JP2011031498A - Multilayer film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a multilayer film which has sufficient flexibility for guaranteeing, is hardly broken, excellent in whitening resistance, and exerts high resistance to an impact while having excellent easy moldability and maintaining sufficient surface hardness and strength. <P>SOLUTION: In the multilayer film, a layer (B) formed of a methacryl resin composition (b) containing a methacryl resin and acrylic rubber particles is laminated on at least one side surface of a layer (A) made of a thermoplastic resin composition (a) composed of a thermoplastic resin other than the methacryl resin as a resin component. The glass transition temperature TgA(°C) of the thermoplastic resin composition (a) and the glass transition temperature TgB(°C) of the methacryl resin composition (b) satisfy a formula: TgA-TgB<25, and the average particle diameter of an elastic polymer part in the acrylic rubber particles is 100 nm or smaller. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a multilayer film useful for surface decoration of various plastic products. The present invention also relates to a decorative film and a decorative sheet using the multilayer film, and further to a decorative molded product.

  As one of the methods for decorating the surface of plastic products such as exterior members of home appliances and interior parts of automobiles, for example, a film or sheet that has been previously decorated is three-dimensionally shaped by vacuum molding or pressure molding After pre-molding or without molding, insert into the injection mold and inject molten resin into it to paste the decorative film on the injection-molded product at the same time as forming the injection-molded product A method of performing (injection molding simultaneous bonding method) is known.

  Conventionally, a methacrylic resin excellent in transparency and weather resistance has been preferably used as a decorative film or sheet used in the simultaneous injection molding method as described above, and further, the flexibility of a film made of such a methacrylic resin is flexible. It has been proposed that acrylic rubber particles should be contained in a methacrylic resin in order to improve the property and improve the resistance to cracking (Patent Documents 1 to 3). However, when acrylic rubber particles are contained in a methacrylic resin, there is a problem that whitening is likely to occur due to bending, elongation, heating, or the like during injection molding and simultaneous bonding or pre-molding. In order to solve this problem of whitening, it has been proposed to use rubber particles having a relatively small particle size (Patent Document 4).

JP-A-8-323934 JP-A-10-279766 Japanese Patent Laid-Open No. 11-147237 JP 2002-80678 A

However, when the particle diameter of the acrylic rubber particles contained in the methacrylic resin is designed to be small in accordance with the proposal of Patent Document 4 described above, the original purpose of containing the rubber particles to increase the flexibility of the film and make it difficult to break is achieved. For this purpose, the content of the rubber particles must be increased, which leads to a decrease in surface hardness.
In addition, regardless of the size of the rubber particles, each single-layer film formed of a material containing acrylic rubber particles in a methacrylic resin as described in Patent Documents 1 to 4 has sufficient impact resistance. I couldn't say that.

  Accordingly, the object of the present invention is to provide sufficient flexibility to ensure the difficulty of cracking, excellent whitening resistance, good moldability, while maintaining sufficient surface hardness and strength. Another object of the present invention is to provide a film (multilayer film) that exhibits high impact resistance, and further to provide a decorative film, a decorative sheet, and a decorative molded product using this film.

  The present inventor has intensively studied to solve the above problems. As a result, the particle diameter of the elastic polymer portion of the acrylic rubber particles in the layer comprising the methacrylic resin composition containing the methacrylic resin and the acrylic rubber particles is reduced to a predetermined value or less to ensure sufficient whitening resistance. A layer made of a thermoplastic resin composition containing a thermoplastic resin other than a methacrylic resin such as a polycarbonate resin as a resin component is laminated on the layer made of the methacrylic resin composition. It has been found that a decrease in surface hardness and strength can be avoided, and impact resistance can be significantly improved. In addition, it has been known that the multilayer film in which different layers are laminated in this manner has a problem that the moldability may deteriorate, and the present inventor has determined that the glass transition temperature of the material forming each layer It was found that the moldability could be improved by setting the difference of less than a predetermined value, and the problem of using this multilayer film was solved. The present invention has been completed based on these findings.

That is, this invention consists of the following structures.
(1) A methacrylic resin composition containing a methacrylic resin and acrylic rubber particles on at least one surface of the layer (A) comprising the thermoplastic resin composition (a) containing a thermoplastic resin other than a methacrylic resin as a resin component. A multilayer film in which the layer (B) comprising (b) is laminated, the glass transition temperature TgA (° C.) of the thermoplastic resin composition (a) and the glass transition temperature of the methacrylic resin composition (b). TgB (° C.) satisfies the formula: TgA−TgB <25, and the average particle diameter of the elastic polymer part in the acrylic rubber particles is 100 nm or less.
(2) The multilayer film according to (1), wherein the thermoplastic resin composition (a) comprises a polycarbonate resin as a resin component.
(3) The thermoplastic resin composition (a) contains a polycarbonate resin and a plasticizer in a ratio of polycarbonate resin: plasticizer (weight ratio) = 70: 30 to 99: 1 (2 ) The multilayer film described.
(4) The multilayer film according to (3), wherein the plasticizer is a phosphate ester compound.
(5) The methacrylic resin composition (b) contains methacrylic resin and acrylic rubber particles in a ratio of methacrylic resin: acrylic rubber particles (weight ratio) = 20: 80 to 85:15. The multilayer film in any one of said (1)-(4).
(6) The said methacrylic resin composition (b) contains 0.5-10 weight part of ultraviolet absorbers with respect to a total of 100 weight part of a methacrylic resin and an acrylic rubber particle. The multilayer film in any one.
(7) The multilayer film according to (6), wherein the content of the ultraviolet absorber per unit area in the layer (B) is 0.15 to 1.5 g / m ² .
(8) The multilayer film according to (6) or (7), wherein the ultraviolet absorber is a benzotriazole-based ultraviolet absorber.
(9) The elastic polymer part in the acrylic rubber particles is composed of alkyl acrylate, alkyl methacrylate, monofunctional monomer other than these, and polyfunctional monomer as a total of 100% by weight. 50 to 99.9% by weight, 0 to 49.9% by weight of alkyl methacrylate, 0 to 49.9% by weight of monofunctional monomer, and 0.1 to 10% by weight of polyfunctional monomer The multilayer film according to any one of the above (1) to (8), which contains an elastic polymer obtained by polymerizing.
(10) The acrylic rubber particles are, on the outside of the elastic polymer part, the total of alkyl methacrylate, alkyl acrylate, other monofunctional monomers, and polyfunctional monomers as 100% by weight, 50-100% by weight of alkyl methacrylate, 0-50% by weight of alkyl acrylate, 0-50% by weight of monofunctional monomer, and 0-10% by weight of polyfunctional monomer The multilayer film according to any one of (1) to (9), wherein the multilayer film is a particle having a layer made of a hard polymer.
(11) The total thickness is 20 to 200 μm, the thickness of the layer (A) is 10 to 80% of the total thickness, and the thickness of the layer (B) is 10 μm or more (1 ) To (10).
(12) The multilayer film according to any one of (1) to (11), wherein the thermoplastic resin composition (a) and the methacrylic resin composition (b) are coextruded.

