JP5591525B2 - Matte resin film - Google Patents

Description

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

  One of the methods for decorating the surface of various plastic molded products is a method of imparting design properties such as a sense of quality and depth by making the surface of the molded product matt. In order to make the surface of the molded product matt, there is a method of forming a matt shape (irregularities etc.) directly on the surface of the molded product by thermal processing or the like, but in recent years, it is advantageous in terms of productivity and cost. There is a tendency that a film bonding method such as a simultaneous injection molding method is adopted. For example, in the case of the injection molding simultaneous bonding method, the matte resin film is inserted into an injection mold after being pre-formed into a three-dimensional shape by vacuum molding or pressure forming, or without being molded, By injecting the molten resin, a matte resin film can be bonded to the injection molded product simultaneously with the formation of the injection molded product.

  As the matte resin film used when trying to obtain a molded product having a matte shape on the surface by the film laminating method, a resin film having a multilayer structure including a mat layer (matte layer) is suitable. It is known. This mat layer is generally formed of a material containing a light diffusing material or matting agent (transparent fine particles, etc.) in an acrylic resin. For example, a light diffusing material containing a light diffusing material in an acrylic resin. A matte plate in which a layer (mat layer) is laminated on both sides or one side of a synthetic resin layer has been proposed (Patent Document 1). Here, examples of the synthetic resin layer on which the mat layer is laminated include layers made of acrylic resin, polycarbonate resin, polystyrene resin, and vinyl chloride resin. In general, from the viewpoint of the mechanical strength of the film, polycarbonate is used. It is known that resins are suitable.

Japanese Patent Laid-Open No. 11-179856

  However, in the case of a film in which a mat layer containing an acrylic resin and a light diffusing material is laminated on both sides of a polycarbonate resin layer, when the film is put on a molded product as a matte resin film, There is a problem that the glossiness and glossiness of the product and the glossiness and glossiness of the molded product after bonding are greatly different, and a molded product having a desired appearance cannot be obtained. In addition, in the case of a film in which a mat layer containing a light diffusing material in an acrylic resin is laminated only on one side of a polycarbonate resin layer, an attempt is made to decorate the matte resin film by printing or the like on the polycarbonate resin layer side. In this case, there is a problem that the range of designability that can be imparted becomes narrow because the paint that can be used favorably with respect to the polycarbonate resin is limited.

  Therefore, the object of the present invention is that, when bonded to a molded product, there is little change in glossiness and glossiness before and after the bonding, and a molded product having a desired appearance can be obtained, printing, etc. We provide a matte resin film that can be applied with a wide range of design properties with few restrictions on decoration, and also provides a decorative film, a decorative sheet, and a decorative molded product using this film. There is to do.

  The present inventor has intensively studied to solve the above problems. As a result, in the multilayer film in which the methacrylic resin layer (B) is laminated on one surface of the polycarbonate resin layer (A), the surface (α) located on the polycarbonate resin layer (A) side of the multilayer film has fine irregularities on the surface. By having a matte surface, it is possible to print on a methacrylic resin layer that can be used with a wide range of paints with little restrictions on the paints that can be used when decorating the resulting matte resin film. The arithmetic average roughness Ra1 of this surface (α) and the arithmetic average roughness Ra2 of the other surface (β) located on the methacrylic resin layer (B) side of the multilayer film are expressed by the formula: (Ra1-Ra2) /Ra1>0.10, it has been found that the change in glossiness and glossiness before and after being bonded to a molded product can be suppressed by satisfying a predetermined relationship. It was completed.

