolymerizable therewith. It is preferable that

Examples of the acrylic acid ester constituting (b) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid- t-Butyl, n-pentyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate , Dodecyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, acrylate-2- Hydroxypropyl, stearyl acrylate, glycidyl acrylate , 2-aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of acrylic acid, trifluoromethylmethyl acrylate, acrylic acid-2 -Trifluoromethylethyl, acrylic acid-2-perfluoroethylethyl, acrylic acid-2-perfluoroethyl-2-perfluorobutylethyl, acrylic acid 2-perfluoroethyl, acrylic acid perfluoromethyl, acrylic acid diper Fluoromethylmethyl, acrylate-2-perfluoromethyl-2-perfluoroethylmethyl, acrylate-2-perfluorohexylethyl, acrylate-2-perfluorodecylethyl, acrylate-2-perfluorohexadecylethyl And so on. These may be used alone or in combinations of two or more. Among these, -n-butyl acrylate is preferable in terms of flexibility, whitening resistance and availability of the formed film.

Examples of the vinyl monomer copolymerizable with the acrylic ester which constitutes (b) include methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, N-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-pentyl methacrylate,
Methacrylic acid-n-hexyl, cyclohexylmethacrylate, methacrylic acid-n-heptyl, methacrylic acid
-n-octyl, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, phenyl methacrylate, toluyl methacrylate, benzyl methacrylate, isobornyl methacrylate, methacrylic acid Acid-2-methoxyethyl,
Methacrylic acid-3-methoxybutyl, methacrylic acid-
2-hydroxyethyl, 2-hydroxypropyl methacrylate, stearyl methacrylate, glycidyl methacrylate, 2-aminoethyl methacrylate, γ-
(Methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of methacrylic acid, trifluoromethylmethyl methacrylate, methacrylic acid-2-trifluoromethylethyl, methacrylic acid Acid-2-perfluoroethylethyl, methacrylic acid 2
-Perfluoroethyl-2-perfluorobutylethyl,
Methacrylic acid-2-perfluoroethyl, methacrylic acid perfluoromethyl, methacrylic acid diperfluoromethylmethyl, methacrylic acid-2-perfluoromethyl
-Methacrylic acid ester such as 2-perfluoroethylmethyl, methacrylic acid-2-perfluorohexylethyl, methacrylic acid-2-perfluorodecylethyl, methacrylic acid-2-perfluorohexadecylethyl; styrene, α-methylstyrene, p-methylstyrene, p-
Aromatic alkenyl compounds such as methoxystyrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; conjugated diene compounds such as butadiene and isoprene; vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene, vinylidene fluoride, etc. Halogen-containing unsaturated compounds; Silicon-containing unsaturated compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid, fumaric acid, monoalkyl esters of fumaric acid, and Unsaturated dicarboxylic acid compounds such as dialkyl esters; vinyl acetate,
Vinyl ester compounds such as vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide,
Examples thereof include various vinyl-based monomers such as maleimide-based compounds such as octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide and cyclohexylmaleimide. These may be used alone or in combinations of two or more. As these vinyl monomers, preferred ones can be selected depending on the glass transition temperature required for the block (b). The glass transition temperature of (b) is preferably 25 ° C or lower, more preferably 0 ° C or lower, and further preferably -20 ° C or lower. When the glass transition temperature is higher than 25 ° C, the flexibility and whitening resistance of the formed film or sheet tend to be lowered.

The method for producing the block copolymer (A) is not particularly limited, but controlled polymerization is preferably used. Examples of the controlled polymerization include living anionic polymerization, radical polymerization using a chain transfer agent, and living radical polymerization recently developed, and living radical polymerization is preferable from the viewpoint of controlling the molecular weight and structure of the block copolymer.

Living radical polymerization is a radical polymerization in which the activity at the polymerization end is maintained without loss. In a narrow sense, living polymerization indicates polymerization in which the terminal always has activity, but generally includes pseudo-living polymerization in which the terminal is inactivated and the activated one is in an equilibrium state. . The definition in the present invention is also the latter. Living radical polymerization has been actively studied in various groups in recent years. Examples thereof include those using a chain transfer agent such as polysulfide, cobalt porphyrin complex (J. Am. Chem. Soc. 1994, 1).
16, 7943) or a radical scavenger such as a nitroxide compound (Macromolecules,
1994, 27, 7228), an atom transfer radical polymerization using an organic halide as an initiator and a transition metal complex as a catalyst (Atom Transfer Radical Po
lymerization: ATRP) and the like. In the present invention, which of these methods is used is not particularly limited, but atom transfer radical polymerization is preferable from the viewpoint of easy control.