(13) Of the multilayer film according to any one of (1) to (12), the layer (A) side of the multilayer film in which the layer (B) is laminated on one surface of the layer (A) A decorative film characterized in that the surface is decorated.
(14) Of the multilayer film according to any one of (1) to (12), either side of the multilayer film in which the layer (B) is laminated on both sides of the layer (A) Decorating film characterized by being decorated.
(15) A decorative sheet, wherein a thermoplastic resin sheet is laminated on the surface on the decorative side of the decorative film according to (13) or (14).
(16) A decorative molded product, wherein a thermoplastic resin is injection-molded on the surface on the decorative side of the decorative film according to (13) or (14).
(17) A decorative molded product, wherein a thermoplastic resin is injection-molded on the surface of the decorative sheet according to (15) on the thermoplastic resin sheet side.

  According to the present invention, it has sufficient flexibility to ensure the difficulty of cracking, is excellent in whitening resistance, has good moldability, and retains sufficient surface hardness and strength while being high. A multilayer film exhibiting impact resistance can be provided. And if you use a decorative film or decorative sheet using this multilayer film, it becomes possible to decorate the surface of various plastic products by, for example, injection molding simultaneous bonding method, excellent in design, The effect that a decorative molded product having excellent impact resistance and high surface hardness and strength can be easily produced is obtained.

  The multilayer film of the present invention contains methacrylic resin and acrylic rubber particles on at least one surface of the layer (A) composed of the thermoplastic resin composition (a) containing a thermoplastic resin other than methacrylic resin as a resin component. The layer (B) made of the methacrylic resin composition (b) is laminated.

  The thermoplastic resin composition (a), which is a material for forming the layer (A), may be any material that uses a thermoplastic resin other than a methacrylic resin as a resin component. Here, examples of the thermoplastic resin other than the methacrylic resin include polycarbonate resin, polystyrene resin, aliphatic polyester resin, ABS resin, and the like. Among these, it is preferable to use polycarbonate resin as a resin component in terms of flexibility and impact resistance of the resulting multilayer film. In addition, only 1 type may be sufficient as thermoplastic resins other than a methacryl resin, and 2 or more types may be sufficient as it.

  Examples of the polycarbonate resin include i) those obtained by reacting a dihydric phenol and a carbonylating agent by an interfacial polycondensation method or a melt transesterification method, and ii) a solid phase transesterification method of a carbonate prepolymer. And iii) those obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method. Among these, i) a product obtained by reacting a dihydric phenol and a carbonylating agent by an interfacial polycondensation method or a melt transesterification method is preferable in terms of productivity.

  Examples of the dihydric phenol include hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-dimethyl) phenyl} methane, 1,1 -Bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5- Dibromo) phenyl} propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl} propane, 2,2-bis { 4-hydroxy-3-phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxy) Phenyl) -3,3-dimethylbutane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3, 3,5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydro Cis-3-methyl) phenyl} fluorene, α, α′-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α ′ -Bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfoxide 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl ester, and the like. It can also be used.

Among the above-mentioned dihydric phenols, among those described above, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2 -Bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, , 1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, alone or in combination with a dihydric phenol selected from the group consisting of It is preferable to use two or more kinds. In particular, bisphenol A alone or 1,1-bis (4-hydroxyphenyl) -3,3, -Selected from the group consisting of trimethylcyclohexane, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene Use in combination with one or more dihydric phenols is preferred.
Examples of the carbonylating agent include carbonyl halides such as phosgene, carbonate esters such as diphenyl carbonate, haloformates such as dihaloformates of dihydric phenols, and two or more of them can be used as necessary.

  In addition to the resin component, the thermoplastic resin composition (a), which is a material for forming the layer (A), includes, for example, a plasticizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a silicone compound, and the like. Various additives such as a flame retardant, a filler, glass fiber, and an impact modifier may be contained within a range not impairing the effects of the present invention. In particular, the plasticizer is preferably contained in order to lower the glass transition temperature (TgA) of the thermoplastic resin composition (a) and adjust the value of TgA-TgB described later to be within a predetermined range. .

  Examples of the plasticizer include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate. Phosphate ester compounds; phthalate ester compounds such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis (2-ethylhexyl phthalate), diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalyl ethyl glycolate; Tris (2 -Emethylhexyl) trimellitic acid ester compounds such as trimellitate; dimethyl adipate, dibutyl acetate Pate, diisobutyl adipate, bis (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, diisodecyl adipate, bis (butyldiglycol) adipate, bis (2-ethylhexyl) azelate, dimethyl sebacate, dibutyl sebacate, bis (2- Ethylhexyl) aliphatic dibasic acid ester compounds such as sebacate and diethyl succinate; ricinoleic acid ester compounds such as methylacetylricinoleate; acetic acid ester compounds such as triacetin and octyl acetate; sulfones such as N-butylbenzenesulfonamide Amide compounds; and the like. In particular, when the resin component is a polycarbonate resin, among the plasticizers described above, a phosphoric acid ester-based compound is preferable because of its good compatibility with the polycarbonate resin and good transparency of the resin after the compatibility. In particular, cresyl diphenyl phosphate and tricresyl phosphate are more preferable.

  When the thermoplastic resin composition (a) contains a polycarbonate resin and a plasticizer, the ratio of both is preferably polycarbonate resin: plasticizer (weight ratio) = 70: 30 to 99: 1. It is more preferable that resin: plasticizer (weight ratio) = 90: 10 to 98: 2. If the amount of the plasticizer is less than the above-described ratio, the effect of lowering the glass transition temperature due to plasticization becomes insufficient, and the value of TgA-TgB described later does not fall within a predetermined range. It may be difficult to improve the moldability. On the other hand, when the amount of the plasticizer is larger than the above-described ratio, the fluidity of the thermoplastic resin composition (a) containing the polycarbonate resin is remarkably increased. For example, it is laminated with the methacrylic resin composition (b) described later. When a multilayer film is produced by the extrusion molding method, the appearance may be impaired.

