JP5158852B2 - Acrylic resin composition, acrylic resin film, matte acrylic resin film for thermoforming, photocurable acrylic resin film, and laminate obtained by laminating these - Google Patents

Description

  The present invention relates to an acrylic resin composition, an acrylic resin film having excellent heat resistance and molding whitening resistance, a matte acrylic resin film for thermoforming, a photocurable acrylic resin film, and a laminate thereof. About.

  As a method for imparting design properties to a molded product at a low cost, there are an insert molding method and an in-mold molding method. In the insert molding method, a film or sheet of polyester resin, polycarbonate resin, acrylic resin or the like that has been decorated such as printing is formed in advance into a three-dimensional shape by vacuum molding or the like, and unnecessary film or sheet portions are removed. After that, it is a method of transferring into an injection mold and integrating a resin as a base material by injection molding to obtain a molded product. On the other hand, the in-mold molding method is a method in which a film or sheet of polyester resin, polycarbonate resin, acrylic resin or the like subjected to decoration such as printing is placed in an injection mold, vacuum-molded, and then in the same mold In this method, a resin as a base material is integrated by injection molding to obtain a molded product.

  As an acrylic resin film that has excellent surface hardness, heat resistance, and excellent molding whitening resistance that can be used for insert molding and in-mold molding, a rubber-containing polymer having a specific composition and a thermoplastic having a specific composition An acrylic resin film obtained by mixing a polymer with a specific ratio is disclosed (for example, see Patent Document 1). The acrylic resin film not only imparts decorativeness to the molded product, but also has a function as an alternative material for clear coating, and the following (1) to (3) as compared with conventional acrylic resin films Since it is unlikely to cause a decrease in designability due to molding whitening, it has a high industrial utility value.

(1) In insert molding, to remove an acrylic resin film or a laminated sheet laminated with an acrylic resin film after vacuum molding, and in in-mold molding, punching to remove the acrylic resin film protruding from the base resin Whitening occurs at the end of the molded product.

(2) Whitening occurs when a molded product having an undercut design is removed from the mold.

(3) When using a concave or convex mold to obtain a molded product having a convex or concave design such as letters, the acrylic resin film follows the mold even in the concave or convex part after vacuum or pressure forming. In addition, since the base resin must be injection molded in a state where the temperature of the acrylic resin film is Tg or less, whitening is likely to occur when the film is stretched by the resin pressure, and cracks may occur in some cases.

  However, when the acrylic resin film of Patent Document 1 is used, particularly when insert molding is performed, in a punching process for removing unnecessary portions of the acrylic resin film or a laminated sheet including the same after vacuum forming (hereinafter simply referred to as “trimming”). In some cases, the acrylic resin film may be cracked or cracked, and there is room for improvement in trimming processability during molding.

In particular, a matte acrylic resin film for thermoforming provided with a matting layer containing a matting agent and a curable binder resin as an outermost layer on one surface of the acrylic resin film, or a photocurable resin layer was provided. In the case of a photo-curable acrylic resin film, there is a tendency that the generation rate of cracks / cracks tends to be high, and the optimum processing condition width such as the angle at which the blade is applied, the press pressure at the time of punching, and the clearance with the blade is narrow. In addition, improvement has been demanded because it is necessary to pay close attention to the maintenance of the blade used.
JP 2005-163003 A

  The present invention is an acrylic resin film that is excellent in surface hardness, heat resistance and transparency, and that has a molded product that does not whiten when subjected to insert molding or in-mold molding, and has excellent trimming processability during molding. An object of the present invention is to provide an acrylic resin composition suitable for obtaining a resin film.

  Furthermore, this invention aims at providing the acrylic resin film using this acrylic resin composition, the matte acrylic resin film for thermoforming, a photocurable acrylic resin film, and a laminated body using these.

  The gist of the present invention is as follows.

  An acrylic resin composition comprising the following rubber-containing polymer (I) and rubber-containing polymer (II), having a rubber content of 25% by mass or more and a gel content of less than 70% by mass.

Rubber-containing polymer (I);
The following monomer mixture (IA), monomer mixture (IB) and monomer mixture (IC) are combined into monomer mixture (IA) and monomer mixture (IB). ) And the monomer mixture (IC) in this order.

Monomer mixture (IA)
(I-A1) Acrylic acid alkyl ester 50-99.9% by mass
(I-A2) Methacrylic acid alkyl ester 0 to 49.9% by mass
(I-A3) Other monomer having copolymerizable double bond 0 to 20% by mass
(I-A4) Polyfunctional monomer 0 to 10% by mass
(I-A5) Graft crossing agent 0.1 to 10% by mass
In addition, the glass transition temperature calculated | required by the formula of FOX of the polymer obtained from (I-A1)-(I-A3) is less than 25 degreeC.

Monomer mixture (IB)
(I-B1) Acrylic acid alkyl ester 9.9 to 90% by mass
(I-B2) Methacrylic acid alkyl ester 9.9 to 90% by mass
(I-B3) Other monomer having copolymerizable double bond 0 to 20% by mass
(I-B4) Polyfunctional monomer 0 to 10% by mass
(I-B5) Graft crossing agent 0.1 to 10% by mass
In addition, the glass transition temperature calculated | required by the formula of FOX of the polymer obtained from (I-B1)-(I-B3) is 25-100 degreeC.

Monomer mixture (IC)
(I-C1) Methacrylic acid alkyl ester 80-100% by mass
(I-C2) Acrylic acid alkyl ester 0 to 20% by mass
(I-C3) Other monomer having copolymerizable double bond 0 to 20% by mass

Rubber-containing polymer (II);
A rubber-containing polymer obtained by polymerizing a monomer mainly composed of alkyl acrylate and then polymerizing a monomer mainly composed of alkyl methacrylate.

In addition, the glass transition temperature calculated | required by the formula of FOX of the polymer obtained from the monomer which has acrylic acid alkyl ester as a main component is less than 25 degreeC.

The acrylic resin composition containing the rubber-containing polymer (I) and the rubber-containing polymer (II) of the present invention is excellent in surface hardness, heat resistance and transparency, and molded when subjected to insert molding or in-mold molding. Can be provided, and an acrylic resin film excellent in trimming processability during molding, a matte acrylic resin film for thermoforming, a photocurable acrylic resin film, and a laminate using these films can be provided. Furthermore, compared to conventional products, the occurrence of cracks and cracks in trimming processing is small, and the selection range of processing conditions in trimming processing is wide and the industrial utility value is extremely large.

  The gist of the present invention includes an acrylic resin composition and an acrylic resin containing the following rubber-containing polymer (I) and rubber-containing polymer (II), having a rubber content of 25% by mass or more and a gel content of less than 70% by mass It exists in the film, the matte acrylic resin film for thermoforming, the photocurable acrylic resin film, and a laminated body using these. Hereinafter, the present invention will be described in detail.

Rubber-containing polymer (I);
The following monomer mixture (IA), monomer mixture (IB) and monomer mixture (IC) are combined into monomer mixture (IA) and monomer mixture (IB). ) And the monomer mixture (IC) in this order.

Monomer mixture (IA)
(I-A1) Acrylic acid alkyl ester 50-99.9% by mass
(I-A2) Methacrylic acid alkyl ester 0 to 49.9% by mass
(I-A3) Other monomer having copolymerizable double bond 0 to 20% by mass
(I-A4) Polyfunctional monomer 0 to 10% by mass
(I-A5) Graft crossing agent 0.1 to 10% by mass
In addition, the glass transition temperature (henceforth Tg) calculated | required by the formula of FOX of the polymer obtained from (I-A1)-(I-A3) is less than 25 degreeC.

Monomer mixture (IB)
(I-B1) Acrylic acid alkyl ester 9.9 to 90% by mass
(I-B2) Methacrylic acid alkyl ester 9.9 to 90% by mass
(I-B3) Other monomer having copolymerizable double bond 0 to 20% by mass
(I-B4) Polyfunctional monomer 0 to 10% by mass
(I-B5) Graft crossing agent 0.1 to 10% by mass
In addition, Tg calculated | required by the formula of FOX of the polymer obtained from (I-B1)-(I-B3) is 25-100 degreeC.

Monomer mixture (IC)
(I-C1) Methacrylic acid alkyl ester 80-100% by mass
(I-C2) Acrylic acid alkyl ester 0 to 20% by mass
(I-C3) Other monomer having copolymerizable double bond 0 to 20% by mass

The acrylic acid alkyl ester (I-A1) may have either a linear or branched alkyl group. Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. These can be used individually or in mixture of 2 or more types. Of these, n-butyl acrylate is preferred.

  The methacrylic acid alkyl ester (I-A2) may have either a linear or branched alkyl group. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate. These can be used individually or in mixture of 2 or more types. Of these, methyl methacrylate is preferred.

  Examples of other monomers having a copolymerizable double bond (I-A3) include acrylic monomers such as lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, and methacrylic acid, styrene, alkyl-substituted styrene, Examples thereof include unsaturated dicarboxylic anhydrides such as acrylonitrile, methacrylonitrile, maleic anhydride and itaconic anhydride, N-phenylmaleimide, N-cyclohexylmaleimide and the like. These can be used individually or in mixture of 2 or more types.

  The polyfunctional monomer (I-A4) is a monomer having two or more copolymerizable double bonds in one molecule. As specific compounds, alkylene glycol dimethacrylates such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and propylene glycol dimethacrylate are preferable. Polyvinylbenzene such as divinylbenzene and trivinylbenzene can also be used. In addition, triallyl cyanurate, triallyl isocyanurate and the like are also effective. These can be used individually or in mixture of 2 or more types. Of these, 1,3-butylene glycol dimethacrylate is preferred. Even when the polyfunctional monomer (I-A4) does not act at all, as long as the graft crossing agent (I-A5) is present, a fairly stable rubber-containing polymer (I) is obtained. The polyfunctional monomer (I-A4) is particularly effective, for example, when the hot strength is strictly required.

  The graft crossing agent (I-A5) is a monomer having two or more different copolymerizable double bonds in one molecule. Specific examples thereof include allyl, methallyl or crotyl ester of copolymerizable α, β-unsaturated carboxylic acid or dicarboxylic acid. Particularly preferred are allyl esters of acrylic acid, methacrylic acid, maleic acid or fumaric acid. Of these, allyl methacrylate is preferable because of its excellent effect. In addition, triallyl cyanurate, triallyl isocyanurate and the like are also effective. These can be used individually or in mixture of 2 or more types. In the graft crossing agent (I-A5), the conjugated unsaturated bond of the ester mainly reacts and chemically bonds much faster than the allyl group, methallyl group or crotyl group.

  Other chain transfer agents can be used. The chain transfer agent can be selected from those used for normal radical polymerization. Specific examples include alkyl mercaptans having 2 to 20 carbon atoms, mercapto acids, thiophenol, carbon tetrachloride and the like.

  The content of the acrylic acid alkyl ester (I-A1) in the monomer mixture (I-A) is 50 to 99.9% by mass. From the viewpoint of resistance to molding whitening of the acrylic resin film, 55% by mass or more is preferable, and 60% by mass or more is more preferable. The upper limit is preferably 79.9% by mass or less, more preferably 69.9% by mass or less, from the viewpoint of the surface hardness and heat resistance of the acrylic resin film.

  Content of the methacrylic acid alkyl ester (I-A2) in a monomer mixture (IA) is 0-49.9 mass%. Preferably it is 20 mass% or more, Most preferably, it is 30 mass% or more. Moreover, the upper limit becomes like this. Preferably it is 44.9 mass% or less, More preferably, it is 39.9 mass% or less.

  The content of the other monomer (IA3) having a copolymerizable double bond in the monomer mixture (IA) is 0 to 20% by mass. More preferably, it is 15 mass% or less.

  Content of the polyfunctional monomer (IA-4) in a monomer mixture (IA) is 0-10 mass%. From the viewpoint of resistance to molding whitening of the acrylic resin film, 0.1% by mass or more is more preferable, and 3% by mass or more is particularly preferable. Further, from the viewpoint of imparting sufficient flexibility and toughness to the acrylic resin film, the upper limit is preferably 6% by mass or less, and particularly preferably 5% by mass or less.

  The content of the graft crossing agent (IA-5) is 0.1 to 10% by mass in the monomer mixture (IA). By setting the content of the graft crossing agent (I-A5) to 0.1% by mass or more, the whitening resistance of the acrylic resin film is improved, and the optical properties such as transparency are not deteriorated. Can do. More preferably, it is 0.5 mass% or more. Moreover, sufficient softness | flexibility and toughness can be provided to an acrylic resin film by content of a graft crossing agent (I-A5) being 10 mass% or less. More preferably, it is 5 mass% or less, Most preferably, it is 2 mass% or less.

  Tg calculated | required by the formula of FOX of the polymer obtained from (I-A1)-(I-A3) is less than 25 degreeC. Furthermore, 10 degrees C or less is preferable and 0 degrees C or less is more preferable. If Tg is 10 degrees C or less, the acrylic resin film obtained will exhibit the outstanding impact resistance. Tg is a polymer handbook [Polymer HandBook, J. et al. Brandup, Interscience, 1989], using the value described in FOX.

  The amount of the monomer mixture (IA) used is the total amount of the monomer mixture (IA), monomer mixture (IB) and monomer mixture (IC) (100% by mass). ) Is preferably 15 to 50% by mass. By setting it as 15 mass% or more, shaping | molding whitening resistance can be provided to an acrylic resin film, and film forming property and toughness required for insert molding or in-mold molding can be made compatible. Moreover, by setting it as 50 mass% or less, the film which has the surface hardness and heat resistance required for the laminated body of the member for vehicles is obtained. More preferably, it is 35 mass% or less.

  When the monomer mixture (IA) is polymerized, the monomer mixture (IA) can be polymerized in a lump, but it is preferable to polymerize in two or more stages. When the polymerization is performed in two or more stages, it is preferable that the constitutional ratio of the monomer units in each polymerization stage is different.

  When the monomer mixture (IA) is polymerized in two or more stages, a single amount used in the first stage from the viewpoint of molding whitening resistance, impact resistance, heat resistance and surface hardness of the acrylic resin film The above-described Tg obtained from the body mixture (IA-1) is preferably lower than the Tg obtained from the monomer mixture (IA-2) used in the second stage. Specifically, the Tg obtained from the monomer mixture (IA-1) used in the first stage is preferably less than −30 ° C. from the viewpoint of molding whitening resistance and impact resistance, and two stages. Tg calculated | required from the formula of Fox of the polymer obtained from the monomer mixture (IA-2) used for eyes is -15 degreeC-10 degreeC from a viewpoint of surface hardness and heat resistance.

  In the monomer mixture (IA), the amount of the monomer mixture (IA-1) used in the first stage is preferably 1 to 20% by mass, and the monomer used in the second stage The amount of the mixture (IA-2) used is preferably 80 to 99% by mass.