Atom transfer radical polymerization is carried out by using an organic halide or a sulfonyl halide compound as an initiator and a metal complex having an element of Group 8, 9, 10 or 11 of the periodic table as a central metal as a catalyst. To be done. (For example,
Matyjaszewski et al. Am. Chem.
Soc. 1995, 117, 5614, Macromo
leules 1995, 28, 7901, Scie
nce 1996, 272, 866, or Sawa
moto et al., Macromolecules 1995,
28, 1721). According to these methods, the polymerization generally has a very high polymerization rate, and although the polymerization is a radical polymerization in which a termination reaction such as a coupling between radicals is likely to occur, the polymerization proceeds in a living manner and has a narrow molecular weight distribution Mw / Mn.
= 1.1-1.5, a polymer having a molecular weight of about 1.1 to 1.5 can be obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

In the atom transfer radical polymerization method, as the organic halide or sulfonyl halide compound used as an initiator, a monofunctional, difunctional or polyfunctional compound can be used. These may be used properly according to the purpose, but in the case of producing a diblock copolymer, a monofunctional compound is preferable, and an ab-a type triblock copolymer or a b-a-b type triblock copolymer is preferable. When manufacturing a triblock copolymer, it is preferable to use a bifunctional compound, and when manufacturing a branched block copolymer, it is preferable to use a polyfunctional compound.

Examples of the monofunctional compound include compounds represented by the formulas: C ₆ H ₅ -CH ₂ X, C ₆ H ₅ -C (H) (X) -CH ₃ , C ₆ H.
_5- C (X) (CH ₃ ) ₂ , R ¹ -C (H) (X) -COO
R ² , R ¹ -C (CH ₃ ) (X) -COOR ² , R ¹ -C (H)
(X) -CO-R ² , R ¹ -C (CH ₃ ) (X) -CO-R ² ,
R ¹ -C ₆ H ₄ -SO ₂ X (In the formula, C ₆ H ₄ represents a phenylene group (which may be ortho-substituted, meta-substituted or para-substituted). R ¹ represents a hydrogen atom or a carbon number of 1 to 20. Alkyl group of 6 to 20 carbon atoms
Or an aralkyl group having 7 to 20 carbon atoms. X represents chlorine, bromine, or iodine. R ² represents a monovalent organic group having 1 to 20 carbon atoms. ) And the like.

[0024] As bifunctional compounds, for example, the _{formula: X-CH 2 -C 6 H} 4 -CH 2 -X, X-CH (CH 3) -C 6 H 4 -
_{CH (CH 3) -X, X} -C (CH 3) 2 -C 6 H 4 -C (C
_{H 3) 2 -X, X-} CH (COOR 3) - (CH 2) n -CH
(COOR ³ ) -X, X-C (CH ₃ ) (COOR ³ )-(C
_{H 2) n -C (CH 3} ) (COOR 3) -X, X-CH (CO
_{^{R 3) - (CH 2)}} n -CH (COR 3) -X, X-C (C
^{_{H 3) (COR 3) -}} (CH 2) n -C (CH 3) (COR 3)
_{-X, X-CH 2 -CO-} CH 2 -X, X-CH (CH 3) -CO
_{-CH (CH 3) -X, X} -C (CH 3) 2 -CO-C (C
_{H 3) 2 -X, X-} CH (C 6 H 5) -CO-CH (C 6 H 5) -
_{X, X-CH 2 -COO- (} CH 2) n -OCO-CH 2 -X, X
_{-CH (CH 3) -COO- (CH} 2) n -OCO-CH (CH
_{3) -X, X-C (} CH 3) 2 -COO- (CH 2) n -OCO-
_{C (CH 3) 2 -X,} X-CH 2 -CO-CO-CH 2 -X, X-
CH (CH ₃ ) -CO-CO-CH (CH ₃ ) -X, X-C
_{(CH 3) 2 -CO-CO} -C (CH 3) 2 -X, X-CH 2 -C
_{OO-C 6 H 4 -OCO-} CH 2 -X, X-CH (CH 3) -CO
_{O-C 6 H 4 -OCO-} CH (CH 3) -X, X-C (CH 3) 2
_{-COO-C 6 H 4 -OCO-} C (CH 3) 2 -X, X-SO 2 -C
₆ H ₄ -SO ₂ -X (In the formula, R ³ is an alkyl group having 1 to 20 carbon atoms, and 6 carbon atoms.
~ 20 aryl group or a C7-20 aralkyl group. C ₆ H ₄ represents a phenylene group (which may be ortho-substituted, meta-substituted or para-substituted). C ₆ H ₅ represents a phenyl group. n represents an integer of 0 to 20. X is chlorine,
Represents bromine or iodine. ) And the like.