The said methacrylic resin composition (b) which is a forming material of a layer (B) contains a methacrylic resin as a resin component.
The methacrylic resin is a polymer mainly composed of methacrylic acid ester, may be a homopolymer of methacrylic acid ester, or may be a copolymer of methacrylic acid ester and other monomers. Good. Here, as the methacrylic acid ester, an alkyl ester of methacrylic acid is usually used. In addition, only 1 type may be sufficient as a methacryl resin, and 2 or more types may be sufficient as it.

  As the alkyl methacrylate, those having an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 are usually used. Specific examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and the like. Among these, methyl methacrylate is preferable. Two or more kinds of alkyl methacrylates may be used as necessary.

Examples of the monomer other than the methacrylic acid ester include alkyl acrylate, and a monomer copolymerizable with alkyl methacrylate or alkyl acrylate.
As the alkyl acrylate, those having an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms are usually used. Specific examples include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like. Two or more kinds of alkyl acrylates may be used as necessary.

  The monomer copolymerizable with the alkyl methacrylate or the alkyl acrylate may be a monofunctional monomer, that is, a compound having one polymerizable carbon-carbon double bond in the molecule. Although it may be a functional monomer, that is, a compound having at least two polymerizable carbon-carbon double bonds in the molecule, a monofunctional monomer is preferably used. Here, examples of the monofunctional monomer include aromatic alkenyl compounds such as styrene, α-methylstyrene, and vinyl toluene; alkenyl cyan compounds such as acrylonitrile and methacrylonitrile; acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimides; and the like. Examples of polyfunctional monomers include polyunsaturated carboxylic acid esters of polyhydric alcohols such as ethylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate; allyl acrylate, allyl methacrylate, cinnamon Alkenyl esters of unsaturated carboxylic acids such as allyl acid; polyalkenyl esters of polybasic acids such as diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate; aromatic polyalkenyl compounds such as divinylbenzene; etc. Is mentioned. Two or more types of monomers that can be copolymerized with alkyl methacrylate or alkyl acrylate may be used as necessary.

  The composition of the monomer components constituting the methacrylic resin (the methacrylate ester, the alkyl acrylate, and the monomer copolymerizable with the alkyl methacrylate or alkyl acrylate) is the sum of all monomers. As 100% by weight, the alkyl methacrylate is 50 to 100% by weight, the alkyl acrylate is 0 to 50% by weight, and the alkyl methacrylate or the monomer copolymerizable with the alkyl acrylate is 0 to 49% by weight. More preferably, the alkyl methacrylate is 50 to 99.9% by weight, the alkyl acrylate is 0.1 to 50% by weight, and the monomer copolymerizable with the alkyl methacrylate or the alkyl acrylate is 0 to 49% by weight. % Should be good.

  The methacrylic resin can be prepared by polymerizing the above-described monomer components by a known method such as suspension polymerization, emulsion polymerization, or bulk polymerization. At that time, a chain transfer agent is preferably used at the time of polymerization in order to adjust to a desired glass transition temperature or to obtain a viscosity exhibiting suitable moldability when producing a multilayer film. The amount of the chain transfer agent may be appropriately determined according to the type of monomer component and the composition thereof.

  The methacrylic resin composition (b), which is a material for forming the layer (B), also contains acrylic rubber particles having an elastic polymer part together with the methacrylic resin. Such acrylic rubber particles have a layer (elastic polymer layer) made of an elastic polymer mainly composed of an acrylate ester, and may be single-layer particles made only of an elastic polymer or elastic. Particles having a multilayer structure composed of a polymer layer and a layer made of a hard polymer (hard polymer layer) may be used, but considering the surface hardness of the layer (B) disposed on the surface of the multilayer film It is preferable that the particles have a multilayer structure. In addition, only 1 type may be sufficient as acrylic rubber particle, and 2 or more types may be sufficient as it.

  When the acrylic rubber particles have a multilayer structure, the layer structure is not particularly limited. For example, a two-layer structure including an inner layer (elastic polymer layer) / outer layer (hard polymer layer), an inner layer (hard) Polymer layer) / outer layer (elastic polymer layer) two-layer structure, inner layer (hard polymer layer) / intermediate layer (elastic polymer layer) / outer layer (hard polymer layer) three-layer structure, inner layer ( 3 layer structure consisting of elastic polymer layer) / intermediate layer (hard polymer layer) / outer layer (elastic polymer layer), inner layer (elastic polymer layer) / inner layer side intermediate layer (hard polymer layer) / outer layer side intermediate Examples thereof include a four-layer structure consisting of a layer (elastic polymer layer) / outer layer (hard polymer layer). In addition, in the structure in which the outermost layer is a hard polymer layer among these layer structures, the outer surface is further covered with a hard polymer layer having a different composition, specifically, for example, an inner layer (elastic polymer layer). / 3 layer structure consisting of intermediate layer (hard polymer layer) / outer layer (hard polymer layer), inner layer (hard polymer layer) / inner layer side intermediate layer (elastic polymer layer) / outer layer side intermediate layer (hard polymer) Layer) / outer layer (hard polymer layer) may be used.

  The elastic polymer portion in the acrylic rubber particles is a portion containing at least an elastic polymer. Specifically, when the acrylic rubber particles are single-layer particles made of only an elastic polymer, the acrylic polymer portion Means all of the rubber particles, and on the other hand, when the acrylic rubber particles are particles having a multilayer structure, the outermost elastic polymer layer of the layers constituting the acrylic rubber particles and the elastic polymer It shall mean the interior covered by the layer. That is, the elastic polymer portion of the acrylic rubber particles includes all elastic polymer layers constituting the rubber particles. For example, when the acrylic rubber particles have a two-layer structure consisting of an inner layer (elastic polymer layer) / outer layer (hard polymer layer), only the inner layer corresponds to the elastic polymer portion, and the acrylic rubber particles are the inner layer. In the case of a three-layer structure consisting of (hard polymer layer) / intermediate layer (elastic polymer layer) / outer layer (hard polymer layer), the inner layer and the intermediate layer correspond to the elastic polymer portion, and acrylic rubber When the particles have a three-layer structure comprising an inner layer (elastic polymer layer) / intermediate layer (hard polymer layer) / outer layer (hard polymer layer), only the inner layer corresponds to the elastic polymer portion.