  Acrylic acid alkyl ester (I-B1), methacrylic acid alkyl ester (I-B2), other monomer having a copolymerizable double bond (I-B3), multifunctional monomer (I-B4) ) And the graft crossing agent (I-B5) are the above-mentioned alkyl acrylate ester (I-A1), alkyl methacrylate ester (I-A2), and other monomers having a copolymerizable double bond (I -A3), a polyfunctional monomer (I-A4), and the same thing as a graft crossing agent (I-A5) are mentioned.

  Other similar chain transfer agents can be used.

  The content of the acrylic acid alkyl ester (I-B1) in the monomer mixture (IB) is 9.9 to 90% by mass. From the viewpoint of molding whitening resistance, surface hardness and heat resistance of the acrylic resin film, 19.9% by mass or more is preferable, and 29.9% by mass or more is more preferable. Moreover, the upper limit becomes like this. Preferably it is 60 mass% or less, More preferably, it is 50 mass% or less.

  Content of the methacrylic acid alkyl ester (I-B2) in a monomer mixture (IB) is 9.9-90 mass%. From the viewpoint of molding whitening resistance, surface hardness and heat resistance of the acrylic resin film, 39.9% by mass or more is preferable, and 49.9% by mass or more is more preferable. Moreover, the upper limit becomes like this. Preferably it is 80 mass% or less, More preferably, it is 70 mass% or less.

  The content of the other monomer (IB3) having a copolymerizable double bond in the monomer mixture (IB) is 0 to 20% by mass. Preferably it is 15 mass% or less.

  Content of the polyfunctional monomer (I-B4) in a monomer mixture (IB) is 0-10 mass%. From the viewpoint of imparting sufficient flexibility and toughness to the acrylic resin film, it is preferably 6% by mass or less, and more preferably 3% by mass or less.

  The content of the graft crossing agent (I-B5) in the monomer mixture (IB) is 0.1 to 10% by mass. By setting the content of the graft crossing agent (I-B5) to 0.1% by mass or more, the whitening resistance of the acrylic resin film is improved and the optical properties such as transparency are not deteriorated. Can do. More preferably, it is 0.5 mass% or more. Moreover, sufficient softness | flexibility and toughness can be provided to an acrylic resin film by content of a graft crossing agent (I-B5) being 10 mass% or less. Preferably it is 5 mass% or less, More preferably, it is 2 mass% or less.

  Tg calculated | required by the formula of FOX of the polymer obtained from (I-B1)-(I-B3) is 25-100 degreeC. When Tg is 25 ° C. or higher, the surface hardness and heat resistance of the acrylic resin film are at a level required for the vehicle member. Preferably it is 40 degreeC or more, More preferably, it is 50 degreeC or more. Moreover, if Tg is 100 degrees C or less, the acrylic resin film with favorable shaping | molding whitening-proof property and film forming property will be obtained. Preferably it is 80 degrees C or less, More preferably, it is 70 degrees C or less.

  When polymerizing the monomer mixture (IB), the amount of the monomer mixture (IB) used is the monomer mixture (IA), the monomer mixture (IB) and the single amount. 5-35 mass% is preferable in the total amount (100 mass%) of a body mixture (IC). Within this range, the functions of molding whitening resistance, surface hardness and heat resistance can be expressed, and film forming properties and toughness required for insert molding or in-mold molding can be imparted. it can. More preferably, it is 20 mass% or less.

  When the monomer mixture (IB) is polymerized, the monomer mixture (IB) can be polymerized in a lump or in two or more stages.

  The methacrylic acid alkyl ester (I-C1), the acrylic acid alkyl ester (I-C2), and the other monomer (I-C3) having a copolymerizable double bond are the same as the methacrylic acid alkyl ester (I- Examples thereof include those similar to A2), alkyl acrylate ester (I-A1), and other monomer (I-A3) having a copolymerizable double bond.

  Other similar chain transfer agents can be used.

  The content of the methacrylic acid alkyl ester (I-C1) in the monomer mixture (1-C) is 80 to 100% by mass. From the viewpoint of the surface hardness and heat resistance of the acrylic resin film, 90% by mass or more is preferable, and 93% by mass or more is more preferable. Moreover, the upper limit becomes like this. Preferably it is 99 mass% or less.

  Content of the acrylic acid alkylester (I-C2) in a monomer mixture (1-C) is 0-20 mass%. Preferably it is 1 mass% or more. Moreover, the upper limit becomes like this. Preferably it is 10 mass% or less, More preferably, it is 7 mass% or less.

  The content of the other monomer (I-C3) having a copolymerizable double bond in the monomer mixture (1-C) is 0 to 20% by mass. More preferably, it is 15 mass% or less.

  Chain transfer agents can also be used. As for the usage-amount of a chain transfer agent, 0.01-5 mass% is preferable in a monomer mixture (1-C). More preferably, it is 0.2 mass% or more, Most preferably, it is 0.4 mass% or more.

  Tg calculated | required by the formula of FOX of the polymer obtained from (I-C1)-(I-C2) has preferable 60 degreeC or more. If it is 60 degreeC or more, the acrylic resin film which has the surface hardness and heat resistance suitable for the member for vehicles will be obtained. More preferably, it is 80 degreeC or more, Most preferably, it is 90 degreeC or more.

  When polymerizing the monomer mixture (IC), the amount of the monomer mixture (IC) used is the monomer mixture (IA), the monomer mixture (IB) and the single amount. 15-80 mass% is preferable in the total amount (100 mass%) of a body mixture (IC). If it is 15 mass% or more, the surface hardness and heat resistance of an acrylic resin film will become favorable. More preferably, it is 45 mass% or more. When it is 80% by mass or less, an acrylic resin film having resistance to whitening can be obtained, and toughness necessary for insert molding or in-mold molding can be imparted.

  When polymerizing the monomer mixture (IC), the monomer mixture (IC) can be polymerized in a lump or in two or more stages.

  The gel content of the rubber-containing polymer (I) is preferably 50% by mass or more, and more preferably 60% by mass or more from the viewpoint of obtaining more excellent molding whitening resistance. From the viewpoint of molding whitening resistance, the larger the gel content, the more advantageous. However, from the viewpoint of moldability, the presence of a certain amount or more of free polymer is necessary, so the gel content should be 80% by mass or less. preferable. The gel content means that a predetermined amount (mass before extraction) of the rubber-containing polymer (I) is extracted under reflux in an acetone solvent, the treated solution is separated by centrifugation, and after drying, the mass of insoluble acetone. (Mass after extraction) is a value calculated by the following formula.

Gel content (mass%) = mass after extraction (g) / mass before extraction (g) × 100
The mass average particle diameter of the rubber-containing polymer (I) is preferably 0.03 μm to 0.3 μm. From the viewpoint of the mechanical properties of the acrylic resin film, it is more preferably 0.07 μm or more, particularly preferably 0.09 μm or more. Further, from the viewpoint of forming whitening resistance of the acrylic resin film, transparency, and maintaining transparency during heat molding in insert molding or in-mold molding, it is more preferably 0.15 μm or less, particularly preferably 0.13 μm or less. The mass average particle diameter is measured by a dynamic light scattering method using a light scattering photometer DLS-700 (trade name) manufactured by Otsuka Electronics Co., Ltd.

  As a polymerization method of the rubber-containing polymer (I), a sequential multi-stage polymerization method by emulsion polymerization is the most suitable polymerization method, but is not particularly limited thereto. For example, a monomer mixture (1-A ) And (1-B) after emulsion polymerization, an emulsion suspension polymerization method in which the polymerization of the monomer mixture (IC) is converted into a suspension polymerization system can also be performed.

  When the rubber-containing polymer (I) is produced by emulsion polymerization, an emulsion prepared by previously mixing the monomer mixture (IA) in the rubber-containing polymer (I) with water and a surfactant is prepared. A method is preferred in which the monomer mixture (IB) and the monomer mixture (IC) are sequentially supplied to the reactor and polymerized after being supplied to the reactor for polymerization.

  When an emulsion prepared by mixing the monomer mixture (1-A) with water and a surfactant in advance is supplied to a reactor and polymerized to be dispersed in acetone, The rubber-containing polymer (I) in which the number of particles having a diameter of 55 μm or more present in 1 to 50 per 100 g of the rubber-containing polymer (I) can be easily obtained. The acrylic resin film using the rubber-containing polymer (I) thus obtained as a raw material has a characteristic that the number of fish eyes in the film is small, and in particular, a light-colored wood grain pattern with low printing pressure in which printing omission is likely to occur. Even when a gravure printing or a solid gravure printing such as a metallic tone or a jet black tone is performed, printing omission is small and a high level of printability is preferable.

  As the surfactant used in preparing the emulsion, anionic, cationic and nonionic surfactants can be used, and anionic surfactants are particularly preferable. Examples of anionic surfactants include rosin soap, potassium oleate, sodium stearate, sodium myristate, N-lauroyl sarcosine sodium, alkenyl succinate dipotassium salt, sulfate ester salt such as sodium lauryl sulfate, etc. , Sodium dioctyl sulfosuccinate, sodium dodecylbenzenesulfonate, sulfonates such as sodium alkyldiphenyl ether disulfonate, phosphate esters such as sodium polyoxyethylene alkylphenyl ether phosphate, sodium polyoxyethylene alkyl ether phosphate And phosphoric acid ester salts. Of these, phosphate ester salts such as sodium polyoxyethylene alkyl ether phosphates are preferred. Examples of the surfactant include NC-718 manufactured by Sanyo Chemical Industries, Ltd., Phosphanol LS-529, Phosphanol RS-610NA, Phosphanol RS-620NA, Phosphorus manufactured by Toho Chemical Industry Co., Ltd. Fanol RS-630NA, Phosphanol RS-640NA, Phosphanol RS-650NA, Phosphanol RS-660NA, Latemu P-0404, Latemulu P-0405, Latemulu P-0406, Latemulu P manufactured by Kao Corporation -0407 (above, product name).

  The method of preparing the emulsion is: a method in which a monomer component is charged in water and then a surfactant is added; a method in which a surfactant is charged in water and then a monomer component is charged; or a monomer component Any method may be used in which water is added after the surfactant is charged therein. Among these, a method in which a monomer component is charged in water and then a surfactant is charged, and a method in which a monomer component is charged after a surfactant is charged in water are preferable.

  Examples of the apparatus for preparing the emulsion include various forced emulsifiers such as a homogenizer and a homomixer, and a membrane emulsifier.

  The emulsion may be either W / O type in which water droplets are dispersed in the monomer component oil or O / W type in which monomer component oil droplets are dispersed in water. The O / W type in which oil droplets are dispersed and the diameter of the oil droplets in the dispersed phase is preferably 100 μm or less.

  As a polymerization initiator used when polymerizing the monomer mixture (IA), (IB) and (IC), a peroxide, an azo initiator, or an oxidizing agent / reducing agent is combined. Among these, redox initiators are preferred, and in particular, sulfoxylate initiators that combine ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, longalite, hydroperoxide are used. preferable. The usage-amount of a polymerization initiator is suitably determined according to polymerization conditions etc. Moreover, the addition method of a polymerization initiator may be either a method of adding to either one or both of an aqueous phase and a monomer phase (oil phase).

  As a method for polymerizing the rubber-containing polymer (I), in particular, the temperature of the aqueous solution containing ferrous sulfate, ethylenediaminetetraacetic acid disodium salt and Rongalite charged in the reactor is raised to the polymerization temperature, and then the monomer mixture An emulsion prepared by mixing (IA) and a polymerization initiator such as peroxide with water and a surfactant is supplied to the reactor for polymerization, and then the monomer mixture (IB) is prepared. A method in which a polymerization initiator such as a peroxide is supplied to the reactor for polymerization, and then the monomer mixture (IC) is supplied to the reactor together with a polymerization initiator such as a peroxide for polymerization. preferable.

  The polymerization temperature varies depending on the type or amount of the polymerization initiator, but is usually preferably 40 ° C or higher, more preferably 60 ° C or higher, preferably 120 ° C or lower, and more preferably 95 ° C or lower.

  The polymer latex containing the rubber-containing polymer (I) obtained by the above method is preferably treated using a filtration device. This filtration treatment can remove from the latex scales and raw materials generated during the polymerization, and foreign matters mixed from the outside during the polymerization. As the filtration device, a GAF filter system of ISP Filters PTA Ltd. using a bag-like mesh filter, a cylindrical filter medium is arranged on the inner surface of the cylindrical filter chamber, and a stirring blade is arranged in the filter medium A centrifugal filtration device or a vibration type filtration device in which the filter medium performs a horizontal circular motion and a vertical amplitude motion with respect to the filter medium surface is preferable.

  The rubber-containing polymer (I) can be produced by recovering the rubber-containing polymer (I) from the polymer latex produced by the above method. Examples of the method for recovering the rubber-containing polymer (I) from the polymer latex include salting out, acid precipitation coagulation, spray drying, freeze drying and the like. According to these methods, the rubber-containing polymer (I) is recovered in powder form.

  When the rubber-containing polymer (I) is recovered by salting out using a metal salt, the residual metal content in the finally obtained rubber-containing polymer (I) is preferably 800 ppm or less. In particular, when a metal salt with strong affinity with water such as magnesium salt or sodium salt is used as a salting-out agent, a whitening phenomenon occurs when the acrylic resin film is immersed in boiling water unless the residual metal content is reduced as much as possible. This is a practical problem. Although salting out using calcium salt or aciding out coagulation using sulfuric acid shows a relatively good tendency, in any case, in order to give excellent water whitening resistance, the residual metal content is 800 ppm. It is necessary to make it below.

Rubber-containing polymer (II)
The rubber-containing polymer (II) is obtained by polymerizing a monomer or monomer mixture mainly composed of alkyl acrylate and then polymerizing a monomer or monomer mixture mainly composed of methacrylic acid alkyl ester. It is the multistage polymer obtained by doing this.

  In addition, Tg calculated | required by the formula of FOX of the polymer obtained from the monomer or monomer mixture which has acrylic acid alkylester as a main component is less than 25 degreeC.

Hereinafter, the rubber-containing polymer (IIa) will be described as a specific example of the rubber-containing polymer (II).

  As the alkyl acrylate ester used for the rubber-containing polymer (IIa), various conventionally known alkyl esters are used. In particular, n-butyl acrylate, 2-ethylhexyl acrylate and the like are preferable. The amount of the acrylic acid alkyl ester used is preferably 35 to 100% by mass, more preferably 50 to 100% by mass in the monomer or monomer mixture (excluding the crosslinkable monomer). What is the lower limit of these ranges? This is significant in terms of molding whitening resistance and the like.

  Other vinyl monomers copolymerizable with acrylic acid alkyl esters can be used. Other vinyl monomers are preferably methacrylic acid alkyl esters such as methyl methacrylate, n-butyl methacrylate and cyclohexyl methacrylate, styrene, acrylonitrile and the like. These can be used alone or in combination of two or more. The amount of the other vinyl monomer used is preferably 65% by mass or less in the monomer mixture (excluding the crosslinkable monomer).