That is, this invention consists of the following structures.
(1) A methacrylic resin layer (B) made of a resin material (B) containing methacrylic resin as a resin component is laminated on one side of a polycarbonate resin layer (A) made of a resin material (A) containing polycarbonate resin as a resin component. The surface (α) of the multilayer film located on the polycarbonate resin layer (A) side of the multilayer film is a mat surface having fine irregularities on the surface, and the arithmetic average roughness Ra1 of this surface (α) And the arithmetic average roughness Ra2 of the surface (β) located on the methacrylic resin layer (B) side of the multilayer film satisfies the formula: (Ra1-Ra2) / Ra1> 0.40 Eraser resin film.
(2) The matte resin film according to (1), wherein the arithmetic average roughness Ra2 is 0.25 or less.
(3) The glass transition temperature TgA (° C.) of the resin material (A) and the glass transition temperature TgB (° C.) of the resin material (B) satisfy the formula: TgA−TgB <25 (1) or ( The matte resin film as described in 2).
(4) The matte resin film according to (3), wherein the resin material (A) contains a plasticizer in a ratio of polycarbonate resin: plasticizer (weight ratio) = 70: 30 to 99: 1.
(5) The matte resin film according to (4), wherein the plasticizer is a phosphate ester compound.
(6) Said surface ((alpha)) which is a mat surface is comprised from the mat layer (C) which consists of a resin material (C) which uses methacrylic resin as a resin component and contains transparent fine particles, (1)-(5) ) The matte resin film according to any one of the above.
(7) The resin material (B) contains transparent fine particles (however, the TgB of the resin material (B) is a value measured in a state not containing the transparent fine particles) (1) to (6 ) The matte resin film according to any one of the above.
(8) The content ratio of the methacrylic resin and the transparent fine particles in the resin material (B) and / or the resin material (C) is methacrylic resin: transparent fine particles (weight ratio) = 60: 40 to 99: 1 The matte resin film as described in (6) or (7).
(9) The matte according to any one of (6) to (8), wherein the volume average particle diameter of the transparent fine particles contained in the resin material (B) and / or the resin material (C) is 3 to 10 μm. Resin film.
(10) The matte resin film according to any one of (6) to (9), wherein the transparent fine particles contained in the resin material (B) and / or the resin material (C) are acrylic crosslinked particles.
(11) The difference (| Nd−Nb |) between the refractive index (Nd) of the transparent fine particles and the refractive index (Nb) of the methacrylic resin in the resin material (B) and / or the resin material (C) is 0.01. The matte resin film according to any one of the above (6) to (10).
(12) The resin material (B) and / or the resin material (C) contains acrylic rubber particles in a ratio of methacrylic resin: acrylic rubber particles (weight ratio) = 20: 80 to 99: 1. The matte resin film according to any one of (1) to (11).
(13) The acrylic rubber particles are alkyl acrylate, alkyl methacrylate, monofunctional monomer and polyfunctional monomer other than these as 100% by weight, and alkyl acrylate is 50 to 99.9%. %, 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 matte resin film according to (12), wherein the matte resin film is a particle having an elastic polymer portion including an elastic polymer layer.
(14) The acrylic rubber particles, on the outside of the elastic polymer layer, the total of alkyl methacrylate, alkyl acrylate, other monofunctional monomer and polyfunctional monomer 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 are polymerized. The matte resin film according to the above (13), which is a particle having a multilayer structure provided with a hard polymer layer.
(15) The acrylic rubber particles are, on the inner side of the elastic polymer layer, the alkyl methacrylate, alkyl acrylate, other monofunctional monomer and polyfunctional monomer as a total of 100% by weight, 70-100% by weight of alkyl methacrylate, 0-30% by weight of alkyl acrylate, 0-30% by weight of monofunctional monomer, and 0-10% by weight of polyfunctional monomer are polymerized. The matte resin film according to the above (13) or (14), which is a particle having a multilayer structure having a hard polymer layer.
(16) The matte resin film according to any one of (13) to (15), wherein the number average particle diameter of the elastic polymer portion is 100 nm or less.
(17) The resin material (B) and / or the resin material (C) contains 0.5 to 10% by weight of an ultraviolet absorber with respect to the total amount of the resin material for each resin material. The matte resin film according to any one of (1) to (16).
(18) The thickness of the entire matte resin film is 20 to 200 μm, the thickness of the polycarbonate resin layer (A) is 10 to 90% of the thickness of the entire matte resin film, and the methacrylic resin layer (B ) The matte resin film according to any one of (1) to (17), wherein the thickness is 5 μm or more.
(19) The matte resin film according to any one of (1) to (18), wherein each resin material constituting the multilayer film is coextruded.

(20) A decorative film, wherein the surface (β) of the matte resin film according to any one of (1) to (19) is decorated.
(21) A decorative sheet, wherein a thermoplastic resin sheet is laminated on a surface on the decorative side of the decorative film according to (20).
(22) A decorative molded product, wherein a thermoplastic resin is injection-molded on the surface on the decorative side of the decorative film according to (20).
(23) A decorative molded product, wherein a thermoplastic resin is injection-molded on a surface of the decorative sheet according to (21) on the thermoplastic resin sheet side.

  According to the present invention, when bonded to a molded product, there is little change in glossiness and glossiness before and after bonding, and a molded product having a desired appearance can be obtained, and addition by printing or the like can be performed. It is possible to provide a matte resin film with few restrictions on decoration and capable of imparting a wide range of design properties. And if a decorative film or a decorative sheet using this matte resin film is used, it has a desired gloss and gloss as expected from the film, and a wide range of design properties are given by printing or the like. The effect that various plastic molded articles can be obtained easily is acquired.

  The matte resin film of the present invention has a methacrylic resin layer made of a resin material (B) containing a methacrylic resin as a resin component on one side of a polycarbonate resin layer (A) made of a resin material (A) containing a polycarbonate resin as a resin component. (B) is a multilayer film laminated at least. In the present invention, of the two surfaces of the multilayer film, a surface located on the polycarbonate resin layer side is referred to as a surface (α), and a surface located on the methacrylic resin layer (B) side is referred to as a surface (β).

  In the matte resin film of the present invention, the surface (α) located on the polycarbonate resin layer (A) side is a mat surface having fine irregularities on the surface. In this way, when the polycarbonate resin layer (A) side (in other words, the opposite side of the methacrylic resin layer (B)) is the mat surface, the matte resin film obtained is subjected to decoration such as printing. Since it is applied to the methacrylic resin layer, there are few restrictions on the paints that can be used, and it is possible to print favorably using various paints, and there is an advantage that the range of design properties that can be imparted is widened.

  For the fine irregularities on the surface (α), for example, i) a material that contains transparent fine particles together with the resin component is used as a material for forming the layer constituting the surface (α), or ii) the surface (α) is formed. After forming the layer forming material into a film, it can be formed by either embossing the surface or using i) and ii) in combination. In particular, the method of i) containing transparent fine particles is preferable because it is simple and can employ coextrusion molding described later. More preferably, a material containing methacrylic resin as a resin component is also used in the method i). That is, the surface (α) in the matte resin film of the present invention is preferably composed of a mat layer (C) made of a resin material (C) containing methacrylic resin as a resin component and containing transparent fine particles. . In addition, about the resin material (C), the same description as the resin material (B) mentioned later can be applied fundamentally.