The elastic polymer layer constituting the rubber particles includes an alkyl acrylate and a polyfunctional monomer, and polymerizes a monomer component including an alkyl methacrylate and other monofunctional monomers as necessary. It is preferable that the elastic polymer is formed.
Examples of the alkyl acrylate used when forming the elastic polymer layer include the same ones as described above as the alkyl acrylate constituting the methacrylic resin, and among them, butyl acrylate and acrylic acid, among others. Those having an alkyl group having 4 to 8 carbon atoms such as 2-ethylhexyl are preferred. In addition, only 1 type may be sufficient as alkyl acrylate, and 2 or more types may be sufficient as it.

  As the polyfunctional monomer used when forming the elastic polymer layer, the polyfunctional monomer constituting the methacrylic resin (a monomer copolymerizable with alkyl methacrylate or alkyl acrylate) is described above. Any monomer that exhibits a function as a so-called crosslinking agent or grafting agent may be used. Specific examples include the same polyfunctional monomers that constitute the methacrylic resin, and among them, alkenyl esters of unsaturated carboxylic acids and polyalkenyl esters of polybasic acids are preferably exemplified. In addition, only 1 type may be sufficient as a polyfunctional monomer, and 2 or more types may be sufficient as it.

Examples of the alkyl methacrylate optionally used for forming the elastic polymer layer include the same ones as described above as the alkyl methacrylate constituting the methacrylic resin. In addition, only 1 type may be sufficient as the alkyl methacrylate, and 2 or more types may be sufficient as it.
The other monofunctional monomer optionally used in forming the elastic polymer layer includes a monofunctional monomer constituting the methacrylic resin (a monomer capable of copolymerization with an alkyl methacrylate or an alkyl acrylate). Examples of such a compound are the same as those described above, and aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene are particularly preferable. In addition, only 1 type may be sufficient as another monofunctional monomer, and 2 or more types may be sufficient as it.

  A preferable composition of the monomer component forming the elastic polymer layer in the acrylic rubber particles is, for example, a total of alkyl acrylate, alkyl methacrylate, other monofunctional monomers, and polyfunctional monomers. Is 100% by weight, alkyl acrylate is 50 to 99.9% by weight, alkyl methacrylate is 0 to 49.9% by weight, monofunctional monomer is 0 to 49.9% by weight, and polyfunctional monomer is 0.1 to 10% by weight.

The hard polymer layer constituting the rubber particles usually contains an alkyl methacrylate, and if necessary, a monomer component containing an alkyl acrylate or other monofunctional monomer and polyfunctional monomer. It is preferably formed of a hard polymer obtained by polymerizing.
Examples of the alkyl methacrylate used for forming the hard polymer layer include the same as those described above as the alkyl methacrylate constituting the methacrylic resin, and among them, methyl methacrylate is preferably mentioned. . In addition, only 1 type may be sufficient as the alkyl methacrylate, and 2 or more types may be sufficient as it.

Examples of the alkyl acrylate optionally used for forming the hard polymer layer include the same as those described above as the alkyl acrylate constituting the methacrylic resin. What has the alkyl group which is -4 is mentioned preferably. In addition, only 1 type may be sufficient as alkyl acrylate, and 2 or more types may be sufficient as it.
As the monofunctional monomer optionally used in forming the hard polymer layer, the monofunctional monomer constituting the methacrylic resin (a monomer copolymerizable with alkyl methacrylate or alkyl acrylate) Are the same as those described above. In addition, only 1 type may be sufficient as another monofunctional monomer, and 2 or more types may be sufficient as it.

  The polyfunctional monomer optionally used in forming the hard polymer layer is a polyfunctional monomer constituting the methacrylic resin (a monomer copolymerizable with an alkyl methacrylate or an alkyl acrylate). Are the same as those described above. In addition, only 1 type may be sufficient as a polyfunctional monomer, and 2 or more types may be sufficient as it.

  A preferred composition of the monomer component forming the hard polymer layer in the acrylic rubber particles is, for example, when the hard polymer layer is present outside the elastic polymer portion, alkyl methacrylate, alkyl acrylate, The total amount of monofunctional monomers and polyfunctional monomers other than these is 100% by weight, alkyl methacrylate is 50 to 100% by weight, alkyl acrylate is 0 to 50% by weight, and monofunctional monomer is 0%. -50% by weight, polyfunctional monomer is 0-10% by weight, on the other hand, when the hard polymer layer is present inside the elastic polymer part (that is, the elastic polymer part is the hard polymer layer) ), Alkyl methacrylate, alkyl acrylate, monofunctional monomer other than these, and polyfunctional monomer as a total of 100% by weight, alkyl methacrylate is 70 to 100% by weight. , Alkyl acrylate 0-30% by weight, the monofunctional monomer is 0-30 wt%, a polyfunctional monomer is 0-10 wt%.

  The weight ratio of the elastic polymer layer and the hard polymer layer constituting the acrylic rubber particles is not particularly limited. For example, the ratio of the elastic polymer layer and the hard polymer layer that are adjacent to each other is elastic. The hard polymer is usually 10 to 400 parts by weight, preferably 20 to 200 parts by weight, based on 100 parts by weight of the polymer.

  The acrylic rubber particles as described above can be synthesized into the latex by, for example, a known emulsion polymerization method, and then coagulated by an appropriate recovery operation (for example, salting out, aciding out, freezing, etc.) It can be obtained by a method of isolating as a powder by performing filtration and then washing, a method of collecting by spray drying, or the like. In the emulsion polymerization, polymerization may be performed in order from the monomer component constituting the polymer that becomes the inner (center side) layer of the acrylic rubber particles. For example, inner layer (elastic polymer layer) / outer layer (hard) In the case of rubber particles having a two-layer structure composed of a polymer layer), first, a monomer component constituting an elastic polymer as an inner layer is polymerized to obtain a latex containing elastic polymer particles, and then this latex The monomer component constituting the hard polymer as the outer layer may be added and polymerized to graft the hard polymer onto the elastic polymer particles. The polymerization for forming each layer may be carried out by a single-stage reaction or by a multi-stage reaction of two or more stages. In the case of performing the reaction in two or more stages, the composition of the monomer used in each stage is not particularly limited, and the composition of all the monomer components used in the multistage reaction for forming the layer is within the predetermined range described above. It only has to be inside.