Examples of the polyfunctional compound include compounds represented by the formulas: C ₆ H _3- (CH ₂ -X) ₃ , C ₆ H _3- (CH (CH ₃ )-
X) ₃ , C ₆ H _3- (C (CH ₃ ) ₂ -X) ₃ , C ₆ H _3- (OC
_{O-CH 2 -X) 3,} C 6 H 3 - (OCO-CH (CH 3) -X)
₃ , C ₆ H _3- (OCO-C (CH ₃ ) ₂ -X) ₃ , C ₆ H _3- (S
O ₂ —X) ₃ (wherein C ₆ H ₃ is a trisubstituted phenyl group (the position of the substituent is 1
It may be any of the 6th to 6th positions). X is chlorine, bromine,
Or represents iodine. ) And the like.

When an organic halide having a functional group other than the one that initiates polymerization or a sulfonyl halide compound is used, a polymer having a functional group introduced at the terminal can be easily obtained. Examples of such a functional group include an alkenyl group, a hydroxyl group, an epoxy group, an amino group, an amide group and a silyl group.

In the organic halide or sulfonyl halide compound which can be used as the initiator, the carbon to which the halogen is bonded is bonded to the carbonyl group or the phenyl group, and the carbon-halogen bond is activated. Polymerization begins. The amount of the initiator used may be determined from the ratio with the monomer in accordance with the required molecular weight of the block copolymer. That is, the molecular weight of the block copolymer can be controlled depending on the number of molecules of the monomer used per one molecule of the initiator.

The transition metal complex used as a catalyst for the atom transfer radical polymerization is not particularly limited, but preferred are monovalent and zero valent copper, divalent ruthenium, divalent iron and divalent nickel. The complex of is mentioned. Among these, a copper complex is more preferable in terms of cost and reaction control.

Examples of the monovalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide,
Examples include cuprous oxide and cuprous perchlorate. When using a copper compound, in order to increase the catalytic activity 2,2'-
Bipyridyl and its derivative, 1,10-phenanthroline and its derivative, polyamine such as tetramethylethylenetriamine (TMEDA), pentamethyldiethylenetriamine, and hexamethyl (2-aminoethyl) amine may be added as a ligand. Also, 2
A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also preferable as the catalyst.
When using a ruthenium compound as a catalyst, you may add aluminum alkoxide as an activator.
Further, divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ) and divalent nickel bistriphenylphosphine complex (NiCl ₂ (PP
h ₃ ) ₂ ) and a bivalent nickel bistributylphosphine complex (NiBr ₂ (PBu ₃ ) ₂ ) are also preferable as the catalyst. The amounts of the catalyst, the ligand and the activator used are not particularly limited, but may be appropriately determined depending on the relationship between the amount of the initiator, the monomer and the solvent used and the required reaction rate.

The atom transfer radical polymerization can be carried out without solvent (bulk polymerization) or in various solvents. Examples of the solvent include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon solvents such as methylene chloride and chloroform; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. Solvents; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol; nitrile solvents such as acetonitrile, propionitrile, benzonitrile; ester solvents such as ethyl acetate, butyl acetate; ethylene Examples thereof include carbonate solvents such as carbonate and propylene carbonate. These may be used alone or in combination of two or more. As described above, when the polymerization is carried out without a solvent, bulk polymerization is performed. On the other hand, when a solvent is used, the amount to be used may be appropriately determined from the relationship between the viscosity of the entire system and the required stirring efficiency (that is, reaction rate).

The polymerization can be carried out at room temperature to 200 ° C., preferably 50 to 150 ° C.

In order to produce a block copolymer by the above-mentioned polymerization, a method of sequentially adding monomers, a method of polymerizing the next block by using a polymer synthesized in advance as a polymer initiator, and a method of polymerizing separately Examples include a method of binding the coalesced product by a reaction. These methods may be selectively used according to the purpose, but from the viewpoint of simplicity of the production process, the method of sequentially adding the monomers is preferable. The composition ratio of the methacrylic polymer block (a) and the acrylic polymer block (b) constituting the block copolymer (A) used in the present invention is such that the block (a) is 40 to 75% by weight, The block (b) is 60 to 25% by weight, the moldability of the film,
From the viewpoint of dust resistance, flexibility, whitening resistance, etc., preferably,
(A) is 45 to 70% by weight, (b) is 55 to 30% by weight
is there. If the proportion of (a) is less than 40% by weight, the moldability, dustproofness, surface hardness, etc. of the film or sheet will tend to decrease, and if the proportion of (b) is less than 25% by weight, the flexibility of the molded film will be improved. Tends to decrease, and the film tends to crack, and the whitening resistance during stretching and bending (processing) tends to decrease.