In the matte resin film of the present invention, the arithmetic average roughness Ra1 of the surface (α) and the arithmetic average roughness Ra2 of the surface (β) are expressed by the formula: (Ra1-Ra2) / Ra1> 0.40. It is important to satisfy, preferably the formula: (Ra1-Ra2) / Ra1> 0.45. Thereby, the change of the glossiness and glossiness before and after bonding to a molded article can be suppressed.
The value of the arithmetic average roughness Ra1 of the surface (α) and the value of the arithmetic average roughness Ra2 of the surface (β) are not particularly limited, but the glossiness and glossiness before and after being bonded to a molded product are not limited. In order to sufficiently suppress the change, the upper limit of Ra2 is preferably 0.25 or less, and more preferably 0.20 or less. The arithmetic average roughness Ra1 of the surface (α) and the arithmetic average roughness Ra2 of the surface (β) can be measured by, for example, the methods described in the examples described later.

  The resin material (A), which is a material for forming the polycarbonate resin layer (A), uses a polycarbonate resin as a resin component. Thus, by including a polycarbonate resin as a forming material of the polycarbonate resin layer (A), the resulting matte resin film exhibits excellent mechanical strength.

  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. In addition, only 1 type may be sufficient as polycarbonate resin, and 2 or more types may be sufficient as it.

  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.

The resin material (A) preferably contains a plasticizer. Since the glass transition temperature (TgA) of the resin material (A) is lowered when a plasticizer is contained, it is possible to adjust the value of TgA-TgB, which will be described later, within a predetermined range by appropriately containing a plasticizer. As a result, the moldability of the matte resin film obtained can be improved.
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 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-ethylhexyl) trimellitic acid ester compounds such as trimellitate; dimethyl adipate, dibuty Adipate, diisobutyl adipate, bis (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, diisodecyl adipate, bis (butyl diglycol) 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. Among these, a phosphoric acid ester-based compound is preferable in terms of excellent compatibility with the polycarbonate resin and transparency of the resin material (A) after the compatibility, and in particular, cresyl diphenyl phosphate and tricresyl phosphate are preferable. More preferred. In addition, only 1 type may be sufficient as a plasticizer, and 2 or more types may be sufficient as it.

  When the plastic material is contained in the resin material (A), the content is usually set at a ratio of polycarbonate resin: plasticizer (weight ratio) = 70: 30 to 99: 1. Preferably, it is set at a ratio of polycarbonate resin: plasticizer (weight ratio) = 90: 10 to 98: 2. If the amount of the plasticizer is less than the above-described ratio, the matte resin layer film obtained may have insufficient moldability. On the other hand, when the amount of the plasticizer is larger than the above-described ratio, the fluidity of the resin material (A) is remarkably increased. For example, when a film is produced by a method of coextrusion molding of each resin material as described later. The appearance may be damaged.

The resin material (B), which is a material for forming the methacrylic resin layer (B), uses 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, in order to adjust to a desired glass transition temperature or to obtain a viscosity exhibiting suitable moldability, it is preferable to use a chain transfer agent during the polymerization. The amount of the chain transfer agent may be appropriately determined according to the type of monomer component and the composition thereof.

The resin material (B) preferably contains acrylic rubber particles. By including acrylic rubber particles, the flexibility and strength of the resulting matte resin film can be improved.
The acrylic rubber particles may be particles having an elastic polymer portion including at least a layer made of an elastic polymer mainly composed of an acrylate ester (elastic polymer layer). The particle | grains which have a multilayer structure also including the layer (hard polymer layer) which consists of coalescence may be sufficient. 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 including at least an elastic polymer. Specifically, when the acrylic rubber particles are single-layer particles made of only an elastic polymer, Meaning all acrylic rubber particles, 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 weight It shall mean the inside covered with the combined 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.

Specific examples of the acrylic rubber particles include alkyl acrylate, alkyl methacrylate, monofunctional monomer and polyfunctional monomer other than these as 100% by weight, and alkyl acrylate of 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 particle | grains which have an elastic polymer part containing the elastic polymer layer made to be made are mentioned preferably.
More preferably, the acrylic rubber particles are: i) 100% by weight of the total of alkyl methacrylate, alkyl acrylate, other monofunctional monomer and polyfunctional monomer outside the elastic polymer layer. The alkyl methacrylate is 50 to 100% by weight, the alkyl acrylate is 0 to 50% by weight, the monofunctional monomer is 0 to 50% by weight, and the polyfunctional monomer is 0 to 10% by weight. Or ii) an alkyl methacrylate, an alkyl acrylate, a monofunctional monomer other than these, and a polyfunctional monomer. The total of the monomer is 100% by weight, the alkyl methacrylate is 70 to 100% by weight, the alkyl acrylate is 0 to 30% by weight, the monofunctional monomer is 0 to 30% by weight, and the polyfunctional monomer 0-10 It may be between layered particles having a hard polymer layer formed by polymerizing and quantity%. It is also preferable to use particles having a multilayer structure including the hard polymer layer i) outside the elastic polymer layer and the hard polymer layer ii) inside the elastic polymer layer. Of course.

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 this alkyl acrylate, 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, this alkyl methacrylate may be only 1 type, and 2 or more types may be sufficient as it.
The monofunctional monomer optionally used in forming the elastic polymer layer is a monofunctional monomer constituting the methacrylic resin (a monomer copolymerizable with alkyl methacrylate or alkyl acrylate). Examples thereof include those similar to those described above, and among them, aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene are preferable. In addition, only 1 type may be sufficient as this other monofunctional monomer, 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, this polyfunctional monomer may be only 1 type, and 2 or more types may be sufficient as it.