  In the present invention, it is important that the average particle diameter of the elastic polymer portion in the acrylic rubber particles is 100 nm or less. Preferably, the average particle diameter of the elastic polymer part is 90 nm or less. When the average particle diameter of the elastic polymer portion in the acrylic rubber particles exceeds 100 nm, the whitening resistance becomes insufficient and the transparency is also lowered. The average particle diameter of the elastic polymer part in the acrylic rubber particles is controlled by adjusting the amount of emulsifier added, the amount of monomer components used, etc., when the acrylic rubber particles are obtained by emulsion polymerization, for example. Can do.

  When using acrylic rubber particles having a layer structure in which the outermost layer (outer layer) is a hard polymer layer, the average particle diameter of the elastic polymer portion (that is, the outermost layer among the layers constituting the acrylic rubber particles) The average particle diameter of the particles excluding the hard polymer layer outside the elastic polymer layer is mixed with, for example, a methacrylic resin containing the acrylic rubber particles in the methacrylic resin composition (b). In the cross section, the elastic polymer layer is dyed with ruthenium oxide, and then observed with an electron microscope, and can be obtained from the diameter (outer diameter) of the dyed portion. When acrylic rubber particles are mixed with methacrylic resin and the cross section is dyed with ruthenium oxide, the acrylic rubber particles are removed from the hard polymer layer (outermost layer (outer layer)) outside the elastic polymer layer. For example, in the case of rubber particles having a two-layer structure consisting of an inner layer (elastic polymer layer) / outer layer (hard polymer layer), the inner elastic polymer layer Only the dyed particles are observed as single-layered particles, and the rubber particles have a three-layer structure consisting of an inner layer (hard polymer layer) / intermediate layer (elastic polymer layer) / outer layer (hard polymer layer). The hard polymer layer as the outer layer and the hard polymer layer at the center of the particle as the inner layer are not dyed, and only the elastic polymer layer of the intermediate layer is observed as dyed two-layer particles.

  In the methacrylic resin composition (b), the content ratio of the methacrylic resin and the acrylic rubber particles is preferably methacrylic resin: acrylic rubber particles (weight ratio) = 20: 80 to 85:15. More preferably, methacrylic resin: acrylic rubber particles (weight ratio) = 40: 60 to 75:25. Thus, by including a relatively larger amount of acrylic rubber particles than in the past, excellent impact resistance can be exhibited. If the content ratio of the acrylic rubber particles is less than the above range, the impact resistance becomes insufficient, and cracks may occur on the surface of the obtained multilayer film. The surface hardness (pencil hardness) of the film may be reduced.

  The methacrylic resin composition (b) preferably contains an ultraviolet absorber. Thereby, not only the photodegradation of the layer (B) formed with the methacrylic resin composition (b) but also the photodegradation of the layer (A) can be suppressed, and it is difficult to yellow over a long period of time, and has a UV-cutting ability. It can be a film.

  Examples of UV absorbers include benzotriazole UV absorbers, benzoate UV absorbers, salicylic acid derivative UV absorbers, substituted acrylonitrile UV absorbers, nickel complex UV absorbers, benzophenone UV absorbers, and triazines. An ultraviolet absorber etc. are mentioned. Among these, 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] (commercially available products, for example, ADEKA “LA31” and the like, and 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (commercially available products such as Ciba Specialty Chemicals ( Benzotriazole-based UV absorbers such as “Tinuvin 234” manufactured by the same company) are preferred. In addition, only 1 type may be sufficient as an ultraviolet absorber, and 2 or more types may be sufficient as it.

  When the methacrylic resin composition (b) contains an ultraviolet absorber, the content is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight in total of the methacrylic resin and the acrylic rubber particles. More preferably, the content is 1 to 5 parts by weight. If the content of the UV absorber is less than the above range, the UV-cutting ability of the multilayer film tends to be insufficient. On the other hand, if the content is more than the above range, work is performed by the heat volatilization of the UV absorber when manufacturing the multilayer film. There is a risk that the environment may be deteriorated, the equipment may be contaminated, and the resulting film may have problems such as surface roughness.

The content of the ultraviolet absorber in the methacrylic resin composition (b) is preferably 0.15 to 1.5 g / m ² , more preferably as the content per unit area of the layer (B). Is preferably 0.25 to 1 g / m ² . If the content of the UV absorber per unit area is less than the above range, the multilayer film tends to have insufficient UV-cutting ability. On the other hand, if the content exceeds the above range, the appearance and film formability of the resulting multilayer film are likely to be insufficient. Tends to decrease.
The methacrylic resin composition (b) may further contain various additives such as organic dyes, inorganic dyes, pigments, antioxidants, antistatic agents, surfactants, and the like, if necessary. You may make it contain in the range which does not impair an effect.

  In the present invention, the glass transition temperature TgA (° C.) of the thermoplastic resin composition (a) and the glass transition temperature TgB (° C.) of the methacrylic resin composition (b) satisfy the formula: TgA−TgB <25. This is very important. Thereby, the obtained multilayer film will have favorable moldability, for example, a decorative molded product can be easily manufactured by the simultaneous injection molding method. In addition, TgA and TgB can be measured by the method as described in the Example mentioned later, for example.

  The multilayer film of the present invention comprises a layer (A) formed by filming the thermoplastic resin composition (a) and a layer (B) formed by filming the methacrylic resin composition (b). Can be obtained. The production method is not particularly limited. For example, the material for forming each layer (thermoplastic resin composition (a) and methacrylic resin composition (b)) is melted in an extruder, and a feed block method or a multi-manifold method is used. A method of laminating by coextrusion molding (coextrusion molding method), an extrusion molding method of any one of the formation materials (thermoplastic resin composition (a) and methacrylic resin composition (b)) of each layer, etc. A method of coating the surface of the film by dissolving the material for forming the other layer in a solvent as required is preferably employed. In particular, the multilayer film of the present invention is formed by a coextrusion molding method, that is, the one obtained by coextrusion molding of the thermoplastic resin composition (a) and the methacrylic resin composition (b). However, it is preferable in that the manufacturing process is simple.