The methacrylic polymer block (a) constituting the block copolymer (A) used in the present invention
The composition ratio of the acrylic polymer block (b) and the acrylic polymer block (b) can be set according to desired physical properties such as film moldability, secondary processability of the molded film, and required mechanical properties. good. Although the scope of the invention is not limited thereto, for example, the transparency of the laminated film film of the present invention,
When high hardness, dust resistance, ethanol resistance, etc. are required, the methacrylic polymer block (a) is 70 to 7
5% by weight, 30 to 2 of the acrylic polymer block (b)
It is sufficient to use 5% by weight of the film. Especially, when impact resistance and flexibility are required, the methacrylic polymer block (a) is 40 to 45% by weight, and the acrylic polymer block (b) is It is sufficient to use a film of 60 to 55% by weight, which has an excellent balance of moldability, flexibility, impact resistance, dust resistance, transparency, hardness, ethanol resistance, boiling water resistance, etc.
In addition, when a film that is unlikely to be whitened during stretching or bending (processing) is required, the methacrylic polymer block (a) is 45 to 70% by weight and the acrylic polymer block (b) is 55. A film of about 30% by weight may be used. The film containing the methacrylic polymer block (a) in an amount of 45 to 70% by weight and the acrylic polymer block (b) in an amount of 55 to 30% by weight is used as an interior / exterior material for buildings, electric products, miscellaneous goods, It can be suitably used in place of a vinyl chloride sheet which is widely used in various other fields.

The laminate film of the present invention is characterized by containing the block copolymer (A) as an essential component, but may contain other components. When the other component is a thermoplastic resin (B), for example, from the group consisting of polyacrylic resin, polyvinyl chloride resin, polyethylene resin, polypropylene resin, cyclic olefin copolymer resin, aromatic alkenyl compound and vinyl cyanide compound. At least one vinyl-based monomer 70-1 selected
0 to 30% by weight of other vinyl type monomers such as ethylene, propylene and vinyl acetate and / or diene type monomers such as butadiene and isoprene which are copolymerizable with 00% by weight of these vinyl type monomers. Homopolymer or copolymer obtained by polymerizing with, polystyrene resin,
Polyphenylene ether resin, mixture of polystyrene resin and polyphenylene ether resin, polycarbonate resin, polyester resin, mixture of polycarbonate resin and polyester resin, polyamide resin, polyacetal resin, polyphenylene sulfide resin, polysulfone resin, polyimide resin, polyetherimide resin, polyether Ketone resin, polyetheretherketone resin,
Examples thereof include polyamideimide resin and polyarylate resin, which can be used alone or in combination of two or more kinds. In the present invention, the thermoplastic resin is not limited to these, and various thermoplastic resins can be widely used. Among these, acrylic resin such as polymethylmethacrylate, acrylonitrile-styrene copolymer, acrylonitrile, etc., in terms of excellent compatibility with the block copolymer (A) used in the present invention, impact resistance, and mechanical properties. -A resin selected from the group consisting of a butadiene-styrene copolymer, a methylmethacrylate-styrene copolymer, a polycarbonate, a polyester-based resin, and a polyamide-based resin is preferable, and polymethacryl is more excellent in weather resistance and transparency. Acrylic resins such as methyl acid are more preferred.

Examples of the acrylic resin include polymethacrylic acid ester, polyacrylic acid ester, methacrylic acid ester-acrylic acid ester copolymer, methacrylic acid ester-methacrylic acid copolymer, methacrylic acid ester-maleic anhydride copolymer. Examples thereof include polymers, methacrylic acid ester-styrene copolymers, methacrylic acid ester-styrene-substituted maleimide copolymers, methacrylic acid ester-substituted maleimide copolymers, but are not limited thereto. These may be used alone or in combination of two or more. Of these,
It may be selected depending on compatibility with the block copolymer (A) used in the present invention, transparency when combined with the block copolymer (A), and the like, but weather resistance, transparency, mechanical properties, availability A polymethacrylic acid ester and a methacrylic acid ester-acrylic acid ester copolymer are preferable from the viewpoint of properties and easiness of polymerization. From the viewpoint of availability and ease of polymerization, polymethyl methacrylate is preferable as the polymethacrylic acid ester, and as the methacrylic acid ester-acrylic acid ester copolymer, a methacrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms- Acrylic acid alkyl ester copolymers are preferred.