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, this alkyl methacrylate may be only 1 type, 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 this 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 this other 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, this polyfunctional monomer may be only 1 type, and 2 or more types may be sufficient as it.

  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.

  The number average particle diameter of the elastic polymer portion in the acrylic rubber particles is preferably 100 nm or less, and more preferably 90 nm or less. When the number 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 number average particle diameter of the elastic polymer portion 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. be able to.

  When acrylic rubber particles having a layer structure in which the outermost layer (outer layer) is a hard polymer layer are used, the number average particle diameter of the elastic polymer portion (that is, the outermost layer among the layers constituting the acrylic rubber particles) The number average particle diameter of the particles excluding the hard polymer layer outside the elastic polymer layer is mixed with a methacrylic resin containing the acrylic rubber particles in the resin material (B), for example. 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.

When the acrylic rubber particles are contained in the resin material (B), the content is usually set at a ratio of methacrylic resin: acrylic rubber particles (weight ratio) = 20: 80 to 99: 1. It is preferable to set the ratio of methacrylic resin: acrylic rubber particles (weight ratio) = 40: 60 to 75:25. If the amount of acrylic rubber particles is less than the above-mentioned ratio, the effect of improving flexibility and strength may be insufficient. On the other hand, if the amount is more than the above-mentioned ratio, the surface hardness of the matte resin film to be obtained (Pencil hardness) may decrease.
The acrylic rubber particles may be contained in the resin material (C), which is a material for forming the mat layer (C), instead of the resin material (B) or together with the resin material (B).

  The resin material (B) can contain transparent fine particles. About the transparent fine particle which can be contained here, the same description as the transparent fine particle in the resin material (C) mentioned later is applicable.

  The glass transition temperature TgA (° C.) of the resin material (A) and the glass transition temperature TgB (° C.) of the resin material (B) preferably satisfy the formula: TgA−TgB <25. Thereby, the obtained matte resin film will have favorable moldability, for example, a decorative molded product can be easily manufactured by the simultaneous injection molding method. However, when the resin material (B) contains transparent fine particles, the TgB of the resin material (B) is a value measured in a state not containing the transparent fine particles. In addition, TgA and TgB can be measured by the method as described in the Example mentioned later, for example.

  As described above, the resin material (C) that is a material for forming the mat layer (C) contains transparent fine particles in order to provide fine irregularities on the surface of the mat layer (C). Examples of the transparent fine particles include acrylic and styrene-based crosslinked particles, talc, glass beads, silicone particles, and the like. Among these, acrylic-based crosslinked particles are preferable because the refractive index and size can be easily controlled. For example, acrylic or styrene-based crosslinked particles can be produced by a conventionally known method such as an emulsion polymerization method, a suspension polymerization method, a seed polymerization method, or a dispersion polymerization method. In addition, only 1 type may be sufficient as transparent fine particles, and 2 or more types may be sufficient as it.

  The volume average particle diameter of the transparent fine particles is preferably 3 to 10 μm, more preferably 4 to 9 μm, and further preferably 4.5 to 8 μm. When the volume average particle diameter of the transparent fine particles is less than 3 μm, the surface of the mat layer (C) may be insufficiently uneven unless the transparent fine particles are contained in a large amount, and the transparent fine particle content increases. In addition, it is not economical and the resulting matte resin film may be brittle and easily cracked. On the other hand, when the volume average particle diameter of the transparent fine particles exceeds 10 μm, the applied mat feeling may be rough.

  The transparent fine particles have a refractive index (Nd) and methacrylic resin in the resin material (C) (in the case of transparent fine particles contained in the resin material (B), the methacrylic resin in the resin material (B). ) With respect to the refractive index (Nb) (| Nd−Nb |) is preferably 0.01 or less, more preferably 0.008 or less, and even more preferably 0.005 or less. When this difference in refractive index (| Nd−Nb |) exceeds 0.01, when one surface of the resulting matte resin film is decorated, the decorative surface is moved from the opposite mat surface side. When viewed, the decoration may become cloudy and unclear.

  The content of the transparent fine particles in the resin material (C) is usually set at a ratio of methacrylic resin: transparent fine particles (weight ratio) = 60: 40 to 99: 1 in the resin material (C). The ratio is preferably set at a ratio of methacrylic resin: transparent fine particles (weight ratio) = 65: 35 to 98: 2. If the amount of the transparent fine particles is less than the above-mentioned ratio, the fine irregularities on the surface of the mat layer (C) may be insufficient. On the other hand, if the amount is larger than the above-mentioned ratio, the resulting matte resin film may be It may be brittle and easy to break.

  The resin material (A), the resin material (B), and the resin material (C) can each contain various additives within a range that does not impair the effects of the present invention, if necessary. Examples of additives include organic dyes, inorganic dyes, pigments, antioxidants, ultraviolet absorbers, antistatic agents, surfactants, lubricants, flame retardants such as silicone compounds, fillers, glass fibers, and impact resistance. Property modifiers and the like. In particular, the resin material (B) and / or the resin material (C) preferably contains an ultraviolet absorber. Thereby, the photodegradation of a polycarbonate resin layer (A) can also be suppressed, and it can be set as the matte resin film which has the ultraviolet cut ability which is hard to yellow for a long term.