  When a multilayer film is obtained by a coextrusion molding method, the melted layer forming material (thermoplastic resin composition (a) and methacrylic resin composition (b)) is brought into close contact with a roll or belt to form a film. At this time, the number of rolls and belts, the arrangement, the material, etc. are not particularly limited, but for example, each molten layer forming material is contacted and passed between two metal rolls or between a metal roll and a metal belt, It is preferable to transfer the surface of the roll or belt because the surface accuracy of the film surface can be improved and the decorating property can be improved. In addition, using a metal roll and a metal roll with elastic surface (metal elastic roll), if both sides of each layer-forming material melted on the surface are contacted and passed, distortion during molding is reduced, and strength and heat shrinkage are reduced. It is preferable because a film with little property anisotropy can be obtained. Here, the metal elastic roll includes, for example, a shaft roll and a cylindrical metal thin film disposed so as to cover the outer peripheral surface of the shaft roll, and water is provided between the shaft roll and the metal thin film. And a material in which a temperature-controlled fluid such as oil or oil is enclosed, or a material in which a metal belt is wound around the surface of a rubber roll.

  The multilayer film thus obtained preferably has an overall thickness of 20 to 200 μm, more preferably 30 to 150 μm, and even more preferably 50 to 100 μm. If the thickness of the entire multilayer film is too thick, for example, it will take time to mold the interior of automobile interior materials, etc., and the improvement in physical properties and design properties by decoration will be reduced, which is disadvantageous in terms of cost. Tend to be. On the other hand, if the total thickness of the multilayer film is too thin, film formation by extrusion molding or the like becomes mechanically difficult, and the breaking strength of the film tends to be low, and the probability of occurrence of defects during film production tends to increase. . The total thickness of the multilayer film can be adjusted by adjusting the film forming speed, the thickness of the T-die discharge port, the gap between rolls, and the like.

The thickness of the layer (A) in the multilayer film of the present invention is 10 to 80% of the total thickness of the multilayer film, and the thickness of the layer (B) (the layer (B) on both sides of the layer (A)) In the case of arranging, the thickness of each layer (B) is preferably 10 μm or more. If the thickness of the layer (A) is too thin, the multilayer film may be brittle and prone to cracking. On the other hand, if the thickness of the layer (A) is too thick or the thickness of the layer (B) is too thin. The surface hardness of the multilayer film may be insufficient.
The multilayer film of the present invention as described above is preferably used as a decorative film or a decorative sheet.

  The decorative film of the present invention is i) the surface on the layer (A) side of the multilayer film of the present invention, wherein the layer (B) is laminated on one surface of the layer (A). Is decorated (this embodiment is referred to as “first form”), or ii) among the multilayer film of the present invention, the layer (B) is on both sides of the layer (A). One of the surfaces is decorated on the laminated multilayer film (this mode is referred to as “second mode”). Thus, in the decorative film of the present invention, a specific surface is decorated according to the laminated form of the multilayer film. Thereby, since the surface of the layer (B) which mix | blended the acrylic rubber particle will always be located in the surface side in the decoration molded product decorated using this film for decorating, design property is provided. At the same time, the surface hardness can be increased. Moreover, when the ultraviolet absorber is contained in the methacrylic resin composition (b), the surface of the layer (B) is always located on the surface side, so that the entire multilayer film and the decorative layer are well protected from ultraviolet rays. Will be. For example, when the simplicity (decoration property) at the time of decorating, the surface hardness of the decorative molded product to be obtained, and the like are taken into consideration, the second form is preferable.

  The method for decorating the multilayer film is not particularly limited, for example, a method of directly printing various designs such as wood grain on the surface of the multilayer film by continuous gravure printing or silk printing, or vapor deposition. For example, a method of decorating a metal plating tone by sputtering or the like, a method of laminating a resin film previously decorated by printing, vapor deposition, or the like can be employed.

  The decorative sheet of the present invention is obtained by laminating a thermoplastic resin sheet as a backing material on the surface on the decorative side of the decorative film of the present invention. Here, the resin constituting the thermoplastic resin sheet is not particularly limited, and examples thereof include ABS resin, methacrylic resin, polyvinyl chloride resin, polyurethane resin, polyester resin, and polyolefin resin. Further, the thickness of the thermoplastic resin sheet includes the thickness of a so-called film region, and is usually about 0.1 to 2 mm.

  In the decorative molded product of the present invention, the thermoplastic resin is injected on the surface on the decorative side of the decorative film of the present invention or on the surface on the thermoplastic resin sheet side of the decorative sheet of the present invention. It is formed. Thus, by performing injection molding so that the resin layer surface on which the decorative layer is not provided is located on the surface of the resulting decorative molded product, it has good design properties, impact resistance, A decorative molded product having excellent surface hardness and strength can be obtained. Here, the thermoplastic resin used for injection molding is not particularly limited, and examples thereof include ABS resin, methacrylic resin, polyvinyl chloride resin, polyurethane resin, polyester resin, and polyolefin resin.

  As a method for obtaining the decorative molded product of the present invention, an injection molding simultaneous bonding method is preferably employed. Specifically, the injection molding simultaneous bonding method is as follows: i) Inserting a decorative film or decorative sheet into an injection mold without preforming and injecting a molten resin therein to form an injection molded product At the same time, a method of bonding a decorative film or decorative sheet to the molded product (sometimes referred to as “injection molding simultaneous bonding method” in a narrow sense), ii) vacuum forming a decorative film or decorative sheet After preforming by pressure molding etc., insert into injection mold and inject molten resin into it to form injection molded product, and at the same time, paste decorative film or decorative sheet to the molded product (Iii) A decorative film or sheet is pre-molded by vacuum molding or pressure molding in an injection mold, and then a molten resin is added to the decorative film or sheet. Inject And by, at the same time to form an injection molded article, the method for laminating a decorative film or decorative sheet to the molded article (sometimes referred to as "in-mold molding method") can be carried out by such. For further details of the injection molding simultaneous bonding method, for example, according to a conventionally known technique as described in Japanese Patent Publication No. 63-6339, Japanese Patent Publication No. 4-9647, Japanese Patent Application Laid-Open No. 7-9484, etc. That's fine.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited only to a following example. In the following, “parts” and “%” representing the content or amount used mean “parts by weight” and “% by weight” unless otherwise specified.
Various physical properties in the following examples and comparative examples were measured by the following methods.

<Glass transition temperature (TgA and TgB)>
In accordance with JIS-K7121-1987, differential scanning calorimetry was performed, and the extrapolated glass transition start temperature determined at a heating rate of 10 ° C./min was defined as the glass transition temperature (TgA or TgB).