The copolymer of the methacrylic acid alkyl ester-acrylic acid alkyl ester copolymer may be a random copolymer, an alternating copolymer, a comb-shaped graft copolymer containing a branch portion and a trunk portion, an inner layer portion (core portion). And a core-shell particle type graft copolymer containing an outer layer part (shell part) and a methacrylic acid ester containing an acrylic acid ester in a multi-step manner in the presence of an inner layer part (core part) consisting of an acrylic acid ester and a methacrylic acid ester. A copolymer obtained by additional polymerization, a copolymer obtained by additionally polymerizing a monomer mixture consisting of acrylic acid ester and methacrylic acid ester in multiple stages while changing the composition of acrylic acid ester and methacrylic acid ester. A three-layer particle type graph containing a coalescence (gradient copolymer), a central portion, an intermediate layer portion and an outer layer portion. Door copolymer, and the like. These are used alone or in combination of two or more. Further, these may be used depending on the properties of the block copolymer (A) to be combined.

If necessary, the polymer composition constituting the film of the present invention may be other than the block copolymer (A) or the thermoplastic resin (B) as long as it does not impair the effects of the present invention. Other polymers, stabilizers, plasticizers, lubricants,
A flame retardant, a pigment, a filler, a release agent, an antistatic agent, an antibacterial / antifungal agent, etc. may be added. Specifically, styrene-butadiene rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), ethylene-propylene copolymer rubber (EPM), ethylene-propylene-diene copolymer rubber (EPDM), acrylonitrile-butadiene. Copolymer rubber (NBR), chloroprene rubber, butyl rubber (II
R), urethane rubber, silicone rubber, polysulfide rubber, hydrogenated nitrile rubber, fluororubber, tetrafluoroethylene-propylene rubber, tetrafluoroethylene-propylene-vinylidene fluoride rubber, acrylic rubber (ACM), chlorosulfonated Polyethylene rubber, epichlorohydrin rubber (C
O), ethylene-acrylic rubber, norbornene rubber, styrene-based thermoplastic elastomer (SBC), olefin-based thermoplastic elastomer (TPO), urethane-based thermoplastic elastomer (TPU), polyester-based thermoplastic elastomer (TPEE), polyamide-based heat Plastic elastomer (TPAE), 1,2-polybutadiene thermoplastic elastomer, PVC thermoplastic elastomer (TPV)
C), and synthetic rubbers such as fluorinated thermoplastic elastomers; stabilizers such as triphenylphosphite, hindered phenol, dibutyltin maleate; paraffin oils, polybutene oils, diesel oils, spindle oils, machine oils, linseed oils, Plasticizers such as sesame oil, castor oil, camellia oil, dioctyl phthalate, dibutyl phthalate, dioctyl adipate, tricresyl phosphate; lubricants such as polyethylene wax, polypropylene wax, montanic acid wax; triphenyl phosphate, tricresyl phosphate, deca Flame retardants such as bromobiphenyl, decabromobiphenyl ether, antimony trioxide; pigments such as titanium oxide, zinc sulfide, zinc oxide; glass fiber, metal fiber, potassium whisker titanate, asbestos, wallace Knight, mica, talc,
Calcium carbonate, glass flakes, milled fiber,
Examples include fillers such as metal powder.

When the laminated film of the present invention is composed of a polymer composition, the method of blending and producing the polymer composition is not particularly limited, and known methods such as Banbury mixer, roll mill, twin-screw extruder and the like are known. An existing method such as a method of mechanically mixing and shaping into pellets using an apparatus can be used. The temperature at the time of kneading is preferably adjusted according to the melting temperature of the block copolymer (A) used and the like, and for example, it can be produced by melt-kneading at 130 to 300 ° C.

The above-mentioned polymer composition can be molded into a film by any molding method such as extrusion molding, compression molding, blow molding, calender molding, vacuum molding and injection molding. From the viewpoint of processability and cost, it is preferable to form the film by an extrusion molding method. The extrusion molding can be performed by melt-extruding from a die having a desired shape and size such as a T die or a ring die and cooling. It is also possible to stretch in the uniaxial or biaxial direction simultaneously with the extrusion or after the extrusion.

The film of the present invention can be used by being laminated on various substrates. As a substrate for laminating the film, various conventionally known thermoplastic resin substrates can be used. Particularly in the case of wallpaper, polyvinyl chloride, polypropylene, and polyethylene terephthalate are often used from the viewpoint of workability and price. Further, a thermosetting resin that does not heat bond, a base material such as a steel plate, wood, or paper can be attached using an adhesive.

The thickness of the laminated film when the film of the present invention is laminated on a substrate is not particularly limited,
It is preferably about 1 to 300 μm. If it is less than 1 μm, the impact resistance tends to be insufficient, and if it is more than 300 μm, the economical efficiency becomes poor.