  Usually, a crosslinkable monomer is further used. The crosslinkable monomer is not particularly limited, but ethylene glycol dimethacrylate, butanediol dimethacrylate, allyl acrylate, allyl methacrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, Examples include diallyl maleate, trimethylolpropane triacrylate, and allyl cinnamate. These can be used alone or in combination of two or more. The amount of the crosslinkable monomer used is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the monomer or monomer mixture (excluding the crosslinkable monomer). From the viewpoint of resistance to molding whitening, 0.3 part by mass or more is more preferable. Further, even if the amount used exceeds 10 parts by mass, there is no particular problem in physical properties, but since the improvement of the effect accompanying the increase in the amount used is small, 10 parts by mass or less is preferable from the viewpoint of addition efficiency.

  The monomer or monomer mixture mainly composed of an acrylic acid alkyl ester may be polymerized in two or more stages. When the polymerization is performed in two or more stages, the amount of the alkyl acrylate in the monomer or monomer mixture mainly composed of the alkyl acrylate is preferably 35% by mass or more, more preferably 50% by mass or more. preferable.

After polymerizing a monomer or monomer mixture containing a monomer containing methacrylic acid alkyl ester as a main component, a monomer or monomer mixture containing acrylic acid alkyl ester as a main component may be polymerized. . For example, a polymer having an average particle diameter of less than 0.2 μm as disclosed in Japanese Patent Application Laid-Open No. 7-149994 can be used although it is not described for use in painting substitute applications.
The monomer or monomer mixture containing a methacrylic acid alkyl ester as a main component may be polymerized in at least one step after the above polymerization.

  The amount of the methacrylic acid alkyl ester used in the monomer or monomer mixture is preferably 50% by mass or more. Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and the like.

  When polymerizing a monomer or monomer mixture mainly composed of alkyl methacrylate, other vinyl monomers copolymerizable with alkyl methacrylate can be used in combination. Examples of other vinyl monomers include alkyl acrylates such as methyl acrylate, n-butyl acrylate, and cyclohexyl acrylate, styrene, acrylonitrile, and the like. These can be used alone or in combination of two or more. The amount of the other vinyl monomer used is preferably 50% by mass or less in the monomer mixture.

  The monomer or monomer mixture mainly composed of methacrylic acid alkyl ester is 10 to 400 parts by mass with respect to 100 parts by mass of the monomer or monomer mixture mainly composed of alkyl acrylate. It is preferably 20 to 200 parts by mass. The lower limit of these ranges is significant in terms of preventing deterioration of transparency due to aggregation of the rubber-containing polymer.

  The rubber-containing polymer (IIa) preferably has a mass average particle diameter of 0.03 μm to 0.3 μm. From the viewpoint of the mechanical properties of the acrylic resin film, it is more preferably 0.07 μm or more, particularly preferably 0.09 μm or more. Further, from the viewpoint of forming whitening resistance of the acrylic resin film, transparency, and maintaining transparency during heat molding in insert molding or in-mold molding, the thickness is more preferably 0.15 μm or less, and particularly preferably 0.13 μm or less.

In particular, the following rubber-containing polymer (IIb) is preferably used as the rubber-containing polymer (II) in order to impart a good balance of trimming processability and molding whitening resistance during molding to the acrylic resin film. preferable. Hereinafter, the rubber-containing polymer (IIb) will be described.

Rubber-containing polymer (IIb)
The following monomer mixture (IIb-A), monomer mixture (IIb-B) and monomer mixture (IIb-C) are combined into monomer mixture (IIb-A) and monomer mixture (IIb-B). ) And the monomer mixture (IIb-C) in this order.

Monomer mixture (IIb-A)
(IIb-A1) Acrylic acid alkyl ester 50-99.9% by mass
(IIb-A2) Methacrylic acid alkyl ester 0 to 49.9% by mass
(IIb-A3) Other monomer having copolymerizable double bond 0 to 20% by mass
(IIb-A4) Polyfunctional monomer 0 to 10% by mass
(IIb-A5) Graft crossing agent 0.1 to 10% by mass
In addition, Tg calculated | required by the formula of FOX of the polymer obtained from (IIb-A1)-(IIb-A3) is less than 25 degreeC.

Monomer mixture (IIb-B)
(IIb-B1) Acrylic acid alkyl ester 9.9 to 90% by mass
(IIb-B2) Methacrylic acid alkyl ester 9.9 to 90% by mass
(IIb-B3) Other monomer having a double bond capable of copolymerization 0 to 20% by mass
(IIb-B4) Polyfunctional monomer 0 to 10% by mass
(IIb-B5) Graft crossing agent 0.1 to 10% by mass
In addition, Tg calculated | required by the formula of FOX of the polymer obtained from (IIb-B1)-(IIb-B3) is 0-25 degreeC.

Monomer mixture (IIb-C)
(IIb-C1) Methacrylic acid alkyl ester 80 to 100% by mass
(IIb-C2) Acrylic acid alkyl ester 0 to 20% by mass
(IIb-C3) Other monomer having copolymerizable double bond 0 to 20% by mass

Acrylic acid alkyl ester (IIb-A1), methacrylic acid alkyl ester (IIb-A2), other monomer having a copolymerizable double bond (IIb-A3), multifunctional monomer (IIb-A4) ) And the graft crossing agent (IIb-A5), various compounds exemplified in the monomer mixture (IA) of the rubber-containing polymer (I) can be used.

  The monomer mixture (IIb-A) may be polymerized in the presence of a chain transfer agent.

  Content of acrylic acid alkylester (IIb-A1) is 50-99.9 mass% in monomer mixture (IIb-A). From the viewpoint of trimming processability when forming an acrylic resin film, 60% by mass or more is preferable, and 80% by mass or more is more preferable. Further, the upper limit is preferably 97.9% by mass or less, more preferably 94.9% by mass or less, from the viewpoint of the surface hardness and heat resistance of the acrylic resin film.

  The content of the methacrylic acid alkyl ester (IIb-A2) is 0 to 49.9% by mass in the monomer mixture (IIb-A). Preferably it is 2 mass% or more, More preferably, it is 5 mass% or more. Moreover, the upper limit becomes like this. Preferably it is 39.9 mass% or less, More preferably, it is 19.9 mass% or less.

  The other monomer (IIb-A3) having a copolymerizable double bond is 0 to 20% by mass in the monomer mixture (IIb-A). Preferably it is 15 mass% or less.

  Content of a polyfunctional monomer (IIb-A4) is 0-10 mass% in a monomer mixture (IIb-A). From the viewpoint of resistance to molding whitening of the acrylic resin film, 0.1% by mass or more is preferable, and 3% by mass or more is more preferable. Moreover, the upper limit is more preferably 6% by mass or less and further preferably 5% by mass or less from the viewpoint of imparting sufficient flexibility and toughness to the acrylic resin film.

  The content of the graft crossing agent (IIb-A5) is 0.1 to 10% by mass in the monomer mixture (IIb-A). By making the content of the graft crossing agent (IIb-A5) 0.1% by mass or more, the whitening resistance of the acrylic resin film is improved, and it is molded without deteriorating optical properties such as transparency. Can do. More preferably, it is 0.5 mass% or more. Moreover, sufficient softness | flexibility and toughness can be provided to an acrylic resin film by content of a graft crossing agent (IIb-A5) being 10 mass% or less. More preferably, it is 5 mass% or less, Most preferably, it is 2 mass% or less.

  Tg calculated | required by the formula of FOX of the polymer obtained from (IIb-A1)-(IIb-A3) is 0 degrees C or less from a viewpoint of the trimming workability at the time of shaping | molding of an acrylic resin film, -30 degrees C or less Is more preferable.

  The amount of the monomer mixture (IIb-A) is 15 to 50% by mass in the monomer mixture (IIb-A), the monomer mixture (IIb-B), and the monomer mixture (IIb-C). preferable. By setting the amount of the monomer mixture (IIb-A) to 15% by mass or more, it is possible to impart molding whitening resistance to the acrylic resin film, which is necessary for film forming properties and insert molding or in-mold molding. Both toughness can be achieved. Furthermore, it is possible to impart trimming processability during good molding. Moreover, the film which has surface hardness and heat resistance required for the laminated body of a vehicle member by obtaining content of a monomer mixture (IIb-A) to 50 mass% or less is obtained. More preferably, it is 35 mass% or less.

  When the monomer mixture (IIb-A) is polymerized in two or more stages, a single amount used in the first stage from the viewpoint of molding whitening resistance, impact resistance, heat resistance and surface hardness of the acrylic resin film The above-described Tg obtained from the body mixture (IIb-A-1) is preferably lower than the Tg obtained from the monomer mixture (IIb-A-2) used in the second stage. Specifically, Tg obtained from the Fox formula of the polymer obtained from the monomer mixture (IIb-A-1) used in the first stage is-from the viewpoint of molding whitening resistance and impact resistance. The Tg obtained from the monomer mixture (IIb-A-2) used in the second stage is preferably −15 ° C. to 10 ° C. from the viewpoint of surface hardness and heat resistance.

  In the monomer mixture (IIb-A), the amount of the monomer mixture (IIb-A-1) used in the first stage is preferably 1 to 20% by mass, and the monomer used in the second stage The amount of the mixture (IIb-A-2) used is preferably 80 to 99% by mass.

  The monomer mixture (IIb-A) can be polymerized in a lump or in two or more stages.

  Acrylic acid alkyl ester (IIb-B1), methacrylic acid alkyl ester (IIb-B2), other monomer having a copolymerizable double bond (IIb-B3), multifunctional monomer (IIb-B4) ) And the graft crossing agent (IIb-B5), various types exemplified in the monomer mixture (IB) of the rubber-containing polymer (I) can be used.

  The monomer mixture (IIb-B) may be polymerized in the presence of a chain transfer agent.

  Content of acrylic acid alkylester (IIb-B1) is 9.9-90 mass% in monomer mixture (IIb-B). From the viewpoints of trimming processability, molding whitening resistance, surface hardness, and heat resistance when the acrylic resin film is molded, 19.9% by mass or more is preferable, and 29.9% by mass or more is more preferable. Moreover, the upper limit becomes like this. Preferably it is 60 mass% or less, More preferably, it is 50 mass% or less.

  The content of the methacrylic acid alkyl ester (IIb-B2) is 9.9 to 90% by mass in the monomer mixture (IIb-B). From the viewpoints of trimming processability, molding whitening resistance, surface hardness, and heat resistance during molding of the acrylic resin film, 39.9% by mass or more is preferable, and 49.9% by mass or more is more preferable. Moreover, the upper limit becomes like this. Preferably it is 80 mass% or less, More preferably, it is 70 mass% or less.

  The content of the other monomer (IIb-B3) having a copolymerizable double bond is 0 to 20% by mass in the monomer mixture (IIb-B). More preferably, it is 15 mass% or less.

  Content of a polyfunctional monomer (IIb-B4) is 0-10 mass% in a monomer mixture (IIb-B). From the viewpoint of imparting sufficient flexibility and toughness to the acrylic resin film, it is preferably 6% by mass or less, and more preferably 3% by mass or less.

  The content of the graft crossing agent (IIb-B5) is 0.1 to 10% by mass in the monomer mixture (IIb-B). By making the content of the graft crossing agent (IIb-B5) 0.1% by mass or more, the whitening resistance of the acrylic resin film is improved and the optical properties such as transparency are not deteriorated. Can do. More preferably, it is 0.5 mass% or more. Moreover, sufficient softness | flexibility and toughness can be provided to the acrylic resin film obtained by making content of a graft crossing agent (IIb-B5) into 10 mass% or less. Preferably it is 5 mass% or less, More preferably, it is 2 mass% or less.

  Tg calculated | required by the formula of FOX of the polymer obtained from (IIb-B1)-(IIb-B3) exceeds 0 degreeC, and is less than 25 degreeC. If Tg exceeds 0 ° C. and less than 25 ° C., the surface hardness and heat resistance of the acrylic resin film maintain the level required for a vehicle member and have excellent trimming processability during insert molding. It becomes. Moreover, from the viewpoint of the surface hardness and heat resistance of the acrylic resin film, it is preferably 10 ° C. or higher, more preferably 15 ° C. or higher.

  The monomer mixture (IIb-B) is 5% in the total amount (100% by mass) of the monomer mixture (IIb-A), the monomer mixture (IIb-B), and the monomer mixture (IIb-C). -35 mass% is preferable. Within this range, the function of the intermediate polymer (IIb-B), which is important for achieving both the above-described whitening resistance to molding, surface hardness and heat resistance, and good trimming processability during insert molding, is achieved. While being able to express, the other physical property of an acrylic resin film, for example, film forming property, toughness required for insert molding or in-mold molding can be provided. More preferably, it is 20 mass% or less.

  When polymerizing the monomer mixture (IIb-B), the monomer mixture (IIb-B) can be polymerized in a lump or in two or more stages.

  The methacrylic acid alkyl ester (IIb-C1), the acrylic acid alkyl ester (IIb-C2), and the other monomer (IIb-C3) having a copolymerizable double bond are the same as those of the rubber-containing polymer (I). Various examples exemplified in the monomer mixture (IC) can be used.

  The content of the methacrylic acid alkyl ester (IIb-C1) is 80 to 100% by mass in the monomer mixture (IIb-C). 90 mass% or more is more preferable from a viewpoint of the surface hardness of an acrylic resin film, and heat resistance.

  Content of acrylic acid alkylester (IIb-C2) is 0-20 mass% in monomer mixture (IIb-C). More preferably, it is 10 mass% or less.

  The content of the other monomer (IIb-C3) having a copolymerizable double bond is preferably 0 to 20% by mass in the monomer mixture (IIb-C). More preferably, it is 15 mass% or less.

  The molecular weight of the polymer obtained from the monomer mixture (IIb-C) can be adjusted by using a chain transfer agent during the polymerization of the monomer mixture (IIb-C). The chain transfer agent can be selected from those used in normal radical polymerization. Specific examples include alkyl mercaptans having 2 to 20 carbon atoms, mercapto acids, thiophenol, carbon tetrachloride and the like. These can be used individually or in mixture of 2 or more types. As for content of a chain transfer agent, 0.01-5 mass% is preferable with respect to 100 mass% of monomer components which are the raw materials of a hard polymer (IIb-C). More preferably, it is 0.2 mass% or more.

  Tg calculated | required by the formula of FOX of the polymer obtained from monomer mixture (IIb-C1) and monomer mixture (IIb-C2) has preferable 60 degreeC or more. When Tg is 60 ° C. or higher, an acrylic resin film having surface hardness and heat resistance suitable for a vehicle member can be obtained. More preferably, it is 80 ° C. or higher.

  When polymerizing the monomer mixture (IIb-C), the amount of the monomer mixture (IIb-C) depends on the monomer mixture (IIb-A), monomer mixture (IIb-B) and monomer. 15-80 mass% is preferable in the total amount (100 mass%) of mixture (IIb-C). When the amount of the monomer mixture (IIb-C) is 15% by mass or more, the surface hardness and heat resistance of the acrylic resin film are good. More preferably, it is 45 mass% or more. If the amount of the monomer mixture (IIb-C) is 80% by mass or less, the acrylic resin film has anti-molding whitening resistance, toughness required for insert molding or in-mold molding, and good trimming processability during insert molding. Can be granted.