<Average particle diameter of elastic polymer part in acrylic rubber particles>
Acrylic rubber particles are mixed with a methacrylic resin to form a film, and the resulting film is cut into an appropriate size, and the slice is immersed in a 0.5% ruthenium tetroxide aqueous solution at room temperature for 15 hours. The polymer layer was dyed. Further, after cutting the sample to a thickness of about 80 nm using a microtome, the photograph was taken with a transmission electron microscope, and 100 dyed elastic polymer layers were randomly selected from the photograph, After calculating each diameter, the average value was calculated | required and this was made into the average particle diameter of an elastic polymer part.

(Examples 1-9 and Comparative Examples 1-6)
First, a polycarbonate resin composition was prepared as a material for forming the layer (A) as follows (except for Comparative Example 5). That is, a polycarbonate resin (“Caliver 303-10” manufactured by Sumitomo Dow Co., Ltd., glass transition temperature of 145 ° C.) is melted using a 75 mmφ twin screw extruder (manufactured by Toshiba Machine Co., Ltd.) and pumped from the middle of the barrel. A liquid plasticizer (cresyl diphenyl phosphate (“CDP” manufactured by Daihachi Chemical Industry Co., Ltd.)) was fed and mixed with a polycarbonate resin and a plasticizer in the proportions shown in Table 1 (however, for Comparative Example 4) The plasticizer was not mixed), and a polycarbonate resin composition was obtained as pellets. The polycarbonate resin composition had a glass transition temperature (TgA) as shown in Table 1.

  On the other hand, a methacrylic resin composition was prepared as a material for forming the layer (B) as follows (except for Comparative Example 6). That is, methacrylic resin and acrylic rubber particles (1) or (2) are mixed with a super mixer at a ratio shown in Table 1, and melt mixed using a 75 mmφ twin screw extruder (manufactured by Toshiba Machine Co., Ltd.). The methacrylic resin composition was obtained as pellets by smelting (however, in Comparative Examples 1 and 2, acrylic rubber particles were not mixed). The methacrylic resin composition had a glass transition temperature (TgB) as shown in Table 1.

In the preparation of the methacrylic resin composition, as the methacrylic resin, a thermoplastic polymer obtained by bulk polymerization of monomer components composed of 97.8% methyl methacrylate and 2.2% methyl acrylate is used. Pellets (glass transition temperature 104 ° C.) were used.
In the preparation of the methacrylic resin composition, the acrylic rubber particles (1) were obtained by polymerizing a monomer component having an inner layer of 81% butyl acrylate, 17% styrene, and 2% allyl methacrylate. It is an elastic polymer, and the outer layer is a hard polymer obtained by polymerizing a monomer component consisting of 94% methyl methacrylate and 6% methyl acrylate. The inner layer (elastic polymer layer) / outer layer ( Rubber particles having a spherical two-layer structure obtained by an emulsion polymerization method with a weight ratio of (hard polymer layer) of 80/20 were used. It was 80 nm when the average particle diameter of the elastic polymer part (the layer of the elastic polymer as an inner layer) in the acrylic rubber particles (1) was measured.

  In the preparation of the methacrylic resin composition, the acrylic rubber particles (2) include a monomer component whose inner layer is composed of 93.8% methyl methacrylate, 6% methyl acrylate, and 0.2% allyl methacrylate. It is a hard polymer obtained by polymerization, and an intermediate layer is an elastic polymer obtained by polymerizing a monomer component consisting of 81% butyl acrylate, 17% styrene and 2% allyl methacrylate, The outer layer is a hard polymer obtained by polymerizing a monomer component consisting of 94% methyl methacrylate and 6% methyl acrylate. The inner layer (hard polymer layer) / intermediate layer (elastic polymer layer) ) / Outer layer (hard polymer layer) weight ratio of 35/45/20 was used, and spherical three-layer rubber particles obtained by an emulsion polymerization method were used. The average particle diameter of the elastic polymer portion (the hard polymer layer as the inner layer + the elastic polymer layer as the intermediate layer) in the acrylic rubber particles (2) was measured to be 220 nm.

Next, using the 65 mmφ single screw extruder (manufactured by Toshiba Machine Co., Ltd.), the polycarbonate resin composition as the layer (A) forming material is layered using a 45 mmφ single screw extruder (manufactured by Toshiba Machine Co., Ltd.). The methacrylic resin composition as the forming material of (B) is melted and melt-laminated and integrated by a feed block method, extruded through a T-shaped die with a set temperature of 265 ° C., and the resulting film-like product is A film (multilayer film) was produced by sandwiching and molding between a pair of metal rolls having a smooth surface. At this time, in Examples 1 to 3, Examples 7 to 9, Comparative Example 1, and Comparative Examples 3 and 4, the melt lamination was performed so as to have a three-layer configuration of layer (B) / layer (A) / layer (B). In Examples 4 to 6 and Comparative Example 2, fusion lamination was performed so as to obtain a two-layer structure of layer (B) / layer (A). In Comparative Example 5, 1 of layer (B) The melted methacrylic resin composition alone was extruded to have a layer structure, and in Comparative Example 6, the molten polycarbonate resin composition was extruded alone to have a single layer structure of the layer (A).
The following evaluation was performed about each obtained film (multilayer film). The results are shown in Table 1.

<Impact resistance (absorbed energy in Charpy impact test)>
First, a strip-shaped test piece of 10 mm × 120 mm was cut out from the obtained multilayer film with a cutter. At this time, ten test pieces (test pieces in the MD direction) cut out so that the long sides of the test pieces are parallel to the film forming direction, and the long sides of the test pieces are perpendicular to the film forming direction. Ten test pieces (test pieces in the TD direction) cut out so as to be prepared were prepared.
Next, double-sided pressure-sensitive adhesive tape ("bond double-sided tape fixing" Konishi) is attached to the test piece support so that each test piece is impacted from the direction perpendicular to the plane of the test piece (the film surface before cutting). The Charpy impact test was performed according to JIS-K7111, and the absorbed energy (J) required to break the test piece was measured. And the average value of 10 test pieces was calculated | required for every direction, and this was made into the absorbed energy (J) of each direction. It can be said that the larger the absorbed energy (J) in each direction, the stronger the impact resistance and the stronger the film.