The method for laminating on the substrate is not particularly limited, but a known method can be used. Specifically, (1) a method of melt-kneading a polymer composition for producing a laminated film of the present invention with an extruder equipped with a T-die to form a film, and thermocompression-bonding this to a metal plate (in this case, The film may be unstretched, or may be stretched in one direction or in two directions), (2) a method of directly thermocompressing the film discharged from the T-die, and (3) melting the polymer composition to obtain a bar coder or A method of coating with a roll, (4) a method of melting the polymer composition to immerse the substrate,
It is also possible to laminate the polymer composition on a substrate by a method such as dissolving and spin-coating the polymer composition. The laminating method is not particularly limited, but the methods (1) and (2) are preferable from the viewpoint of work efficiency.

When laminating the film of the present invention on a substrate, another known resin film may be provided as an intermediate layer between the film of the present invention and the substrate, if necessary. As a specific laminating method, when using the above methods (1) and (2), a multilayer film of the resin film of the present invention and another resin film is produced by using a multilayer T die. , There is a method of thermocompression bonding. Also,
When the methods (3), (4) and (5) described above are used, it is possible to laminate the thermoplastic resin of the present invention after laminating another resin.

[0044]

EXAMPLES Next, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

The abbreviations used in the following description mean the following substances, respectively. BA; Butyl acrylate MM
A: Methyl methacrylate.

Production Example 1 (MMA-BA block copolymer) The following procedure was carried out to obtain an MMA-BA-MMA type block copolymer (A). After replacing the inside of the polymerization vessel of a 5 l separable flask with nitrogen, 11.4 g (7
9.3 mmol), weighed, and acetonitrile (dried with molecular sieves and then bubbled with nitrogen) 100
mL was added. After heating and stirring at 70 ° C. for 5 minutes, the mixture was cooled to room temperature again, and initiator 5.7 g (15.9 mmol) of diethyl 2,5-dibromoadipate and BA 447.0 g were used.
(500.0 ml) was added. The mixture was heated and stirred at 80 ° C., and the ligand diethylenetriamine 1.7 ml (7.9 mmol)
Was added to initiate polymerization. The polymerization solution was sampled from the polymerization solution at regular intervals from the start of the polymerization to about 0.
2 ml was withdrawn and the conversion of butyl acrylate was determined by gas chromatogram analysis of the sampling solution.
The polymerization rate was controlled by adding triamine from time to time. B
When the conversion rate of A exceeded 90%, MMA 133
3.2 g (1424.3 ml), copper chloride 7.8 g (7
9.3 mmol), 1.7 ml of diethylenetriamine
(7.9 mmol) and 1424.3 ml of toluene (those dried with molecular sieves and then bubbled with nitrogen) were added. Similarly, the conversion rate of MMA was determined. The conversion ratio of BA and MMA is the desired composition ratio, for example, BA / M.
When a polymer having a MA of 40/60 (% by weight) is obtained, BA
Is 100%, MMA is 50%
1500 ml of toluene was added thereto so that the reaction mixture was cooled in a water bath to terminate the reaction. The polymerization solution was always green during the reaction. The copper complex was removed by filtering the reaction solution through activated alumina. The obtained filtrate was added to a large amount of methanol to precipitate the polymer, and the obtained polymer was mixed with 6
The block copolymer used in the following Examples 1 to 5 was obtained by vacuum drying at 0 ° C. for 24 hours.

Production Example 2 (MMA-BA Block Copolymer) The following procedure was carried out to obtain an MMA-BA-MMA type block copolymer (A). After replacing the inside of the polymerization vessel of a 5 liter separable flask with nitrogen, copper bromide 11.3 was added.
g (78.5 mmol) was weighed out and acetonitrile (which was dried with molecular sieves and then bubbled with nitrogen)
180 ml was added. After heating and stirring at 70 ° C for 5 minutes,
After cooling to room temperature again, 5.7 g (15.7 mmol) of diethyl 2,5-dibromoadipate as an initiator and 804.6 g (900.0 ml) of butyl acrylate were added. Heat and stir at 80 ° C to obtain 1.6 ml of ligand diethylenetriamine
(7.9 mmol) was added to initiate polymerization. About 0.2 ml of the polymerization solution for sampling was sampled from the polymerization solution at regular intervals after the initiation of the polymerization, and the conversion rate of butyl acrylate was determined by gas chromatogram analysis of the sampling solution. The polymerization rate was controlled by adding triamine from time to time. When the conversion of butyl acrylate was 95%, 345.7 g (369.3 m) of methyl methacrylate was obtained.
l), copper chloride 7.8 g (78.5 mmol), diethylenetriamine 1.6 ml (7.9 mmol), toluene (nitrogen bubbling after drying with molecular sieves).
1107.9 ml was added. Similarly, the conversion rate of methyl methacrylate was determined. When the conversion of methyl methacrylate was 85% and the conversion of butyl acrylate was 98%, 1500 ml of toluene was added, and the reactor was cooled in a water bath to terminate the reaction. The polymerization solution was always green during the reaction.