  Examples of the ultraviolet absorber include a benzotriazole ultraviolet absorber, a benzoate ultraviolet absorber, a salicylic acid derivative ultraviolet absorber, a substituted acrylonitrile ultraviolet absorber, a nickel complex ultraviolet absorber, a benzophenone ultraviolet absorber, and a triazine. System ultraviolet absorbers and the like. 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 resin material (B) and / or the resin material (C) contains an ultraviolet absorber, the content is usually 0.5 to 10 weights for each resin material relative to the total amount of the resin material. %, Preferably 1 to 5% by weight. When the content of the UV absorber is less than the above range, the UV-cutting ability of the matte resin film tends to be insufficient. On the other hand, when the content is more than the above range, the UV absorber can be used when producing the matte resin film. The heat volatilization may cause deterioration of the working environment and equipment contamination, and may cause problems such as surface roughness on the resulting film.

  The matte resin film of the present invention comprises at least a polycarbonate resin layer (A) formed by filming the resin material (A), and a methacrylic resin layer (B) formed by filming the resin material (B). As described above, the mat layer (C) formed by forming the resin material (C) into a film can also be laminated. The production method is not particularly limited. For example, the material for forming each layer (resin material (A), resin material (B), and if necessary, resin material (C)) is melted in an extruder, and a feed block is formed. One of the layer forming materials (coextrusion molding method) by the co-extrusion method or the multi-manifold method, and the other layer is formed on the surface of this film. A method of coating the forming material by dissolving the forming material in a solvent as required is preferably employed. In particular, the matte resin film of the present invention is preferably formed by co-extrusion of each resin material in terms of a simple manufacturing process.

  When a matte resin film is obtained by a coextrusion molding method, the melted layer forming material (resin material (A), resin material (B) and, if necessary, resin material (C)) is brought into close contact with a roll or belt. Turn into. At this time, the number, arrangement, material and the like of the rolls and belts are not particularly limited. For example, the melt (melted layer forming material) is brought into contact between the two metal rolls or between the metal roll and the metal belt. It is preferable to allow the surface of the roll or belt to be transferred by passing the film because the surface accuracy of the film surface can be improved and the decorating property can be improved. In addition, when a metal rigid roll (ordinary metal roll) and a metal elastic roll (metal roll having an elastic surface) are used, both sides of the melt (melted layer forming materials) are brought into contact with each other and formed. It is preferable because a film with less time distortion and less anisotropy in strength and heat shrinkability 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. When the melt is sandwiched between the metal elastic roll and the metal rigid roll, the metal elastic roll is elastically deformed into a concave shape along the outer peripheral surface of the metal rigid roll via the melt. Thereby, since a metal rigid roll and a metal elastic roll are crimped | bonded by surface contact with respect to a melt, the melt pinched | interposed between these rolls will be shape | molded, pressing uniformly in planar shape.

  In particular, when the mat layer (C) is provided using the resin material (C), the above-described coextrusion molding method may be, for example, a melt extruded from a die (resin material (A), resin material (B). ) And the resin material (C)) are sandwiched between a first cooling roll that is a metal elastic roll and a second cooling roll that is a metal rigid roll, and then the second cooling roll is brought into close contact with the second cooling roll while being wound. What is necessary is just to pinch | interpose between a cooling roll and a 3rd cooling roll, and to wind around a 3rd cooling roll after that and to cool it, and also to use a 4th or subsequent cooling roll. In that case, between the 1st cooling roll and the 2nd cooling roll, the resin material (C) which forms a mat | matte layer (C) is a side which contacts a 1st cooling roll, and a side which contacts a 2nd cooling roll. Although it may be located on any side, it is preferably located on the side in contact with the second cooling roll. When the resin material (C) is positioned on the side in contact with the second cooling roll, the resin material (C) is then positioned outside the third cooling roll. The transparent fine particles pressed into the resin material between the two cooling rolls protrude to the surface of the resin material outside the third cooling roll, and as a result, fine irregularities on the surface of the mat layer (C) Is formed. In addition, in the process in which the resin material (C) is located on the side in contact with the second cooling roll, since a fine uneven shape is formed on the surface of the mat layer (C), on the side in contact with the second cooling roll. Unlike the normal extrusion molding, it is desirable that the resin material (C) cooled in this way is not brought into close contact with the roll between the second cooling roll and the third cooling roll that pass thereafter. Specifically, the roll interval between the second cooling roll and the third cooling roll is preferably maintained larger than the total thickness of the film, and more preferably maintained twice or more the total thickness of the film. Thereby, the surface state of the mat layer (C) has moderate unevenness.

  The matte resin film thus obtained preferably has a total thickness of 20 to 200 μm, more preferably 30 to 150 μm, and even more preferably 50 to 130 μm. If the thickness of the entire matte resin film is too thick, it may take a long time for molding when decorating with the matte resin film, which tends to be disadvantageous in terms of cost. On the other hand, when the thickness of the entire matte resin film is too thin, film formation by extrusion molding etc. becomes mechanically difficult, and the breaking strength of the film is lowered, and the probability of occurrence of defects during film production tends to increase. There is. Note that the thickness of the entire matte resin film can be adjusted by adjusting the film forming speed, the thickness of the discharge port of the T-shaped die, the gap between the rolls, and the like.

The thickness of the polycarbonate resin layer (A) in the matte resin film of the present invention is 10 to 90% of the total thickness of the matte resin film, and the thickness of the methacrylic resin layer (B) (the mat layer ( When C) is provided, the thickness of the mat layer (C) is preferably 5 μm or more. If the thickness of the polycarbonate resin layer (A) is too thin, the matte resin film may be brittle and easily broken, while the polycarbonate resin layer (A) is too thick or the methacrylic resin layer (B). If the thickness of the mat layer (C) is too thin, the surface hardness of the matte resin film may be insufficient. Furthermore, when the thickness of the methacrylic resin layer (B) is too thin, there is a possibility that good printing cannot be performed on the layer (B).
The matte resin film of the present invention as described above is preferably used as a decorative film or a decorative sheet.