<Strength (tensile fracture strain)>
First, a strip-shaped test piece of 10 mm × 150 mm was cut out from the obtained multilayer film with a cutter. At this time, five test pieces (test pieces in the MD direction) cut out so that the long sides of the test pieces are parallel to the film forming direction, and the long sides of the test pieces are perpendicular to the film forming direction. Five test pieces (test pieces in the TD direction) cut out so as to be prepared were prepared.
Next, each test piece was tested according to JIS-K7127 using an Instron universal testing machine (Instron "INSTRON5500R") under conditions of 50 mm between chucks, temperature 25 ° C, and speed 50 mm / min. The film was stretched until it was broken, and the tensile fracture strain (%) or the preliminary strain at tensile fracture (%) was measured. And the average value of five test pieces was calculated | required for each direction, and this was made into the tensile fracture strain (%) of each direction. It can be said that the larger the tensile fracture strain (%) in each direction, the better the elongation and the stronger the strong film.

<Flexibility>
According to JIS-K5600-5-1: 1999, the bending resistance when the obtained multilayer film was folded in half was evaluated according to the following criteria.
○: The film does not break and the flexibility is good ×: The film breaks and lacks flexibility

<Whitening resistance>
According to JIS-K5600-5-1: 1999, the bending resistance when the obtained multilayer film was folded in half was evaluated according to the following criteria.
○: The bent portion of the film is transparent without whitening. ×: Whitening is observed at the bent portion of the film.

<Crack>
The obtained multilayer film was folded in half, and the presence or absence of cracks in the vicinity of the crease or breakage of the film was visually observed and evaluated according to the following criteria.
○: No cracks are observed △: Slightly negligible micro cracks are observed ×: Cracks are observed

<Surface hardness (pencil hardness)>
It measured according to JIS-K-5600-5-4.

<Ease of forming (maximum stress)>
From the obtained multilayer film, a strip-shaped test piece of 10 mm × 150 mm was cut out with a cutter so that the long side thereof was parallel to the film forming direction, and the obtained test piece was converted into an Instron universal testing machine ( Using an Instron "INSTRON 5500R"), the test piece was stretched under the conditions of 50 mm between chucks, a temperature of 140 ° C, and a speed of 50 mm / min until the maximum stress (kgf) during stretching was measured. In the normal injection molding simultaneous bonding method, the temperature of the film surface at the time of preforming such as vacuum forming or pressure forming is about 140 to 160 ° C. Therefore, the smaller the maximum stress at stretching at 140 ° C., the easier the forming. It can be said that.

Claims (17)

A methacrylic resin composition (b) containing a methacrylic resin and acrylic rubber particles on at least one surface of the layer (A) comprising the thermoplastic resin composition (a) containing a thermoplastic resin other than the methacrylic resin as a resin component. A multilayer film in which a layer (B) comprising:
The glass transition temperature TgA (° C.) of the thermoplastic resin composition (a) and the glass transition temperature TgB (° C.) of the methacrylic resin composition (b) satisfy the formula: TgA-TgB <25, and the acrylic A multilayer film, wherein the average particle diameter of the elastic polymer part in the rubber-based rubber particles is 100 nm or less.   The multilayer film according to claim 1, wherein the thermoplastic resin composition (a) comprises a polycarbonate resin as a resin component.   The multilayer according to claim 2, wherein the thermoplastic resin composition (a) contains a polycarbonate resin and a plasticizer in a ratio of polycarbonate resin: plasticizer (weight ratio) = 70: 30 to 99: 1. the film.   The multilayer film according to claim 3, wherein the plasticizer is a phosphate ester compound.   The methacrylic resin composition (b) contains methacrylic resin and acrylic rubber particles in a ratio of methacrylic resin: acrylic rubber particles (weight ratio) = 20: 80 to 85:15. The multilayer film in any one of -4.   The multilayer according to any one of claims 1 to 5, wherein the methacrylic resin composition (b) contains 0.5 to 10 parts by weight of an ultraviolet absorber with respect to 100 parts by weight of the total of the methacrylic resin and the acrylic rubber particles. the film. The multilayer film of the content of the ultraviolet absorber per unit area in the layer (B) is, according to claim 6, wherein the 0.15~1.5g / m ^2.   The multilayer film according to claim 6 or 7, wherein the ultraviolet absorber is a benzotriazole-based ultraviolet absorber.   The elastic polymer part in the acrylic rubber particles has an alkyl acrylate of 50 to 99, with the total of alkyl acrylate, alkyl methacrylate, monofunctional monomer other than these, and polyfunctional monomer being 100% by weight. .9% by weight, 0 to 49.9% by weight of alkyl methacrylate, 0 to 49.9% by weight of monofunctional monomer, and 0.1 to 10% by weight of polyfunctional monomer The multilayer film in any one of Claims 1-8 containing the elastic polymer formed.   The acrylic rubber particles are formed on the outer side of the elastic polymer part, and the total amount of alkyl methacrylate, alkyl acrylate, other monofunctional monomer, and polyfunctional monomer is 100% by weight. 50-100% by weight, alkyl acrylate 0-50% by weight, monofunctional monomer 0-50% by weight, polyfunctional monomer 0-10% by weight The multilayer film according to any one of claims 1 to 9, which is a particle having a layer made of a polymer.   The total thickness is 20 to 200 µm, the thickness of the layer (A) is 10 to 80% of the total thickness, and the thickness of the layer (B) is 10 µm or more. The multilayer film in any one.   The multilayer film according to any one of claims 1 to 11, wherein the thermoplastic resin composition (a) and the methacrylic resin composition (b) are coextruded.   The multilayer film according to any one of claims 1 to 12, wherein the surface on the layer (A) side is decorated with respect to the multilayer film in which the layer (B) is laminated on one surface of the layer (A). A decorative film characterized by being applied.   Of the multilayer film according to any one of claims 1 to 12, a decoration is applied to either side of the multilayer film in which the layer (B) is laminated on both sides of the layer (A). A decorative film characterized in that   A decorative sheet comprising a thermoplastic resin sheet laminated on a surface on the decorative side of the decorative film according to claim 13 or 14.   A decorative molded product, wherein a thermoplastic resin is injection-molded on the surface of the decorative film of the decorative film according to claim 13 or 14.   A decorative molded product, wherein a thermoplastic resin is injection-molded on the surface of the decorative sheet according to claim 15 on the side of the thermoplastic resin sheet.