The copper complex was removed by filtering the reaction solution through activated alumina. The obtained filtrate was added to a large amount of methanol to precipitate the polymer, and the obtained polymer was heated at 60 ° C.
By vacuum-drying for 24 hours at
The block copolymer used in 7 was obtained. (Molecular weight / molecular weight distribution) Chloroform as mobile phase
GPC measurement using a polystyrene gel column
The polystyrene equivalent molecular weight was determined. (Composition ratio (% by weight) of BA and MMA) By ¹ H-NMR, the weight fraction of butyl polyacrylate and methyl polymethacrylate in the block copolymer was confirmed.

Production Example 3 (MMA-BA Free Polymer and MMA-BA Core-Shell Graft Copolymer) In order to improve impact resistance, a core-shell graft copolymer was dispersed in a methacrylate ester resin. The polymer was obtained by the following procedure.

After adding 200 parts by weight of distilled water and 1.0% by weight of sodium dioctylsulfosuccinate as an emulsifier to an 8 liter polymerization vessel equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, a monomer addition device, and a reflux condenser, 85% by weight of butyl acrylate and 15% by weight of methyl methacrylate,
Triallyl isocyanurate 0.1 as a crosslinkable monomer
30 parts by weight of a monomer mixture containing 10% by weight and cumene hydroperoxide (0.
1% by weight of monomer mixture) and added into the polymerization vessel,
The polymerization temperature is set to 40 ° C. while stirring in a nitrogen stream. Then, a solution of sodium formaldehyde sulfoxylate (0.1 wt% vs. monomer mixture) dissolved in a small amount of water was gradually added to initiate polymerization, and the addition rate became 95% or more in about 4 hours. The polymerization was completed. The gel content of the crosslinked elastic emulsion thus obtained was 9
The swelling degree was 6.4%, the average particle size of the emulsion was 1450Å. Next, the polymerization temperature is raised to 80 ° C., 20 parts by weight of a monomer mixture containing 50% by weight of methyl methacrylate and 50% by weight of butyl acrylate, and cumene hydroperoxide (0.3% by weight per unit amount as a catalyst). Body mixture) is dissolved in the monomer mixture. Separately from this, sodium formaldehyde sulfoxylate (0.
2% by weight (monomer mixture) is dissolved in a small amount of water and added in advance to the polymerization vessel. Then, the monomer mixture was added in a nitrogen stream by a monomer addition pump with stirring for about 2 hours to carry out polymerization. Then, 50 parts by weight of a monomer mixture in which 80% by weight of methyl methacrylate, 20% by weight of butyl acrylate and cumene hydroperoxide (0.3% by weight of monomer mixture) as a catalyst were dissolved by an additional pump. Additional polymerization was carried out in about 4 hours. The polymerization-completed liquid thus obtained was salted out with a calcium chloride solution, washed with water and dried to obtain a dry powder of the polymer (B) used in Comparative Example 1 below. (Gel content of crosslinked elastic body) A predetermined amount of the crosslinked elastic body was sampled on a 100-mesh wire net, immersed in methyl ethyl ketone for 48 hours, dried under reduced pressure to remove methyl ethyl ketone, and then the constant weight was read to obtain the following formula. It was calculated by Gel content = (A) × 100 / (B) (A): Weight after re-drying (B): Weight of collected sample (glass transition temperature) “Polymer Handbook [Pol
ymer Hand Book (J. Brandrup,
Interscience, 1989] ”(MMA; 105 ° C., BA; −54 ° C.) was calculated using the Fox equation.

The measurements and evaluations in Examples and Comparative Examples were carried out under the following conditions and methods. The polymers used in Examples and Comparative Examples were those produced by the methods described in Production Examples 1 to 3. Film production is from Production Example 1
Irganox 1 as a stabilizer to the polymer obtained in 3
After blending 0.2 parts by weight of 010 (manufactured by Ciba-Geigy Co., Ltd.) and 2.0 parts by weight of TINUVIN 234 (manufactured by Ciba-Geigy Co., Ltd.) and roll-kneading at a set temperature of 230 ° C. for 5 minutes, the resulting kneaded product is set at a set temperature Obtained by hot press molding at 230 ° C.