  The monomer mixture (IIb-C) can be polymerized in a lump or in two or more stages.

  The gel content, mass average particle diameter and production method of the rubber-containing polymer (IIb) are the same as those of the rubber-containing polymer (I).

  Thus, by blending a specific amount of the rubber-containing polymer (IIb) with the above-mentioned rubber-containing polymer (I), the surface hardness and heat resistance suitable for a vehicle member, during insert molding or in-mold molding. An acrylic resin film excellent in anti-molding whitening performance and trimming performance during insert molding can be obtained.

  From the viewpoints of film-forming properties, surface hardness of the resulting acrylic resin film, heat resistance, etc., thermoplastic polymer (III) (hereinafter simply referred to as “thermoplastic polymer (III)”) mainly composed of alkyl methacrylate ester. May be included).

Thermoplastic polymer (III)
The thermoplastic polymer (III) has a methacrylic acid alkyl ester as a main component. Specifically, C1-C4 methacrylic acid alkyl ester 50-100 mass%, acrylic acid alkyl ester 0-50 mass%, and other monomer 0-50 mass% which has a copolymerizable double bond And a reduced viscosity (0.1 g of a polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) of 0.15 L / g or less. Coalescence is preferred. By including such a thermoplastic polymer (III), the surface hardness and heat resistance of the acrylic resin film can be increased. Accordingly, the Tg of the thermoplastic polymer (III) is preferably 80 ° C. or higher, more preferably 90 ° C. or higher.

  Examples of the methacrylic acid alkyl ester include those listed in (I-A2). Of these, methyl methacrylate is preferred. These can be used individually or in mixture of 2 or more types.

  Examples of the acrylic acid alkyl ester include those listed in (I-A1). Of these, methyl acrylate is preferred. These can be used individually or in mixture of 2 or more types.

  Examples of the other monomer having a copolymerizable double bond include those listed in (I-A3).

  From the viewpoint of the surface hardness and heat resistance of the acrylic resin film, the content of the alkyl methacrylate ester is 50 to 100% by mass in the monomer component (100% by mass) that is the raw material of the thermoplastic polymer (III). preferable. More preferably, it is 80 mass% or more, and the upper limit is 99.9 mass% or less.

  The content of the acrylic acid alkyl ester is a monomer component (100) that is a raw material of the thermoplastic polymer (III) from the viewpoint of imparting the film formability of the acrylic resin film and toughness necessary for insert molding or in-mold molding. % To 50% by mass is preferable. More preferably, it is 0.1 mass% or more, and the upper limit is more preferably 20 mass% or less.

  The content of the other monomer having a copolymerizable double bond is preferably 0 to 50% by mass in the monomer component (100% by mass) which is a raw material of the thermoplastic polymer (III).

  The reduced viscosity of the thermoplastic polymer (III) (0.1 g of the polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) is from the viewpoint of insert moldability, in-mold moldability and film-formability of the acrylic resin film. 0.15 L / g or less is preferable and 0.1 L / g or less is more preferable. Moreover, 0.01 L / g or more is preferable from a viewpoint of film forming property, and 0.03 L / g or more is more preferable.

  It does not specifically limit as a manufacturing method of thermoplastic polymer (III), Methods, such as normal suspension polymerization, emulsion polymerization, block polymerization, are mentioned.

  The present invention is suitable for obtaining an acrylic resin film which is excellent in surface hardness, heat resistance and transparency, does not whiten the molded product when subjected to insert molding or in-mold molding, and has excellent trimming workability during molding. An acrylic resin composition is provided.

  Furthermore, the present invention defines the rubber content and gel content of the acrylic resin composition within a specific range in order to satisfy these multiple performances at a high level.

  That is, the rubber content of the acrylic resin composition of the present invention needs to be 25% by mass or more from the viewpoint of trimming processability during molding. On the other hand, from the viewpoint of surface hardness, heat resistance, etc., the rubber content of the acrylic resin composition is preferably 50% by mass or less, and more preferably 40% by mass or less.

  The “rubber content” as used in the present invention is defined as the proportion of the polymer having a Tg determined by the FOX formula of the polymer obtained from the monomer mixture in the rubber-containing polymer of less than 25 ° C.

  In addition, the gel content of the acrylic resin composition of the present invention needs to be less than 70% by mass from the viewpoint of film forming properties and trimming processability during molding. On the other hand, 40 mass% or more is preferable and 50 mass% or more is more preferable from the viewpoint of molding whitening resistance during insert molding or in-mold molding.

  In the present invention, the “gel content” is as defined in the section of the rubber-containing polymer (I).

  In the present invention, even when each of the rubber-containing polymer (I) or the rubber-containing polymer (II) is used, it is possible to obtain the rubber content and the gel content within the specified range described above. Form of the present invention in which the rubber-containing polymer (I) and the rubber-containing polymer (II) are used in combination in order to satisfy these contradictory performances such as molding whitening resistance, trimming processability, surface hardness, and heat resistance. It can only be achieved.

  The mass ratio of the rubber-containing polymer (I) and the rubber-containing polymer (II) constituting the acrylic resin composition of the present invention (hereinafter also simply referred to as “(I) / (II)”) is not particularly limited. 10/90 to 90/10 are preferable. When (I) / (II) is 10/90 or more, the acrylic resin film has excellent molding whitening resistance, heat resistance and surface hardness. More preferably, it is 30/70 or more.

Thermoplastic polymer (IV)
In addition to the rubber-containing polymer (I), rubber-containing polymer (II), and thermoplastic polymer (III), the acrylic resin composition of the present invention has a reduced viscosity (0.1 g of polymer dissolved in 100 mL of chloroform). And measured at 25 ° C.) may contain a thermoplastic polymer (IV) exceeding 0.15 L / g.

  The thermoplastic polymer (IV) is specifically composed of a composition of 50 to 100% by mass of methyl methacrylate and 0 to 50% by mass of another monomer having a double bond copolymerizable therewith. It is obtained by polymerizing the monomer component. The other monomer which has a copolymerizable double bond can be used individually or in mixture of 2 or more types.

  The thermoplastic polymer (IV) is a component that makes the film formability better. The thermoplastic polymer (IV) is used in the range of 0 to 20 parts by mass with respect to 100 parts by mass in total of the rubber-containing polymer (I), the rubber-containing polymer (II) and the thermoplastic polymer (III). It is preferable to do. By setting it to 20 parts by mass or less, an increase in the viscosity of the acrylic resin can be suppressed, and a decrease in film film formability can be prevented. More preferably, it is the range of 1-10 mass parts from a film film forming viewpoint.

<Acrylic resin film>
As for the thickness of the acrylic resin film of this invention, 10-500 micrometers is preferable. By setting the thickness of the acrylic resin film to 500 μm or less, rigidity suitable for insert molding or in-mold molding can be obtained, and the film can be manufactured more stably. Moreover, by making the thickness of the acrylic resin film 10 μm or more, a sense of depth can be more sufficiently imparted to the molded product together with the protection of the base material. The thickness of the acrylic resin film is more preferably 30 μm or more, and most preferably 50 μm or more. Moreover, the thickness of the acrylic resin film is more preferably 300 μm or less, and most preferably 200 μm or less.

  Usually, in order to form a coating film with a sufficient thickness for the purpose of imparting a sense of depth to the molded product by painting, it may be necessary to perform overcoating 10 or more times. not good. On the other hand, since the acrylic resin film itself can substitute for the coating film, the acrylic laminated molded product of the present invention can easily form a very thick coating film and has high industrial utility value.

(Combination agent)
The acrylic resin film of the present invention may be prepared by using commonly used compounding agents, for example, stabilizers, lubricants, processing aids, plasticizers, foaming agents, fillers, antibacterial agents, antifungal agents, mold releasing agents, as necessary. Additives such as an agent, an antistatic agent, a colorant, an ultraviolet absorber, a light stabilizer, a matting agent, and a light diffusing agent may be included.

  From the viewpoint of protecting the substrate, it is preferable to add an ultraviolet absorber in order to impart weather resistance. A well-known thing can be used as a ultraviolet absorber, A copolymer type thing can also be used. The molecular weight of the ultraviolet absorber is preferably 300 or more, more preferably 400 or more. When an ultraviolet absorbent having a molecular weight of 300 or more is used, mold contamination due to volatilization of the ultraviolet absorbent during vacuum molding or pressure molding in an injection mold can be prevented. In general, a UV absorber having a higher molecular weight is less prone to long-term bleed-out after being processed into a film state, and its UV absorption performance lasts longer than that having a lower molecular weight. Furthermore, when the molecular weight of the ultraviolet absorber is 300 or more, the amount of the ultraviolet absorber that volatilizes before the acrylic resin film is extruded from the T die and cooled by the cooling roll is small.

  Therefore, since the amount of the remaining ultraviolet absorber is sufficient, good performance is exhibited. In addition, the volatilized UV absorber recrystallizes on the chain that suspends the T die at the top of the T die and the exhaust hood and grows over time. This eventually falls on the film and becomes a defect in appearance. This also reduces the problem.

  Although the kind of ultraviolet absorber is not particularly limited, a benzotriazole-based or triazine-based one having a molecular weight of 400 or more can be particularly preferably used. Specific examples of the former include a trade name of Chivas Specialty Chemicals, Inc .: Tinuvin 234, a trade name of Asahi Denka Kogyo Co., Ltd .: ADK STAB LA-31, and specific examples of the latter include a trade name of Ciba Specialty Chemicals, Inc. 1577 etc. are mentioned.

  When the acrylic resin film of the present invention is used for vehicle applications, hair-styling resistance and fragrance resistance that meet the vehicle standards of various automobile manufacturers are required. Considering these characteristics, it is preferable to use an ultraviolet absorber having a melting point of 180 ° C. or lower. Such ultraviolet absorbers are difficult to crystallize when the hair styling agent or fragrance is applied to the acrylic resin film. Brand names manufactured by Ciba Specialty Chemicals: Tinuvin 234, Tinuvin 329, and Tinuvin 1577 are particularly preferable. By using such an ultraviolet absorber, the appearance hardly changes when a hair styling agent or a fragrance is attached.

  The amount of the ultraviolet absorber added is the sum of the rubber-containing polymer (I), the rubber-containing polymer (II), the thermoplastic polymer (III) and the thermoplastic polymer (IV) (hereinafter simply referred to as “acrylic resin raw material”). (It is also called) It is preferable to use in the range of 0.1-10 mass parts with respect to 100 mass parts. From the viewpoint of improving weather resistance, the amount is more preferably 0.5 parts by mass, and most preferably 1 part by mass or more. On the other hand, it is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, from the viewpoint of roll contamination during film formation, chemical resistance, and transparency.

  Moreover, it is preferable that the light stabilizer is added. Known light stabilizers can be used, but radical scavengers such as hindered amine light stabilizers are preferably used in order to improve not only the light resistance of the acrylic resin film but also the chemical resistance. . For example, the appearance change when the hairdressing material adheres is remarkably improved. Examples of such light stabilizers include ADK STAB LA57, ADK STAB LA67, SANOL LS770, and the like.

  The addition amount of the hindered amine light stabilizer is preferably used in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the acrylic resin raw material. From the viewpoint of improving light resistance and chemical resistance, the addition amount is more preferably 0.1 parts by mass, and most preferably 0.2 parts by mass or more. On the other hand, from the viewpoint of roll contamination during film formation, the upper limit is preferably 2 parts by mass or less, and most preferably 1 part by mass or less.

  As described above, by using an ultraviolet absorber having a melting point of 180 ° C. or less and a hindered amine light stabilizer in combination, an acrylic resin film particularly suitable for vehicle use can be obtained. Examples of the method of adding the compounding agent include a method of feeding the acrylic resin raw material together with the acrylic resin raw material to an extruder for forming an acrylic resin film, and a method of kneading and mixing the mixture obtained by adding the compounding agent in advance to the acrylic resin raw material in various kneaders. It is done. Examples of the kneader used in the latter method include ordinary single screw extruders, twin screw extruders, Banbury mixers, roll kneaders, and the like.

(Production method)
Examples of the method for producing the acrylic resin film of the present invention include known methods such as a melt casting method, a melt extrusion method such as a T-die method and an inflation method, and a calendar method. Is preferred.

  When forming an acrylic resin film by the T-die method, the surface smoothness of the acrylic resin film is improved according to a method of forming a film by sandwiching it between a plurality of rolls or belts selected from metal rolls, non-metal rolls and metal belts. And omission of printing when the acrylic resin film is printed. In addition, as a metal roll, it is used by the sleeve touch system which consists of a metal mirror surface touch roll, the metal sleeve (metal thin-film pipe) described in Japanese Patent No. 2808251 or WO97 / 28950, and a molding roll. A roll etc. can be illustrated. Moreover, as a nonmetallic roll, touch rolls, such as silicone rubber property, etc. can be illustrated. Examples of the metal belt include a metal endless belt. A plurality of these metal rolls, non-metal rolls and metal belts can be used in combination.

  In the above-described method for forming a film by sandwiching a plurality of rolls or belts selected from metal rolls, non-metal rolls and metal belts, the acrylic resin raw material after melt extrusion is substantially banked (resin pool). It is preferable to form a film by holding the film in a state where there is no film and transferring the surface without substantial rolling. When the film is formed without forming a bank (resin pool), the acrylic resin raw material in the cooling process is surface-transferred without rolling, so the heat shrinkage rate of the acrylic resin film formed by this method is reduced. You can also

  In addition, when melt extrusion is performed by a T-die method or the like, it is also preferable from the viewpoint of reducing FE in the film that the acrylic resin raw material in a molten state is filtered through a screen mesh of 200 mesh or more.

(Molding resistance to whitening of acrylic resin film)
The acrylic resin film of the present invention has excellent molding whitening resistance. As an index of resistance to molding whitening, whitening of a crease portion when a film (thickness: 125 μm) is rapidly bent by 180 degrees at room temperature can be mentioned. In the acrylic resin film of the present invention, the crease in the bending test is not whitened at all or slightly whitened, and the whitening that occurs in the process of insert molding or in-mold molding is hardly noticeable. Moreover, the molded product excellent in the designability can be obtained without the printed pattern disappearing.

(Surface hardness of acrylic resin film)
The acrylic resin film of the present invention preferably has a surface hardness of a pencil hardness (measured based on JIS K5400) higher than B. Furthermore, HB or more is more preferable, and F or more is most preferable.

  When an acrylic resin film having a pencil hardness higher than B is used, it is difficult to be scratched during the process of insert molding or in-mold molding, and the molded product has good scratch resistance. Moreover, the pencil hardness of the matte acrylic resin film or photocurable acrylic resin film for thermoforming of the present invention is also increased.

  When used for a vehicle, the pencil hardness of the acrylic resin film of the present invention is more preferably HB or higher. When the acrylic resin film has a pencil hardness of HB or more, the acrylic resin film, matte acrylic resin film or photocurable acrylic resin film of the present invention, and laminates using these films are used for door waist garnish, front control panel, power It can be suitably used for various vehicle members such as window switch panels and airbag covers.