  In the decorative film of the present invention, i) the surface (β) of the matte resin film of the present invention is decorated. By using such a decorative film, various plastic molded products that have a desired gloss and luster as expected from the film and that are given a wide range of design properties by printing, etc. can be easily obtained by, for example, the injection molding simultaneous bonding method. Can be obtained.

  The method for decorating the matte resin film is not particularly limited. For example, various designs such as wood grain tone are directly printed on the surface of the matte resin film by continuous gravure printing or silk printing. A method, a method of decorating a metal plating tone by vapor deposition or sputtering, a method of laminating a resin film that has been 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, but for example, ABS (acrylonitrile-butadiene-styrene copolymer) resin, olefin resin, acrylic resin, vinyl chloride resin, polyurethane resin. And polyester resins. Moreover, the thickness of the said thermoplastic resin sheet is 0.1-2 mm normally.

  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 positioned on the surface of the resulting decorative molded product, the desired glossiness and gloss as expected from the film. And a decorative molded product to which a wide range of design properties are imparted by printing or the like is obtained. Here, there is no restriction | limiting in particular as a thermoplastic resin used for injection molding, For example, an ABS resin, an olefin resin, an acrylic resin, a vinyl chloride resin, a polyurethane resin, a polyester resin etc. are mentioned.

  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 Examples and Comparative Examples were measured by the following methods.
<Glass transition temperature>
According to JIS-K7121-1987, differential scanning calorimetry was performed, and the extrapolated glass transition start temperature (° C.) determined at a heating rate of 10 ° C./min was defined as the glass transition temperature.

<Arithmetic mean roughness of film (Ra1, Ra2)>
The obtained film was cut into a 50 mm square with a cutter to prepare a test piece, and the arithmetic average roughness of both surfaces of the film was measured using a surface roughness measuring machine (“SJ-201P” manufactured by Mitutoyo Corporation). did. In the measurement, the cut-off value was 0.8 mm and the evaluation length was 4 mm based on JIS-B0601: 1994. The arithmetic mean roughness value of the surface (α) on the mat layer (C) side (second cooling roll contact side) is Ra1 (μm), and the methacrylic resin layer (B) side (first cooling roll contact side). The arithmetic mean roughness value of the surface (β), which is the surface of, was Ra2 (μm).

In Examples and Comparative Examples, the following were used as methacrylic resin, acrylic rubber particles, and transparent fine particles.
<Methacrylic resin>
The methacrylic resin was obtained by bulk polymerization of a monomer component consisting of 97.8% methyl methacrylate and 2.2% methyl acrylate, having a glass transition temperature of 104 ° C. and a refractive index (Nb) of 1. A 490 thermoplastic polymer pellet was used.

<Acrylic rubber particles>
As the acrylic rubber particles, the inner layer is an elastic polymer obtained by polymerizing a monomer component consisting of 81% butyl acrylate, 17% styrene, and 2% allyl methacrylate, and the outer layer is methyl methacrylate 94. % And 6% of methyl acrylate are polymerized, and the weight ratio of inner layer (elastic polymer layer) / outer layer (hard polymer layer) is 60 / 40, the rubber particles having a spherical two-layer structure obtained by the emulsion polymerization method were used.
The number average particle diameter of the elastic polymer portion (the elastic polymer layer as the inner layer) in the acrylic rubber particles was measured by the following method and found to be 80 nm.

[Number average particle diameter of elastic polymer part in acrylic rubber particles]
Acrylic rubber particles are mixed with the above methacrylic resin to form a film, and the resulting film is cut into an appropriate size, and the slice is immersed in an aqueous 0.5% ruthenium tetroxide solution at room temperature for 15 hours. The elastic 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 number average particle diameter of an elastic polymer part.

<Transparent fine particles>
As the transparent fine particles, crosslinked polymethyl methacrylate particles (“MBX-5H” manufactured by Sekisui Plastics Co., Ltd .; refractive index (Nd) 1.495, volume average particle size 5.1 μm) were used.

(Examples 1 and 2 and Comparative Examples 1 and 2)
First, the resin material (A) was prepared as a forming material of the polycarbonate resin layer (A) as follows. That is, 95 parts of a polycarbonate resin (“Caliver 303-10” manufactured by Sumitomo Dow Co., Ltd., glass transition temperature 145 ° C.) was melted using a 75 mmφ twin screw extruder (manufactured by Toshiba Machine Co., Ltd.) 5 parts of a liquid plasticizer (cresyl diphenyl phosphate (“CDP” manufactured by Daihachi Chemical Industry Co., Ltd.)) was fed with a pump to obtain a resin material (A) in which a polycarbonate resin and a plasticizer were mixed as pellets.
The resin material (A) had a glass transition temperature (TgA) of 117 ° C.

On the other hand, resin materials (resin materials (B) and (C)) were prepared as materials for forming the methacrylic resin layer (B) and the mat layer (C) as follows. That is, methacrylic resin, acrylic rubber particles and transparent fine particles were mixed with a super mixer at a ratio shown in Table 1, and melt kneaded using a 75 mmφ twin screw extruder (manufactured by Toshiba Machine Co., Ltd.) Resin materials (resin materials (B) and (C)) in which methacrylic resin and acrylic rubber particles also contained transparent fine particles were obtained as pellets. One resin material thus obtained (referred to as “resin material (B · C)”) was shared as the resin material (B) and the resin material (C).
The glass transition temperature (TgB) of the resin material (B) was measured using pellets prepared in the same manner as described above except that transparent fine particles were not used, and the results were as shown in Table 1.