(Tensile Property) The average value of the values measured at n = 3 was adopted by applying the method described in JIS K7133. The test piece used was a No. 2 (1/3) shape with a film thickness of 200 to 300 μm. The test was performed at 0 ° C. and a test speed of 500 mm / min. As a general rule, the test piece used was conditioned at a temperature of 23 ° C. and 2 ° C. and a relative humidity of 50 ° C. and 5% for 48 hours or more and further at 0 ° C. for 1 hour before use. (Whitening resistance) The molded film was subjected to the tensile test described above to evaluate the whitening of the fractured part after the tensile test.

(Hardness) The surface hardness of the film is ASTM-
Applying the method described in D2240, at 23 ° C, type D
It was measured using a durometer hardness tester. The measurement is 2
Test pieces having a thickness of 00 to 300 μm were stacked to make a thickness of 1 mm.

(Transparency) Using a haze meter manufactured by Nippon Denshoku Industries Co., Ltd., the total light transmittance (TT) and the haze value (haze) of the film were measured by a conventional method. Measured at 23 ° C, unit is%.

(Ethanol resistance) The film was immersed in ethanol for 5 hours, and the film after immersion was visually evaluated for whitening, swelling, wrinkles and the like according to the following criteria. ◯: The film is not clouded or whitened, and has no blisters or wrinkles. La: The film is cloudy or whitened. Alternatively, the film has blisters or wrinkles.

(Boiling resistant aqueous solution) The film was immersed in boiling water for 1 hour and then in water for 5 minutes. The film after the test was visually evaluated for whitening, swelling, wrinkles and the like according to the following criteria. ◯: The film is not clouded or whitened, and has no blisters or wrinkles. La: The film is cloudy or whitened. Alternatively, the film has blisters or wrinkles.

(Dustproofness) The dustproofness of the film was evaluated by the following criteria based on the tackiness of the film (whether the film sticks to the finger when the film is pressed with the finger). ○: The film has no tackiness. La: The film has a tacky feel.

[0058]

[Table 1] As is clear from the results shown in Examples 1 to 7 and Comparative Example 1 in Table 1, the film of the present invention represented by Examples has weather resistance, moldability, flexibility, impact resistance, dust resistance, It is excellent in transparency, ethanol resistance, boiling water resistance, and the like, and is less likely to become cloudy or change in transparency during stretching or bending (during processing), and can be suitably used as a laminate film.

Continued front page    F-term (reference) 4F071 AA33X AA75 BA01 BB03                       BB04 BB05 BB06 BC01                 4F100 AB01B AH01 AH02 AH03                       AK01A AK01B AK25A AL01A                       AL02A AL05A AP01B BA07                       BA41 CA05 CA30A EJ17                       EJ42 GB07 JB07 JB16B                       JD04 JK01 JL01 JL06 JL09                       JN01 YY00A                 4J026 HA05 HA06 HA09 HA10 HA11                       HA12 HA15 HA16 HA17 HA25                       HA29 HA32 HA35 HA38 HA39                       HA48 HB05 HB06 HB09 HB10                       HB11 HB12 HB15 HB16 HB17                       HB25 HB29 HB32 HB35 HB42                       HB45 HB48 HE02

Claims (7)

[Claims] 1. A methacrylic polymer block (a) 4
0 to 75% by weight and acrylic polymer block (b) 6
A laminated film formed by molding a block copolymer (A) comprising 0 to 25% by weight. 2. The block copolymer (A) comprises 45 to 70% by weight of a methacrylic polymer block (a) and 55 to 30% by weight of an acrylic polymer block (b). Item 2. The laminated film according to item 1. 3. A methacrylic polymer block (a) comprises 50 to 100% by weight of methyl methacrylic acid and another methacrylic acid ester copolymerizable therewith and / or another vinylic monomer 0 to 50. And the acrylic polymer block (b) is butyl acrylate 50 to 50% by weight.
100% by weight and 0 to 50% by weight of other acrylic acid ester and / or vinyl monomer copolymerizable therewith
The laminated film according to claim 1 or 2, which comprises a polymer block consisting of 4. The block copolymer (A) is produced by atom transfer radical polymerization.
The laminated film according to 2 or 3. 5. A polymer block in which the methacrylic polymer block (a) is composed of methyl methacrylate and the acrylic polymer block (b) is composed of butyl acrylate. Or the laminated film according to item 4. 6. The block copolymer (A) is a triblock copolymer, wherein the block copolymer (A) is a triblock copolymer.
Or the laminated film according to item 5. 7. A laminate film formed by molding a thermoplastic resin composition comprising the block copolymer (A) according to claim 1, 2, 3, 4, 5 or 6 and a thermoplastic resin (B).