  Furthermore, if the pencil hardness is F or higher, scratches are not noticeable even when scratched with a cloth with a rough surface such as gauze, and impart scratch resistance equivalent to a molded article using an acrylic resin film with a pencil hardness of 2H. Therefore, industrial use value is increased.

(Haze value of acrylic resin film)
As for the acrylic resin film of this invention, it is preferable that the haze value of the acrylic resin film measured by the test method of JIS K7136 is 2% or less. Such an acrylic resin film has an appearance equivalent to that of clear coating. More preferably, it is 1% or less, More preferably, it is 0.5% or less, Most preferably, it is 0.4% or less. Furthermore, the acrylic resin film of the present invention is excellent in transparency retention after heat molding in insert molding or in-mold molding. As an index, after the acrylic resin film is heated to 160 ° C., the haze value measured by the above test method is preferably 1% or less. More preferably, it is 0.5% or less, and most preferably 0.4% or less. Such an acrylic resin film is preferable because even if a blackish pattern layer such as jet black is provided, the pattern layer looks clear and faithful without being affected by the acrylic resin film.

(Heat resistance of acrylic resin film)
The acrylic resin film of the present invention preferably has a heat distortion temperature (measured based on ASTM D648) of 80 ° C. or higher. When the heat distortion temperature is 80 ° C. or higher, whitening and clouding are not observed on the surface of the acrylic resin film when exposed at a high temperature for a long time. In addition, in a vehicle application, when the thermal deformation temperature of the acrylic resin film is 80 ° C. or higher, the acrylic resin film, the matte acrylic resin film, and a laminate using these films are exposed to direct sunlight in the vehicle such as a front control panel. Can also be used on the receiving part. Furthermore, it is more preferable that the heat distortion temperature is 90 ° C. or higher from the viewpoint of expanding the application. The above-described measurement of the heat distortion temperature is carried out using a heat distortion temperature measurement specimen obtained by forming a raw material pellet of an acrylic resin film by injection molding and annealing at 60 ° C. for 4 hours. Is usually the same as the thermal deformation temperature of the acrylic resin film.

<Matte acrylic resin film>
The matte acrylic resin film of the present invention forms a matte layer containing a matting material and a curable binder resin as an outermost layer on one surface of the acrylic resin film.

(Matte layer)
The thickness of the matte layer is preferably 0.1 to 5 μm. When the thickness of the matte layer is 0.1 μm or more, surface properties such as scratch resistance can be exhibited when molded into a laminate. More preferably, it is 0.5 μm or more, and most preferably 0.8 μm or more. On the other hand, if the thickness of the matte layer is 5 μm or less, the upper limit of the thickness can reduce the occurrence of cracks in the matte layer even when the matte layer is formed into a deep drawing shape by insert molding or in-mold molding. The thickness of the matte layer is preferably 3 μm or less, more preferably less than 2 μm. Moreover, since the coating amount per unit area used in the coating is reduced, it is possible to reduce the physical property deterioration of the acrylic resin film due to the solvent. In addition, when the thickness of the matte layer is 5 μm or less, good matting properties can be expressed. By reducing the thickness of the matte layer, the matte property can be expressed well, so that the amount of the matte material per unit volume can be reduced. Further, by reducing the thickness of the matte layer, the effect of adding the wax is enhanced, so that good scratch resistance is exhibited.

  The thickness of the matte layer is determined by observing the cross section of the film with a transmission electron microscope, measuring the thickness at five locations, and averaging them. When the thickness of the matting layer is smaller than the mass average particle diameter of the matting material, the thickness is measured by observing a portion where the matting material is not present, that is, a portion consisting only of the binder resin.

(Matte material)
As the matting material, it is preferable to use an organic or inorganic material having a mass average particle diameter of 0.5 to 50 μm. From the viewpoint of matteness and appearance, the mass average particle diameter is more preferably 2 μm or more. By making the mass average particle diameter 2 μm or more, not only the matteness will be good, but also the reflection of fluorescent lamps will be reduced. For example, when combined with a metallic pattern, the appearance of scraping aluminum It becomes close to, and it looks like a luxury. On the other hand, the mass average particle diameter is more preferably 30 μm or less, and particularly preferably 10 μm or less, from the viewpoints of formability when forming the matte layer, appearance, and removal of the matting material from the binder resin. By making it 10 μm or less, not only the moldability of the matte layer will be improved, but also the reflection of the fluorescent lamp will be slightly visible, so when it is combined with a metallic pattern, for example, it looks close to the appearance of scraping aluminum The appearance looks stunning. For example, when a matte acrylic resin film is obtained by gravure coating or gravure reverse coating, the mass average particle diameter is more preferably 30 μm or less, and particularly preferably 10 μm or less, from the viewpoint of reducing doctor lines. Moreover, it is preferable to use the thing which does not contain the coarse grain of 20 micrometers or more from a viewpoint of coating omission generation | occurrence | production in the case of coating, or a doctor streak generation | occurrence | production.

  Examples of the organic matting material include silicone resin, styrene resin, styrene / acrylic resin, acrylic resin, fluororesin, benzoguanamine / formaldehyde condensate, benzoguanamine / melamine / formaldehyde condensate, and melamine / formaldehyde condensate. In order to make it clear, it is preferable to select a resin having a refractive index as close as possible to that of the binder resin. For example, when an acrylic resin is used as the binder resin, it is preferable to select beads made of crosslinked polymethyl methacrylate (crosslinked PMMA) as the matting material. On the contrary, the matte material can be selected according to the type of the pattern, such as a matte layer having a white feeling by using a matte material having a slightly different refractive index.

  Examples of inorganic matting materials include mica, talc, silica, calcium carbonate, titanium oxide, and iron oxide. In addition, inorganic particles surface-treated with acrylic resin, polyurethane resin, surfactant or the like can be used, but it is necessary to select a material to be surface-treated from the viewpoint of yellowing during heating. It is preferable to use a non-surface treated inorganic matting material from the viewpoint of yellowing during heating. Of these, silica is particularly preferred from the viewpoints of the appearance and physical properties of the matte acrylic resin film. Examples of silica include Mizukasil manufactured by Mizusawa Chemical Co., Ltd., Cicilia manufactured by Fuji Silysia Chemical Co., Ltd., and Cyrossphere. Further, the shape of silica may be any of a spherical shape, a scale shape, a plate shape, and an indefinite shape, and can be appropriately selected. Specifically, from the viewpoint of the efficiency of the matte appearance, it is preferable to select silica having an irregular shape, and the contact area between the matte surface and contaminants such as fingerprints is reduced, and the design of the contaminated part is reduced. From the viewpoint of suppressing the decrease, it is preferable to select spherical silica.

  When inorganic particles are used as a matting material, a unique whiteness can be imparted to the matte acrylic resin film, so that the design can be increased depending on the type of pattern, and the industrial utility value is high. In addition, when the matte material of inorganic particles is kneaded into the acrylic resin film substrate to obtain a matte film, the film itself becomes quite white, and thus the design is impaired when the pattern layer is formed.

  The addition amount of the matting material is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the binder resin. More preferably, it is 5 parts by mass or more, and particularly preferably 10 parts by mass or more. On the other hand, the amount of the matting material added is from the viewpoint of in-mold moldability and insert moldability, or a matte acrylic resin film is obtained by gravure coating, gravure reverse coating, kiss reverse coating, microgravure coating, etc. In the case, from the viewpoint of reducing doctor muscles, 30 parts by mass or less is more preferable, and 20 parts by mass or less is particularly preferable.

(wax)
As waxes, natural waxes such as carnauba wax, wax, montan wax, paraffin wax, synthetic waxes such as fatty acid amides, polyethylene, polypropylene, polytetrafluoroethylene, silicones such as alkyl-modified silicone oils, polyether-modified silicone oils, etc. Other examples include waxes and other block copolymer waxes containing silicone and fluorine components.

  In the present invention, it is preferable to use a polyolefin wax such as polyethylene, polypropylene, or a composite of polyethylene and polypropylene.

  From the viewpoint of mold contamination at the time of in-mold molding or insert molding, the higher the melting point, the harder it is to bleed by the heat during molding. Therefore, it is preferable that the melting point is 120 ° C. or higher, and 140 ° C. or higher. Is more preferable. In addition, regarding the block copolymer containing a silicone type and a fluorine-type component, it is possible to express the outstanding bleeding resistance even if melting | fusing point is 100 degrees C or less by selecting another copolymer component.

Examples of the wax having such a melting point include polyethylene, polypropylene, a composite of polyethylene and polypropylene, and polytetrafluoroethylene. From the viewpoint of the melting point, a composite of polyethylene and polypropylene is more preferable, and polytetrafluoroethylene is particularly preferable. From the viewpoint of the effect of preventing scratches, polytetrafluoroethylene is more preferable, and polyethylene, polypropylene, and a composite of polyethylene and polypropylene are particularly preferable. Further, by using these in combination, it is possible to develop more excellent scratch resistance, and a combination of polyethylene and polytetrafluoroethylene is particularly preferable.
On the other hand, those having a small specific gravity are preferred from the viewpoint of wax sedimentation during coating. For example, polytetrafluoroethylene having a specific gravity exceeding 2 is likely to settle, although it depends on the viscosity of the liquid at the time of coating. When the wax settles down during coating, the amount of wax contained in the matte layer is reduced, resulting in a decrease in scratch resistance. In addition, white streaks generated by winding up the precipitated wax by the plate roll are matte acrylic resin film Transferred as a defect on top.

  From the above, in the present invention, it is preferable to use polyolefin wax such as polyethylene, polypropylene, and a composite of polyethylene and polypropylene.

  In many cases, wax such as polyethylene, polypropylene, and a composite of polyethylene and polypropylene is used in the form of ultrafine powder obtained by dry pulverization. In the present invention, the mass average particle diameter is larger than the thickness of the matte layer. It is preferable to use a wax having the same. From the viewpoint of scratch resistance, it is more preferable to use a wax having a mass average particle diameter larger than a value obtained by doubling the thickness of the matte layer. Moreover, it is preferable to use the thing which does not contain the coarse grain of 20 micrometers or more from a viewpoint of coating omission generation | occurrence | production in the case of coating, or a doctor streak generation | occurrence | production.

  The addition amount of the wax is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoint of scratch resistance. More preferably, it is 3 parts by mass or more, and particularly preferably 5 parts by mass or more.

(Curable binder resin)
As the curable binder resin, a thermosetting resin or a photocurable resin is preferable from the viewpoint of scratch resistance, chemical resistance, and heat resistance. In addition, when a thermoplastic resin is used for the binder resin, although the moldability is good, the chemical resistance tends to decrease. When used as a vehicle interior, if a fragrance component adheres, the matte layer melts, so that an appearance defect such as a matte return may occur.

  For example, acrylic resin, urethane acrylate resin, silicone acrylate resin, epoxy resin, and ester resin can be used. Of these, urethane acrylate resins are excellent in physical properties.

  In particular, the urethane acrylate resin contains a hydroxyl group-containing acrylic resin having a methacrylic acid alkyl ester unit as a main component, a hydroxyl value of 20 to 120 mgKOH / g, and a Tg of 50 to 110 ° C., and polyisocyanate. A urethane acrylate thermosetting resin is preferred.

  The hydroxyl value of the hydroxyl group-containing acrylic resin is more preferably 50 mgKOH / g or more from the viewpoints of pencil hardness and scratch resistance, and 100 mgKOH / g from the viewpoint of chemical resistance, adhesion and cracking of the matte layer during molding. The following is more preferable.

  The Tg of the hydroxyl group-containing acrylic resin is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoints of heat resistance, film blocking properties, pencil hardness, and scratch resistance.

  As the polyisocyanate (curing agent), known ones can be used. In particular, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine that cause little yellowing during heating. An isocyanurate type polyisocyanate composed of diisocyanate or the like, an adduct type polyisocyanate with trimethylolpropane, or a burette type polyisocyanate is preferred. In addition, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate can be used as they are.

  The polyisocyanate is preferably used so as to have an addition amount corresponding to a range of 0.5 to 1.5 times the molar amount of the isocyanate group with respect to the molar amount of the hydroxyl group in the hydroxyl group-containing acrylic resin. By setting it to 0.5 times or more, since the amount of isocyanate groups is sufficient with respect to the hydroxyl group, the curing is sufficiently advanced and the pencil hardness, scratch resistance, and chemical resistance are improved. Less than 1.5 times the added amount, sufficient pencil hardness, scratch resistance and chemical resistance are exhibited, the matte layer is less likely to crack during molding, and there are problems such as film blocking due to excess polyisocyanate. It becomes difficult to occur.

  In addition, when a thermoplastic resin is used for the binder resin, although the moldability is good, the chemical resistance tends to decrease. When used as a vehicle interior, if a fragrance component adheres, the matte layer melts, so that an appearance defect such as a matte return may occur.

(Method of forming matte layer)
The matte layer is preferably formed by a printing method or a coating method. In this case, a matte layer is formed by preparing a paint by dissolving or dispersing the raw material to be the matte layer in a solvent, applying this to one side of the acrylic resin film, and then removing the solvent by heating and drying. Is done. This method is preferable because the adhesion between the matte layer and the acrylic resin film becomes good.

  Examples of the printing method include known printing methods such as gravure printing, screen printing, and offset printing.

  Coating methods include flow coating, spray coating, bar coating, gravure coating, gravure reverse coating, kiss reverse coating, micro gravure coating, roll coating, blade coating, rod coating, and roll doctor. Examples thereof include a coating method, an air knife coating method, a comma roll coating method, a reverse roll coating method, a transfer roll coating method, a kiss roll coating method, a curtain coating method, and a dipping coating method.

  Among these, the gravure coating method and the gravure reverse coating method which are not easily affected by the winding shape of the acrylic resin film are preferable. According to the gravure coating method and the gravure reverse coating method, coating omission and the like caused by film curling are unlikely to occur.

  As the gravure roll used in the gravure coating method, a known one can be used. In particular, it is preferable to use a diagonal roll having an inch width of 150 lines or more from the viewpoint of reducing the influence of the plate. If a plate is formed on the matte acrylic resin film, the design properties are impaired, and the industrial utility value is lowered. In addition, it is preferable to use the one in which the plate is formed in a slanted line because the plate can be reduced as compared with the case of using a gravure roll having a plate formed in a normal lattice shape.

  Moreover, it is preferable that it is engraved at an angle of 40 to 50 ° with respect to the roll axis direction. By using such a diagonal roll, it is possible to obtain an acrylic resin film having a uniform matte coating surface free from coating spots.

  As a material of the gravure roll, a known material such as a copper-plated hard chrome plate or a ceramic material can be used, but a ceramic material is preferable from the viewpoint of durability. The doctor blade used in the gravure coating method may be a known one made of steel, stainless steel, ceramic, or the like, but it is preferable to use a stainless doctor blade from the viewpoint of doctor muscles. Alternatively, it is also preferable to use a doctor blade in which a material made of ceramic and a lubricant is coated on a stainless doctor blade to improve the slipperiness. Also, a plastic doctor blade can be used.