Next, the resin material (A) for forming the polycarbonate resin layer (A) using a 65 mmφ single screw extruder (manufactured by Toshiba Machine Co., Ltd.) is used using a 45 mmφ single screw extruder (manufactured by Toshiba Machine Co., Ltd.). The resin materials (B and C) for forming the methacrylic resin layer (B) and the mat layer (C) are melted, respectively, and the mat layer (C) / polycarbonate resin layer (A) / methacrylic resin layer (B) 3 It was melt-laminated and integrated by a feed block method so as to have a layer structure, and extruded through a T-shaped die having a set temperature of 265 ° C. Next, the extruded film-like material is formed by passing it through a cooling unit comprising a first cooling roll that is a metal elastic roll, a second cooling roll that is a metal rigid roll, and a third cooling roll that is a metal rigid roll. A matte resin film was prepared.
In addition, the cooling unit used sandwiched the extruded film-like material between the first cooling roll and the second cooling roll, and then tightly wound the second cooling roll and the second cooling roll. It is sandwiched between three cooling rolls, and then wound around a third cooling roll to cool. When melt lamination was integrated by the feed block method, the mat layer (C) side was set to be in contact with the second cooling roll by adjusting the pins of the feed block. In the cooling unit, the first cooling roll and the second cooling roll are in close contact with the film, and the second cooling roll and the third cooling roll are not in close contact with each other, and the film is spaced by 0.5 mm. I tried to pass. The set temperatures of the first, second and third cooling rolls were the temperatures shown in Table 1.

About the thickness of the obtained matte resin film, the obtained film is cut out to a 50 mm square with a cutter, a test piece is produced, the cross section is observed with an optical microscope, the thickness of the whole film, layer (A) When the thickness of the layer and the thickness of the layer (B) were measured, they were as shown in Table 1.
The arithmetic average roughness of each surface of the matte resin film obtained was as shown in Table 2.
The difference (| Nd−Nb |) between the refractive index (Nd) of the transparent fine particles and the refractive index (Nb) of the methacrylic resin in the methacrylic resin layer (B) and the mat layer (C) of the matte resin film obtained. Is 0.005.

The following evaluation was performed about each obtained film (matte resin film). The results are shown in Table 2.
<Haze (H)>
The obtained film was cut into a 50 mm square with a cutter to produce a test piece, and a mat layer (C) side was prepared using a haze meter / reflectometer ("HR-100" manufactured by Murakami Color Research Laboratory Co., Ltd.). Measurement was performed according to JIS-K7136, with (second cooling roll contact side) as the light source side.

<60 degree specular gloss (Gs)>
About the test piece used for the measurement of haze, using a gloss meter ("GM-268" manufactured by Minolta Co., Ltd.), the surface (α) that is the surface on the mat layer (C) side (second cooling roll contact side) (α ) Surface 60 ° specular gloss (Gs (α)) and the surface of the surface of the methacrylic resin layer (B) side (first cooling roll contact side) (β) 60 ° specular gloss (Gs (β)) was measured according to JIS-Z8741.

<60 degree specular gloss at the time of bonding (Gs')>
Water is applied to the surface of the methacrylic resin plate (molded body), and the same test piece (matte resin film cut to 50 mm square) used for haze measurement is placed on the applied water and molded. A matte resin film was adhered to and bonded to the surface of the body to produce a molded article with a film. When placing a test piece (matte resin film) on water, the film mat layer (C) is present on the surface of the resulting molded article with film (in other words, the methacrylic resin layer of the film). (B) in contact with water.
The 60 ° specular glossiness of the film surface (that is, the surface (α) which is the surface on the mat layer (C) side (second cooling roll contact side)) bonded to the obtained molded article with film is the Gs described above. The measurement was performed in the same manner as the measurement method, and the obtained value was defined as 60 ° specular gloss (Gs (α) ′) at the time of bonding. The smaller the difference between Gs (α) 'and Gs (α) (Gs (α)'-Gs (α)), the more glossy and glossy it is before and after bonding when bonded to a molded product. It can be said that there is little change.

<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 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 (Konishi Co., Ltd. “Bonded Both Sides” is applied to each test piece so that impact is applied from the direction perpendicular to the plane of the test piece (film surface before cutting). It was fixed with “for tape fixation”), and a Charpy impact test was conducted 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 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 (“INSTRON5500R” manufactured by Instron) under conditions of 50 mm between chucks, 25 ° C. temperature and 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 obtained film was folded in half on the layer (B) side and the layer (C) side, respectively. Evaluated by criteria.
○: Film does not break and flexibility is good ×: Film breaks and lacks flexibility <Whitening resistance>
According to JIS-K5600-5-1: 1999, the obtained film was folded in half on the layer (B) side and the layer (C) side, respectively. Evaluated by criteria.
○: The bent portion of the film is transparent without whitening. ×: Whitening is observed in the bent portion of the film <Surface hardness (pencil hardness)>
In accordance with JIS-K-5600-5-4, the surface hardness of the surface (α), which is the surface of the resulting film on the mat layer (C) side (second cooling roll contact side), was measured.