In the case where a paint is applied on the acrylic resin film, the amount of the solvent contained in the paint applied per 1 m ^{2 of} the acrylic resin film is preferably 30 g or less from the viewpoint of reducing the physical properties of the acrylic resin film due to the solvent. 20 g or less is more preferable, and 10 g or less is particularly preferable. In addition, the amount of the coating material to be applied needs to be an amount such that the thickness of the matte layer after drying is 0.1 to 5 μm. When the coating amount is such that the matte layer has a thickness of 0.1 μm or more, the surface physical properties in the case of a laminate can be expressed. Preferably it is 0.5 micrometer or more, More preferably, it is 0.8 micrometer or more. If the amount of paint is such that the thickness of the matte layer is 5 μm or less, the amount of paint per unit area used in coating is reduced, so that the physical property deterioration of the acrylic resin film due to the solvent can be reduced. it can. The thickness of the matte layer is preferably 3 μm or less, more preferably less than 2 μm.

  As the solvent, a solvent having a boiling point not higher than 80 ° C., preferably not higher than 30 ° C., higher than the Tg of the binder resin is preferable because the solvent hardly remains in the matte acrylic resin film. In particular, each component of the binder resin and the matting material can be dissolved or uniformly dispersed, and the physical properties (mechanical strength, transparency, etc.) of the acrylic resin film are not adversely affected in practice. A volatile solvent having a boiling point which is not higher than 80 ° C., preferably not higher than 30 ° C., higher than the Tg of the resin component which is the main component of the acrylic resin film is preferable.

  For example, alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butanol and ethylene glycol, aromatic solvents such as xylene, toluene and benzene, aliphatic hydrocarbon solvents such as hexane and pentane, chloroform and carbon tetrachloride Halogenated hydrocarbon solvents such as phenol, phenol solvents such as phenol and cresol, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, acetone and cyclohexanone, diethyl ether, methoxytoluene, 1,2-dimethoxyethane, 1,2- Ether solvents such as dibutoxyethane, 1,1-dimethoxymethane, 1,1-dimethoxyethane, 1,4-dioxane, tetrahydrofuran (THF), fatty acid solvents such as formic acid, acetic acid, propionic acid, acetic anhydride, etc. Acid anhydride solvents, Ester solvents such as ethyl acetate, n-propyl acetate, butyl acetate and butyl formate, nitrogen-containing solvents such as ethylamine, toluidine, dimethylformamide and dimethylacetamide, sulfur-containing solvents such as thiophene and dimethyl sulfoxide, diacetone alcohol, 2 -Methoxyethanol (methyl cellosolve), 2-ethoxyethanol (ethyl cellosolve), 2-butoxyethanol (butyl cellosolve), diethylene glycol, 2-aminoethanol, acetocyanohydrin, diethanolamine, morpholine, 1-acetoxy-2-ethoxyethane, 2- Examples thereof include a solvent having two or more functional groups such as acetoxy-1-methoxypropane, water, and the like. These can be used alone or in combination of two or more solvents.

  Among these, a solvent mainly composed of ethyl acetate, n-propyl acetate, isopropyl alcohol, methyl ethyl ketone, and methyl isobutyl ketone is preferable because it can reduce deterioration of physical properties of the acrylic resin fill substrate due to the solvent. Moreover, it is preferable to use butyl acetate and methyl isobutyl ketone together from the viewpoint of adhesion between the matte layer and the acrylic resin fill substrate. Also, from the viewpoint of gloss after coating, it is preferable to use a medium boiling solvent such as butyl acetate and methyl isobutyl ketone, and a high boiling solvent such as 2-acetoxy-1-methoxypropane and cyclohexanone.

  When coating a paint on an acrylic resin film, from the viewpoint of the appearance of the matte layer, the viscosity of the paint is 10 seconds or less in terms of flow time with an Iwata cup viscometer (Anest Iwata, NK-2 model) Preferably it is in the range of 40 seconds. When the viscosity of the coating is 10 seconds or more, the gravure roll pattern is not noticeable when applied by the gravure coating method, and it is preferable because a good matte layer can be formed. In addition, when coating for a long time, paint constituent components such as a binder resin, a matting material, and an anti-scratch agent do not settle with time and are preferable because of excellent production stability. On the other hand, when the viscosity of the coating is 40 seconds or less, the transfer amount of the coating to the acrylic resin film does not decrease, and doctor streaks tend not to occur, and a good matte layer can be formed. preferable.

  The paint is preferably filtered to remove foreign substances and coarse particles of the compound in the paint such as silica and wax from the viewpoint of reducing omission of coating and reducing the generation of doctor streaks. Filtration may be performed after preparation of the paint, or may be performed immediately before coating or while coating. As a filtering device, CPII-10, 03, 01 manufactured by Chisso Filter Co., Ltd. is suitable.

  Additives to improve solution properties such as anti-skinning agents, thickeners, anti-settling agents, anti-sagging agents, antifoaming agents, leveling agents, light stabilizers, UV absorbers, antioxidants Additives for improving coating film performance such as antibacterial agents, antifungal agents, antistatic agents, and flame retardants can be added.

  When applying a coating material on an acrylic resin film, it is preferable to apply after removing foreign substances existing on the film surface in advance. As a result, coating omission due to foreign matters existing on the film surface can be reduced, and the appearance of the matte acrylic resin film is improved.

  The method for removing the foreign matter on the film surface is not particularly limited. For example, when the acrylic resin film is transported, a method in which an adhesive substance is brought into contact with a roll provided on the surface, or the acrylic resin film is vibrated by air. And a method of using a non-contact type web cleaner that releases foreign matter on the film surface and sucks the foreign matter.

  Specific examples of the roll provided with the adhesive substance on the surface include a roll wound with an adhesive tape, a rubber roll, and the like. Specific examples of non-contact type web cleaners include PV cleaner USW-101, USW-102 (PPV cleaner standard pressure type), USW-103 (high pressure type) manufactured by Hugle Electronics Co., Ltd. Can be mentioned. Further, a non-contact type cleaning system manufactured by Shinko Co., Ltd. may be used.

  In addition, for the purpose of facilitating the removal of foreign matter on the surface of the acrylic resin film, or preventing the foreign matter from adhering again after removing the foreign matter, a static electricity removing step using a static eliminator before and / or after the step of removing the foreign matter. May be provided.

  Usually, in order to form a coating film having a sufficient thickness on a molded product by coating, it may be necessary to apply several tens of times, and in this case, the cost is high and the productivity is not so good. On the other hand, the laminate having the matte acrylic resin film layer of the present invention can easily form a very thick coating film because the matte acrylic resin film itself can be used as a substitute for the coating film. High utility value.

(Pencil hardness of matte acrylic resin film)
The matte acrylic resin film of the present invention preferably has a pencil hardness (measured based on JIS K5600) higher than B. Furthermore, HB or more is more preferable, and F or more is most preferable.

  By using a matte acrylic resin film having a pencil hardness higher than B, scratches are less likely to occur in the insert molding or in-mold molding process, and the scratch resistance of the laminate is also improved. In order to obtain a matte acrylic resin film having such a pencil hardness, the pencil hardness of the acrylic resin film serving as a base material is important. The acrylic hardness of the acrylic resin film serving as the base material is preferably higher than B, more preferably HB or higher, and most preferably F or higher.

<Photocurable acrylic resin film>
The photocurable acrylic resin film of the present invention includes an acrylic resin film and generally known photocurable resins such as formaldehyde resin, amino resin, phenol resin, epoxy resin, polyurethane resin, urea resin, melamine resin, alkyd resin, Saturated polyester, acrylic resin, or the like can be used. In general, it can be laminated by screen printing, gravure printing, etc., but in particular, by applying pattern printing by the printing method etc. and sequentially irradiating a plurality of ultraviolet rays having different wavelengths, a high degree of stereoscopic effect etc. A design can also be given.

  From the viewpoint of wear resistance, scratch resistance, surface adhesion, storage stability, mold followability (hereinafter also referred to as moldability) during vacuum molding such as insert molding or in-mold molding, and process contamination. The curable resin layer is obtained from a photocurable resin composition (Z) containing a thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain and a photopolymerization initiator (z-2). It is preferable that

  Said photocurable resin composition (Z) contains the thermoplastic resin (z-1) which has a radically polymerizable unsaturated group in a side chain, and a photoinitiator (z-2), The said (z-1) It is preferable that it is a thing which does not contain crosslinkable compounds other than) substantially. In this invention, a photocurable acrylic resin film can be obtained by laminating | stacking the layer of this photocurable resin composition (Z) on an acrylic resin film.

  In the photocurable resin composition (Z) in the present invention, since a structure having a radically polymerizable unsaturated group is introduced into the polymer side chain as described above, a crosslinking reaction proceeds between the polymer side chains. A photocurable acrylic resin that provides good abrasion resistance and scratch resistance, and does not need to contain a low molecular weight crosslinkable compound having a reactive vinyl group, and therefore has no surface tackiness and excellent storage stability. It has the advantage that a film is obtained.

  The thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain has, for example, a radically polymerizable unsaturated group in the polymer having a Tg of 25 to 175 ° C., preferably 30 to 150 ° C. Things. Specifically, a polymer obtained by polymerizing or copolymerizing the following compounds (1) to (7) as a polymer with a radically polymerizable unsaturated group introduced by the methods (a) to (d) described later. Can be used. “(Meth) acrylate” represents acrylate or methacrylate, “(meth) acrylic acid” represents acrylic acid or methacrylic acid, “(meth) acrylamide” represents acrylamide or methacrylamide, and “( “(Meth) acryloyloxy” represents acryloyloxy or methacryloyloxy.

(1) Monomers having a hydroxyl group: N-methylolacrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (2) Monomers having a carboxyl group: (meth) acrylic acid, acryloyloxyethyl monosuccinate, etc. (3) Monomers having an epoxy group: glycidyl (meth) acrylate, 3,4- (4) Monomers having an aziridinyl group: 2-aziridinylethyl (meth) acrylate, allyl 2-aziridinylpropionate, etc. (5) Monomers having an amino group: (Meth) acrylamide, diacetone acrylamide, di Methylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc. (6) Monomer having sulfone group: 2-acrylamido-2-methylpropanesulfonic acid, etc. (7) Monomer having isocyanate group: 2, Adducts of radically polymerizable monomers having diisocyanate and active hydrogen, such as equimolar adducts of 4-toluene diisocyanate and 2-hydroxyethyl acrylate, 2-isocyanate ethyl (meth) acrylate, and the like.

  Furthermore, in order to adjust the Tg of the polymer or copolymer of the above compound or to harmonize the physical properties of the photocurable film, it may be copolymerized with a monomer copolymerizable with the above compound. it can. Examples of such copolymerizable monomers include (meth) acrylates such as methyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and isobornyl (meth) acrylate, N-phenylmaleimide, and cyclohexylmaleimide. And imide derivatives such as N-butylmaleimide, olefinic monomers such as butadiene, and aromatic vinyl compounds such as styrene and α-methylstyrene.

  A radically polymerizable unsaturated group can be introduced into the above-described polymer or copolymer by the following methods (i) to (d).

  (A) In the case of the polymer or copolymer of the monomer (1) having a hydroxyl group, the monomer (2) having a carboxyl group such as (meth) acrylic acid is subjected to a condensation reaction.

  (B) In the case of a polymer or copolymer of the monomer (2) having a carboxyl group and the monomer (6) having a sulfone group, the monomer (1) having the above hydroxyl group is condensed. React.

  (C) In the case of the polymer or copolymer of the monomer (3) having an epoxy group, the monomer (7) having an isocyanate group, or the monomer (4) having an aziridinyl group, The monomer (1) having a hydroxyl group or the monomer (2) having a carboxyl group is subjected to an addition reaction.

  (D) In the case of a polymer or copolymer of a monomer having a hydroxyl group or a carboxyl group, the monomer (3) having an epoxy group, the monomer (4) having an aziridinyl group, or an isocyanate group The monomer (7) or the equimolar adduct of a diisocyanate compound and a hydroxyl group-containing acrylate monomer is subjected to an addition reaction.

  (E) In the case of the polymer or copolymer of the monomer (5) having an amino group, the monomer (2) having the carboxyl group described above is subjected to a condensation reaction.

  (F) In the case of the polymer or copolymer of the monomer (5) having an amino group, the above-mentioned monomer (3) having an epoxy group or a monomer having an acetoacetoxy group is added to the reaction. Let

  The above reaction is preferably carried out while adding a small amount of a polymerization inhibitor such as hydroquinone and sending dry air.

  The amount of the radically polymerizable unsaturated group in the side chain of the thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain is the double bond equivalent (per one side chain radically polymerizable unsaturated group). The average molecular weight) is preferably an average of 3000 g / mol or less as calculated from the charged value from the viewpoint of improving scratch resistance and wear resistance. A more preferable range of double bond equivalent is an average of 1200 g / mol or less, and a more preferable range is an average of 800 g / mol or less.

  In this way, by introducing a plurality of radically polymerizable unsaturated groups involved in crosslinking into the thermoplastic resin, it is not necessary to use a low molecular weight crosslinking compound, and at the time of long-term storage and thermoforming described later. Moreover, it becomes possible to improve hardened | cured material property efficiently, without having surface adhesiveness.

  The number average molecular weight of the thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain is preferably in the range of 5,000 to 2,500,000, and in the range of 10,000 to 1,000,000. Is more preferable. When insert or in-mold molding a photocurable acrylic resin film formed using a photocurable resin composition (Z) containing a thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain The number average molecular weight is preferably 5,000 or more from the viewpoint of improving mold releasability and improving the surface hardness of the insert or in-mold molded product after photocuring. On the other hand, the number average molecular weight is preferably 2,500,000 or less from the viewpoint of ease of synthesis and appearance, and from the viewpoint of developing adhesiveness with the acrylic resin film-like product (A).

  Moreover, it is preferable that Tg is adjusted to 25-175 degreeC, and it is further more preferable that thermoplastic resin (z-1) which has a radically polymerizable unsaturated group in a side chain is adjusted to 25-175 degreeC. . Tg is 25 ° C. or higher from the viewpoint that the mold releasability of the photocurable acrylic resin film at the time of insert or in-mold molding is improved and the surface hardness of the insert or in-mold molded product after photo-curing is improved. Preferably there is. On the other hand, Tg is preferably 175 ° C. or less from the viewpoint of the handleability of the photocurable acrylic resin film or sheet.

  In consideration of Tg of the thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the obtained side chain, it is possible to use a vinyl polymerizable monomer that has a high Tg as a homopolymer. preferable. Furthermore, from the viewpoint of improving the weather resistance of the thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain, an acrylic resin using (meth) acrylate as a main component as a vinyl polymerizable monomer. It is preferable that As will be described later, when the inorganic fine particles (a-3) are added to the photocurable resin composition (Z) of the present invention, the functional groups (hydroxyl groups, carboxyls) on the surface of the inorganic fine particles (a-3) Group, silanol group, etc.), a vinyl polymerizable monomer having in its molecule at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a halogenated silyl group and an alkoxysilyl group. The monomer acts to further improve the physical properties such as rigidity, toughness, heat resistance, etc. of the resulting photocurable resin composition, so that such a functional group can be used as a part of a vinyl polymerizable monomer component capable of radical polymerization. It may be contained.