<Formability (maximum stress)>
A 10 mm × 150 mm strip-shaped test piece was cut out from the obtained film with a cutter so that the long side thereof was parallel to the film forming direction, and the obtained test piece was cut into an Instron universal testing machine (Instrument tester). Using “INSTRON5500R” manufactured by Ron Co., Ltd., the test piece was stretched under 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. Generally, since the temperature of the film surface at the time of preliminary molding (vacuum molding, pressure forming, etc.) in the ordinary simultaneous injection molding method is about 140 to 160 ° C., the smaller the maximum stress during stretching at 140 ° C., the lower the molding Can be said to be easy.

Claims (20)

A multilayer film in which a methacrylic resin layer (B) made of a resin material (B) containing methacrylic resin as a resin component is laminated on one side of a polycarbonate resin layer (A) made of a resin material (A) containing polycarbonate resin as a resinous component Because
The surface (α) located on the polycarbonate resin layer (A) side of the multilayer film is a mat surface having fine irregularities on the surface, the arithmetic average roughness Ra1 of this surface (α), and the methacrylic surface of the multilayer film. an arithmetic mean roughness Ra2 of the surface located on the resin layer (B) side (beta) has the formula: meets the (Ra1-Ra2) / Ra1> 0.40,
The arithmetic average roughness Ra1 is 0.17 to 0.26, the arithmetic average roughness Ra2 is 0.25 or less,
The surface (α) is composed of a mat layer (C) made of a resin material (C) containing methacrylic resin as a resin component and containing transparent fine particles,
The thickness of the whole film is 20 to 200 μm, the thickness of the polycarbonate resin layer (A) is 10 to 90% of the thickness of the whole film, and the thickness of the methacrylic resin layer (B) is 5 μm or more. Is,
Matte resin film characterized by that. The matte resin according to claim 1, wherein the glass transition temperature TgA (° C) of the resin material (A) and the glass transition temperature TgB (° C) of the resin material (B) satisfy the formula: TgA-TgB <25. the film. The matte resin film according to claim 2 , wherein the resin material (A) contains a plasticizer in a ratio of polycarbonate resin: plasticizer (weight ratio) = 70: 30 to 99: 1. The matte resin film according to claim 3 , wherein the plasticizer is a phosphate ester compound. The resin material (B) contains a transparent fine particles (provided that the TgB of the resin material (B) is a value measured in a state that does not contain transparent fine particles) according to any one of claims 1-4 Matte resin film. The content ratio of the methacrylic resin and the transparent fine particles in the resin material (B) and / or the resin material (C) is methacrylic resin: transparent fine particles (weight ratio) = 60: 40 to 99: 1 . The matte resin film according to any one of 5 . The matte resin film according to any one of claims 1 to 6 , wherein a volume average particle diameter of the transparent fine particles contained in the resin material (B) and / or the resin material (C) is 3 to 10 µm. The matte resin film according to any one of claims 1 to 7 , wherein the transparent fine particles contained in the resin material (B) and / or the resin material (C) are acrylic crosslinked particles. The difference (| Nd−Nb |) between the refractive index (Nd) of the transparent fine particles and the refractive index (Nb) of the methacrylic resin in the resin material (B) and / or the resin material (C) is 0.01 or less. The matte resin film according to any one of claims 1 to 8 . The resin material (B) and / or the resin material (C) contains acrylic rubber particles in a ratio of methacrylic resin: acrylic rubber particles (weight ratio) = 20: 80 to 99: 1. matte resin film according to any one of 1-9. The acrylic rubber particles are alkyl acrylate, alkyl methacrylate, monofunctional monomer and polyfunctional monomer other than these as 100% by weight, alkyl acrylate is 50 to 99.9% by weight, Elastic polymer obtained by polymerizing 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 matte resin film according to claim 10 , which is a particle having an elastic polymer portion comprising a layer of The acrylic rubber particles are formed on the outer side of the elastic polymer layer, and the total amount of alkyl methacrylate, alkyl acrylate, other monofunctional monomer and polyfunctional monomer is 100% by weight, and alkyl methacrylate. 50-100% by weight, alkyl acrylate 0-50% by weight, monofunctional monomer 0-50% by weight, polyfunctional monomer 0-10% by weight The matte resin film according to claim 11 , wherein the matte resin film is a particle having a multilayer structure provided with a polymer layer. The acrylic rubber particles are placed on the inner side of the elastic polymer layer, and the alkyl methacrylate is composed of 100% by weight of the total of alkyl methacrylate, alkyl acrylate, other monofunctional monomer and polyfunctional monomer. 70 to 100% by weight, 0 to 30% by weight of alkyl acrylate, 0 to 30% by weight of monofunctional monomer, and 0 to 10% by weight of polyfunctional monomer The matte resin film according to claim 11 or 12 , which is a particle having a multilayer structure provided with a polymer layer. The matte resin film according to any one of claims 11 to 13 , wherein the number average particle diameter of the elastic polymer part is 100 nm or less. 2. The resin material (B) and / or the resin material (C) contains 0.5 to 10% by weight of an ultraviolet absorber with respect to the total amount of the resin material for each resin material. matte resin film according to any one of 1 to 14. The matte resin film according to any one of claims 1 to 15 , wherein each resin material constituting the multilayer film is coextruded. A decorating film, wherein the surface (β) of the matte resin film according to any one of claims 1 to 16 is decorated. A thermoplastic resin sheet is laminated on the surface on the decorative side of the decorative film according to claim 17 . 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 17 . A decorative molded product, wherein a thermoplastic resin is injection-molded on the surface of the decorative sheet according to claim 18 on the side of the thermoplastic resin sheet.