  Examples of vinyl polymerizable monomers containing such reactive groups in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, vinyltrichlorosilane, Examples include vinyltrimethoxysilane and γ- (meth) acryloyloxypropyltrimethoxysilane.

  As a photoinitiator (z-2) used by this invention, the photoradical polymerization initiator which generates a radical by light irradiation is mentioned.

  As the radical photopolymerization initiator, known compounds can be used, and are not particularly limited, but considering yellowing during curing and deterioration during weathering, such as acetophenone-based, benzophenone-based, acylphosphine oxide-based An initiator containing no amino group in the molecule is preferable. For example, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl Phosphine oxide is preferred. Among these, depending on the molding method, the temperature may be temporarily higher than the boiling point of the compound, and therefore may be appropriately selected according to the molding method. In order to increase the surface hardness of the molded product, an additive such as n-methyldiethanolamine that suppresses polymerization hardening inhibition by oxygen may be added. In addition to these photopolymerization initiators, various peroxides may be added in consideration of curing using heat during molding. When a photocurable acrylic resin film contains a peroxide, it must be cured at 150 ° C. for about 30 seconds. Therefore, a peroxide having a low critical temperature, such as lauroyl peroxide, t-butylperoxy, etc. 2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and the like are preferably used.

  The amount of radical photopolymerization initiator added is preferably 5% by weight or less based on the compound having a radically polymerizable unsaturated group in the side chain, since the residual amount after curing affects the weather resistance. The amount of the amino-based radical photopolymerization initiator related to the change is preferably 1% by weight or less.

  Inorganic fine particles (a-3) can be added to the photocurable resin composition (Z) of the present invention for the purpose of further improving scratch resistance and abrasion resistance. In the inorganic fine particles (a-3) used in the present invention, the type, particle diameter, and form are not particularly limited as long as the obtained photocurable resin composition becomes transparent. Examples of the inorganic fine particles include colloidal silica, alumina, titanium oxide, and the like. These may be used alone or in combination of two or more. Of these, colloidal silica is particularly preferable from the viewpoints of availability, price, transparency of the resulting photocurable resin composition layer, and expression of wear resistance.

  Colloidal silica can be used in the form of a normal aqueous dispersion or in a form dispersed in an organic solvent, but with a thermoplastic resin having a radically polymerizable unsaturated group in the side chain as component (z-1). In order to disperse uniformly and stably, it is preferable to use colloidal silica dispersed in an organic solvent.

  Examples of such organic solvents include methanol, isopropyl alcohol, n-butanol, ethylene glycol, xylene / butanol, ethyl cellosolve, butyl cellosolve, dimethylformamide, dimethylacetamide, methyl ethyl ketone, methyl isobutyl ketone, toluene and the like. Especially, in order to disperse | distribute uniformly with a thermoplastic resin, it is preferable to select the organic solvent which can melt | dissolve the thermoplastic resin (z-1) which has a radically polymerizable unsaturated group in a side chain. Further, as will be described later, when the photocurable acrylic resin film of the present invention is produced, these organic solvents are heated and dried to volatilize, so that the Tg of the resin component which is the main constituent component of the acrylic resin film is 80 ° C. An organic solvent having a boiling point not higher than this, preferably not higher than 30 ° C., is preferably difficult to remain in the photocurable acrylic resin film.

  Colloidal silica in a form dispersed in an organic solvent includes commercially available products dispersed in a dispersion medium, such as methanol silica sol MA-ST, isopropyl alcohol silica sol IPA-ST, n-butanol silica sol NBA-ST, ethylene glycol silica sol EG. -ST, xylene / butanol silica sol XBA-ST, ethyl cellosolve silica sol ETC-ST, butyl cellosolve silica sol BTC-ST, dimethylformamide silica sol DBF-ST, dimethylacetamide silica sol DMAC-ST, methyl ethyl ketone silica sol MEK-ST, methyl isobutyl ketone silica sol MIBK- ST (trade name, manufactured by Nissan Chemical Co., Ltd.) or the like can be used.

  The particle diameter of the inorganic fine particles (a-3) is usually 200 nm or less from the viewpoint of the transparency of the resulting photocurable resin composition layer. More preferably, it is 100 nm or less, More preferably, it is 50 nm or less.

  The added amount of the inorganic fine particles (a-3) is 5 to 400 weights in solid content of the inorganic fine particles relative to 100 weight parts of the solid content of the thermoplastic resin (z-1) having a radical polymerizable unsaturated group in the side chain. The range of parts is preferable, and the range of 10 to 200 parts by weight is particularly preferable. When the addition amount of the inorganic fine particles is less than 5 parts by weight, the effect of improving the wear resistance may not be observed. When the addition amount exceeds 400 parts by weight, the photocurable resin composition (Z ), The moldability of the resulting photocurable acrylic resin film may be reduced.

  Moreover, as an inorganic fine particle (a-3) used by this invention, you may use what the surface was previously processed with the silane compound represented by the following structural formula (a3-1). Use of the surface-treated inorganic fine particles further improves the storage stability of the photocurable resin composition (Z), and also improves the surface hardness and weather resistance of the resulting photocurable acrylic resin film or sheet. preferable.

SiR ¹ _a R ² _b (OR ³ ) _c (a3-1)
(In the above formula, R ¹ and R ² each represent a C 1-10 hydrocarbon residue optionally having an ether bond, an ester bond, an epoxy bond, or a carbon-carbon double bond; ³ represents a hydrogen atom or an ether bond, an ester bond, an epoxy bond, or a hydrocarbon residue having 1 to 10 carbon atoms which may have a carbon-carbon double bond, and a and b are 0 to 3 respectively. And c is an integer of 1 to 4 that satisfies 4-ab.

  Among the silane compounds represented by the structural formula (a3-1), silane compounds represented by the following structural formulas (a3-2) to (a3-7) can be given as preferable examples.

SiR ⁴ _a R ⁵ _b (OR ⁶ ) _c (a3-2)
SiR ⁴ _n (OCH ₂ CH ₂ OCO (R ⁷ ) C═CH ₂ ) _4-n (a3-3)
^{_{CH 2 = C (R 7)}} COO (CH 2) p SiR 8 n (OR 6) 3-n (a3-4)
CH ₂ = CHSiR ⁸ _n (OR ⁶ ) _3-n (a3-5)
HS (CH ₂ ) _p SiR ⁸ _n (OR ⁶ ) _3-n (a3-6)

(In the above formula, R ⁴ and R ⁵ each represent a hydrocarbon residue having 1 to 10 carbon atoms which may have an ether bond, an ester bond or an epoxy bond, and R ⁶ represents a hydrogen atom or a carbon number. Represents a hydrocarbon residue having 1 to 10, R ⁷ represents a hydrogen atom or a methyl group, R ⁸ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and a and b each represent 0 to 3 C is an integer of 1-4 satisfying 4-ab, n is an integer of 0-2, and p is an integer of 1-6).

  Examples of the silane compound represented by the structural formula (a3-2) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, methylethyldiethoxysilane, methylphenyldimethoxysilane, trimethylethoxysilane, methoxyethyltriethoxysilane, acetoxyethyltriethoxysilane, Diethoxyethyldimethoxysilane, tetraacetoxysilane, methyltriacetoxysilane, tetrakis (2-methoxyethoxy) silane, γ-glycidoxy Trimethoxysilane, .gamma.-glycidoxypropylmethyldiethoxysilane, beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

  Examples of the silane compound represented by the structural formula (a3-3) include tetrakis (acryloyloxyethoxy) silane, tetrakis (methacryloyloxyethoxy) silane, methyltris (acryloyloxyethoxy) silane, and methyltris (methacryloyloxyethoxy) silane. Etc.

  Examples of the silane compound represented by the structural formula (a3-4) include β-acryloyloxyethyldimethoxymethylsilane, γ-acryloyloxypropylmethoxydimethylsilane, γ-acryloyloxypropyltrimethoxysilane, and β-methacryloyloxy. Examples include ethyldimethoxymethylsilane and γ-methacryloyloxypropyltrimethoxysilane.

  Examples of the silane compound represented by the structural formula (a3-5) include vinylmethyldimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

  Examples of the silane compound represented by the structural formula (a3-6) include γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, and the like.

  Examples of the silane compound represented by the structural formula (a3-7) include p-vinylphenylmethyldimethoxysilane and p-vinylphenyltrimethoxysilane.

  Such a silane compound is preferably used in a proportion of 0 to 3 mole parts relative to 1 mole part of the solid content of the inorganic fine particles (a-3). When the usage-amount of a silane compound exceeds 3 mol part, the abrasion resistance of the photocurable acrylic resin film or sheet obtained may fall.

Here, the molar part is a value obtained by dividing the mass part of the inorganic fine particles or the silane compound by the molecular weight. For example, 100 parts by mass of solid content of colloidal silica (SiO ₂ ), which is an inorganic fine particle, corresponds to 100 ÷ 60 = 1.666 mol part.

  The inorganic fine particles surface-treated with the silane compound can be obtained by using a commercially available product or by subjecting the inorganic fine particles to a surface treatment by a known method. As a known surface treatment method, for example, the treatment can be performed by heating and stirring the silane compound and the inorganic fine particles in the presence of a small amount of water.

  As a method of adding the inorganic fine particles (a-3) to the thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain, a thermoplastic resin having a radically polymerizable unsaturated group in the side chain in advance. After synthesizing (z-1), inorganic fine particles may be mixed, and the vinyl polymerizable monomer and inorganic constituting the thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain. Any method such as a method of polymerizing under a condition in which fine particles are mixed can be selected.

  In the photocurable resin composition (Z) used in the present invention, a thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain of essential components and a photopolymerization initiator (z-2), Furthermore, in addition to the above-mentioned inorganic fine particles (a-3) that can be used as necessary, sensitizers, modifying resins, dyes, pigments, leveling agents, anti-repelling agents, and ultraviolet absorbers as necessary. Additives such as light stabilizers and oxidation stabilizers can be blended.

  The above sensitizer accelerates the photocuring reaction, and examples thereof include benzophenone, benzoin isopropyl ether, and thioxanthone.

  However, the photocurable resin composition (Z) should not contain substantially any crosslinkable compound other than the thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain. In particular, liquid crosslinkable monomers and oligomers at 40 ° C. and low molecular weight crosslinkable monomers and oligomers having a molecular weight of 2000 or less should not be substantially contained. In particular, when it contains a liquid crosslinkable monomer / oligomer at 40 ° C. or a low molecular weight crosslinkable monomer / oligomer having a molecular weight of 2000 or less, it will have surface tackiness during long-term storage or thermoforming, and printing. In some cases, problems may occur in the process, or the mold may be contaminated during insert molding or in-mold molding. More preferably, it should substantially not contain a liquid crosslinkable monomer or oligomer at 50 ° C., and more preferably it should substantially not contain a liquid crosslinkable monomer or oligomer at 60 ° C.

  In the present invention, since the photocurable resin composition (Z) as described above is used, the photocurable acrylic resin film is formed by laminating the photocurable resin composition on the acrylic resin film. The surface of the photocurable acrylic resin film is not tacky, and the phenomenon that the tackiness of the surface changes with time does not occur, and the storage stability in the roll state is improved.

  Since the photocurable acrylic resin film of the present invention has the above-described configuration, it has excellent moldability and storage stability before photocuring, and excellent surface properties (hardness, weather resistance, etc.) after photocuring. It is a photo-curable acrylic resin film that is compatible with high dimensions. As will be described later, the photocurable acrylic resin film of the present invention is usually obtained by mixing and dissolving a photocurable resin composition (Z) in a solvent such as an organic solvent on the acrylic resin film by various coating methods. It is manufactured by performing heat drying to remove the solvent after coating. At this time, if a large amount of the solvent remains in the photo-curable acrylic resin film, the surface of the photo-curable resin composition (Z) layer before light irradiation becomes sticky, and the yield in the printing process is increased. This causes problems such as lowering, lowering of storage stability in a roll state, and lowering of mold contamination during insert molding or in-mold molding. In addition, surface properties such as scratch resistance, chemical resistance, and weather resistance can be obtained even when photo-curing an insert molded product or an in-mold molded product obtained by insert molding or in-mold molding of a photocurable acrylic resin film. May be inferior. In order to solve such a problem, it is preferable to reduce the amount of the solvent in the photocurable acrylic resin film or sheet as much as possible.

  As a manufacturing method of the photocurable acrylic resin film or sheet of the present invention comprising an acrylic resin film and a photocurable resin composition (Z) layer, for example, heat having a radically polymerizable unsaturated group in the side chain of the essential component The photocurable resin composition (Z) containing the plastic resin (z-1), the photopolymerization initiator (z-2), and if necessary inorganic fine particles (a-3) is sufficiently stirred in a solvent such as an organic solvent. Dissolved, known printing methods such as gravure printing method, screen printing method, offset printing method, flow coating method, spray coating method, bar coating method, gravure coating method, roll coating method, blade coating method, rod coating method, Roll doctor coating method, air knife coating method, comma roll coating method, reverse roll coating method, transfer roll coating method, kiss roll coating method, curtain coating method Law, by a known coating method such as dipping coating was coated on an acrylic resin film, there is a method of the laminated film or sheet and dried by heating for solvent removal.

  It is preferable that an organic solvent having a boiling point not higher than Tg by 80 ° C. or higher, preferably not higher than 30 ° C. hardly remains in the photocurable acrylic resin film.

  As a solvent for stirring and dissolving the photocurable resin composition (Z), each component of the photocurable resin composition (Z) is dissolved or uniformly dispersed, and the physical properties (mechanical strength, transparency of the acrylic resin film) ), Etc., and has a boiling point not higher than 80 ° C., preferably not higher than 30 ° C. than the Tg of the resin component which is the main component of the acrylic resin film. Solvents are preferred. Examples of such solvents include alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butanol and ethylene glycol; aromatic solvents such as xylene, toluene and benzene; aliphatic hydrocarbon solvents such as hexane and pentane; Halogenated hydrocarbon solvents such as chloroform and carbon tetrachloride; phenol solvents such as phenol and cresol; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and acetone; diethyl ether, methoxytoluene, 1,2-dimethoxyethane, 1 Ether solvents such as 1,2-dibutoxyethane, 1,1-dimethoxymethane, 1,1-dimethoxyethane, 1,4-dioxane, THF; fatty acid solvents such as formic acid, acetic acid, propionic acid; acetic anhydride, etc. Acid anhydride solvents; ethyl acetate, butyl acetate, Ester solvents such as butyl acid; nitrogen-containing solvents such as ethylamine, toluidine, dimethylformamide and dimethylacetamide; sulfur-containing solvents such as thiophene and dimethyl sulfoxide; diacetone alcohol, 2-methoxyethanol (methylcellosolve), 2-ethoxy Solvents having two or more functional groups such as ethanol (ethyl cellosolve), 2-butoxyethanol (butyl cellosolve), diethylene glycol, 2-aminoethanol, acetocyanohydrin, diethanolamine, morpholine; or various known solvents such as water are used. be able to.

    In order to eliminate the problems caused by the residual solvent in the photocurable acrylic resin film described above, and to produce a photocurable acrylic resin film in a shorter time for the purpose of improving production efficiency at low cost, It is necessary to reinforce the heat drying conditions for removing the solvent and perform the drying sufficiently. However, at this time, if the photocurable acrylic resin film is continuously heated and dried for 20 seconds or more at a temperature equal to or higher than the thermal deformation temperature of the acrylic resin film, the photocurable acrylic resin film is stretched even with a slight tension. In addition, the photocurable resin composition (Z) layer and the acrylic resin film are not only thinned, but also the photocurable resin composition (Z) after photocuring may have scratch resistance, a decrease in surface hardness, and the like. is there.

  The heat-drying conditions of the photo-curable acrylic resin film are as follows: heat drying at a temperature not exceeding the thermal deformation temperature of the acrylic resin film, or acrylic drying when drying at a temperature higher than the thermal deformation temperature of the acrylic resin film. The heat deformation temperature of the resin film is + 15 ° C. or lower, preferably + 10 ° C. or lower, and the heat drying time at that temperature is 20 seconds or shorter, preferably 10 seconds or shorter, more preferably 5 seconds or shorter.

  When using a flammable organic solvent as a solvent, use a device equipped with an air heating type heat source by steam from the point of safety, and use a method and nozzle that counteracts hot air in the dryer. A method of spraying on a photocurable acrylic resin film or sheet can be used. As the shape of the dryer, a known one such as an arch type or a flat type can be selected and used according to the purpose.

<Acrylic resin laminated film>

<Pattern layer>
A pattern layer may be formed on at least one surface of the acrylic resin film, matte acrylic resin film, or photocurable acrylic resin film of the present invention in order to impart design properties. In the case of a matte acrylic resin film, it is preferable to form a picture layer on the surface opposite to the surface on which the matte layer is provided. In the case of a photocurable acrylic resin film, it is preferable to form a pattern layer on the surface opposite to the photocurable resin layer. Moreover, at the time of manufacture of a laminated body, it is preferable from the point of protection of a decorating surface and provision of a high-class feeling to arrange a pattern layer on the adhesive surface with a base material.

  The pattern layer can be formed by a known method. The pattern layer is preferably a printing layer formed by a printing method and / or a vapor deposition layer formed by a vapor deposition method.

(Print layer)
The printed layer becomes a pattern or characters on the surface of the laminate obtained by insert or in-mold molding. Examples of the print pattern include a pattern made of wood grain, stone grain, cloth grain, sand grain, geometric pattern, letters, full-face solid, metallic and the like.

  As binders for the printing layer, polyvinyl resins such as vinyl chloride / vinyl acetate copolymers, polyamide resins, polyester resins, polyacrylic resins, polyurethane resins, polyvinyl acetal resins, polyester urethane resins, cellulose Examples of the resin include ester resins, alkyd resins, and chlorinated polyolefin resins. As the polyacrylic resin, for example, an acrylic resin composition containing the rubber-containing polymer (I) of the present invention may be used.

  For the formation of the printing layer, a colored ink containing a binder and an appropriate color pigment or dye may be used.

  Examples of the pigment include the following. Examples of yellow pigments include azo pigments such as polyazo, organic pigments such as isoindolinone, and inorganic pigments such as yellow lead. Examples of red pigments include azo pigments such as polyazo, organic pigments such as quinacridone, and inorganic pigments such as petals. Examples of the blue pigment include organic pigments such as phthalocyanine blue and inorganic pigments such as cobalt blue. Examples of the black pigment include organic pigments such as aniline black. Examples of the white pigment include inorganic pigments such as titanium dioxide.

  As the dye, various known dyes can be used as long as the effects of the present invention are not impaired.

  Examples of the method for forming the printing layer include known printing methods such as offset printing, gravure rotary printing, and screen printing, known coating methods such as roll coating and spray coating, flexographic printing, and the like. The thickness of the printing layer may be appropriately determined as necessary, and is usually about 0.5 to 30 μm.

The number of missing prints in the print layer is preferably 10 pieces / m ² or less from the viewpoints of design properties and decorating properties. By setting the number of printing omissions to 10 pieces / m ² or less, the appearance of the laminate using the acrylic resin film and the matte acrylic resin film of the present invention becomes better. The number of missing prints in the print layer is more preferably 5 pieces / m ² or less, and particularly preferably 1 piece / m ² or less. The thickness of the printed layer may be appropriately selected according to the degree of elongation at the time of molding so that a desired surface appearance can be obtained in a laminate obtained by insert or in-mold molding.

(Deposition layer)
The vapor deposition layer is formed of at least one metal selected from the group consisting of aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead, zinc, and the like, or an alloy or compound thereof. . Examples of the method for forming the vapor deposition layer include vacuum vapor deposition, sputtering, ion plating, and plating.

  The vapor deposition layer may be appropriately selected according to the degree of extension during molding so that a desired surface appearance can be obtained in a laminate obtained by insert or in-mold molding.

<Other layers>

(Thermoplastic resin layer)
The acrylic resin film, matte acrylic resin film, and photocurable acrylic resin film of the present invention may be laminated on a thermoplastic resin to form a laminated film or sheet. In particular, in the case of a matte acrylic resin film, the direction of lamination on the thermoplastic resin layer is preferably such that the surface opposite to the surface on which the matte layer is provided is in contact with the thermoplastic resin layer. In particular, in the case of a photocurable acrylic resin film, the direction of lamination on the thermoplastic resin layer is preferably such that the surface opposite to the photocurable resin layer is in contact with the thermoplastic resin layer.

  The thermoplastic resin layer is preferably made of a material having compatibility with the base material for the purpose of improving adhesion with the base material described later. More preferably, the thermoplastic resin layer is made of the same material as the base material. As the thermoplastic resin layer, a known thermoplastic resin film or sheet can be used, for example, an acrylic resin, ABS resin, AS resin, vinyl chloride resin, polyethylene, polypropylene, polybutene, polyolefin resin such as polymethylpentene, Polyethylene copolymers such as ethylene-vinyl acetate copolymer or saponified products thereof, ethylene- (meth) acrylic ester copolymers, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, etc. Resin, polyamide resins such as 6-nylon, 6,6-nylon, 6,10-nylon, 12-nylon, polystyrene resins, cellulose derivatives, fiber derivatives such as nitrocellulose, polyvinyl fluoride, poly Fluoride, polytetrafluoroethylene, ethylene - fluorine-based resin such as tetrafluoroethylene copolymers, or two or more copolymers, or a mixture selected from these, complexes, laminates, and the like.

  Among these, as the thermoplastic resin layer, the formability of the pattern layer (the pattern layer is not formed on the acrylic resin film, matte acrylic resin film, or photocurable acrylic resin film of the present invention, but a thermoplastic resin. Acrylic resin, ABS resin, vinyl chloride resin, polyolefin, and polycarbonate are preferable from the viewpoint of secondary formability of the laminated film or sheet.

  If necessary, the thermoplastic resin layer may contain general compounding agents such as stabilizers, antioxidants, lubricants, processing aids, plasticizers, impact agents, foaming agents, fillers, antibacterial agents, and antifungal agents. An agent, a release agent, an antistatic agent, a colorant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a flame retardant, and the like may be blended.

  The thickness of the thermoplastic resin layer may be appropriately determined as necessary, and is usually preferably about 20 to 500 μm. The thermoplastic resin layer is an acrylic resin film, a matte acrylic resin film, a photocurable acrylic resin film of the present invention that has a completely smooth appearance, absorbs surface defects of the substrate, or a pattern layer during injection molding It is preferable to have such a thickness that does not disappear.

  Examples of a method for obtaining a laminated film or sheet include known methods such as thermal lamination, dry lamination, wet lamination, and hot melt lamination. Moreover, the acrylic resin film of the present invention, the matte acrylic resin film, the photocurable acrylic resin film and the thermoplastic resin layer can be laminated by extrusion lamination.

  The acrylic resin film, matte acrylic resin film, and photocurable acrylic resin film of the present invention are laminated films or sheets, thereby exhibiting sufficient strength for handling against external forces such as impact and deformation. For example, cracks and the like are less likely to occur when the film is vacuum-molded by insert molding or the like and then removed from the mold, or when the vacuum-molded product is mounted on an injection mold. , Handling becomes good. In particular, when using a laminated film or sheet made of the acrylic resin film, matte acrylic resin film, photocurable acrylic resin film of the present invention, during trimming in insert molding, the acrylic resin film, matte acrylic resin film, It becomes possible to remarkably reduce cracks and crack defects in the photocurable acrylic resin film. Furthermore, it is possible to set a wide processing condition width in trimming.

  The trimming method includes a method of burning by irradiating with a laser beam, a method of producing a punching die for trimming and punching it by press working, and a method of removing it by tearing manually. If necessary, the acrylic resin film of the present invention, matte acrylic resin film, one side of a photocurable acrylic resin film, the surface of a thermoplastic resin layer of a laminated film or sheet, for example, corona treatment, ozone treatment, plasma Surface treatments such as treatment, ionizing radiation treatment, dichromic acid treatment, anchoring, and primer treatment may be applied. These surface treatments are acrylic resin film, matte acrylic resin film, between photocurable acrylic resin film and picture layer, between thermoplastic resin layer and picture layer, acrylic resin film, matte acrylic resin film, Adhesion between the photocurable acrylic resin film and the thermoplastic resin layer can be improved.

<Laminated body>
The laminate of the present invention is obtained by laminating the laminated film or sheet of the acrylic resin film, matte acrylic resin film, and photocurable acrylic resin film of the present invention on a substrate. In particular, in the case of a matte acrylic resin film, it is preferable that the surface opposite to the surface on which the matte layer is provided is in contact with the substrate. In particular, in the case of a photocurable acrylic resin film, it is preferable that the surface opposite to the photocurable resin layer is in contact with the substrate.

  Examples of the material for the substrate include resin, wood veneer, wood plywood, particle board, medium density fiber board (MDF) and other wood boards, wood fiber board and other water quality boards, and metals such as iron and aluminum.

  Examples of the resin include polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, polyolefin resin such as olefin thermoplastic elastomer, polystyrene resin, ABS resin, AS resin. General-purpose engineering such as general-purpose thermoplastic or thermosetting resin such as acrylic resin, urethane resin, unsaturated polyester resin, epoxy resin, polyphenylene oxide / polystyrene resin, polycarbonate resin, polyacetal, polycarbonate-modified polyphenylene ether, polyethylene terephthalate Resin, Polysulfone, Polyphenylene sulfide, Polyphenylene oxide, Polyetherimide, Polyimide, Liquid crystal polyester, Polyallyl heat-resistant resin Super engineering resins such as glass fiber or inorganic filler (talc, calcium carbonate, silica, mica, etc.) reinforcing materials such as, complex was added modifiers, such as the rubber component resins or various modified resins.

  Among these, as the material of the base material, a resin that can be melt-bonded is preferable, for example, ABS resin, AS resin, polystyrene resin, polycarbonate resin, vinyl chloride resin, acrylic resin, polyester resin, or a resin mainly composed of these. Is mentioned. In terms of adhesiveness, an ABS resin, an AS resin, a polycarbonate resin, a vinyl chloride resin, or a resin containing these as a main component is preferable, and an ABS resin, a polycarbonate resin, or a resin containing these as a main component is more preferable.

  Even if it is a resin that is not heat-sealed, such as a polyolefin-based resin, it is selected from the group consisting of an acrylic resin film, a matte acrylic resin film, a photocurable acrylic resin film, or a laminated film or sheet thereof by providing an adhesive layer. It is possible to bond one to the substrate during molding.

  As a method for producing the laminate of the present invention, a known method such as thermal lamination can be used in the case of a two-dimensional laminate and when the substrate can be heat-sealed. For example, for wood substrates such as wood veneer, wood plywood, particle board, medium density fiber board (MDF), water quality boards such as wood fiber board, metals such as iron and aluminum, etc. It is possible to bond them through an adhesive layer.

  In the case of a three-dimensional laminate, a known method such as an insert molding method or an in-mold molding method can be used.

  With the insert molding method, a film or sheet that has been decorated such as printing is molded into a three-dimensional shape by vacuum molding or the like in advance, and after removing the unnecessary film or sheet portion, it is transferred into an injection mold. Then, an integrated molded product is obtained by injection molding a resin as a base material.

  The in-mold molding method is a method in which a film or sheet decorated with printing or the like is placed in an injection mold, vacuum-molded, and then a resin as a base material is injection-molded in the same mold. Thus, an integrated molded product is obtained.

  When a three-dimensional shape is imparted to a film by vacuum forming, the acrylic resin film, matte acrylic resin film, photocurable acrylic resin film or laminated film or sheet of the present invention is rich in elongation at high temperatures, Very advantageous.

As a resin used for injection molding, a resin whose shrinkage rate after injection molding is similar to the shrinkage rate of the acrylic resin film, matte acrylic resin film, photocurable acrylic resin film or laminated film or sheet of the present invention, This is preferable because problems such as warpage of a laminate obtained by in-mold molding or insert molding, or peeling of a film or sheet can be solved.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by an Example. In the examples, “part” means “part by mass”. Abbreviations in the examples are as follows.

Abbreviations: Compound MMA: Methyl methacrylate MA: Methyl acrylate n-BA: N-butyl acrylate St: Styrene 1,3-BD: 1,3-butylene glycol dimethacrylate AMA: Allyl methacrylate CHP: Cumene hydroperoxide t-BH: t-butyl hydroperoxide t-HH: t-hexyl hydroperoxide n-OM: n-octyl mercaptan EDTA: disodium ethylenediaminetetraacetate HEMA: 2-hydroxyethyl methacrylate MEK: methyl ethyl ketone MIBK: methyl isobutyl Ketone

[Measurement and evaluation method of physical properties]
Physical properties of rubber-containing polymer (I), rubber-containing polymer (II) and thermoplastic polymer (III), acrylic resin films and matte acrylic resin films obtained in Examples 1-18 and Comparative Examples 1-9 The physical properties of the photocurable acrylic resin film and the laminate were measured and evaluated as follows.

  Evaluation of the laminated body was performed using the laminated body produced for the moldability evaluation shown in the following (17) or (18).

(1) Mass average particle diameter of rubber-containing polymers (I) and (II):
About the polymer latex of rubber-containing polymers (I) and (II) obtained by emulsion polymerization, a dynamic light scattering method using a light scattering photometer DLS-700 (trade name) manufactured by Otsuka Electronics Co., Ltd. It was measured.

(2) Gel content of rubber-containing polymers (I) and (II) and acrylic resin composition:
A predetermined amount (mass before extraction) of rubber-containing polymer (I), rubber-containing polymer (II) (coagulated powder obtained after polymerization) and acrylic resin composition (pellet-like material obtained after extrusion) Extraction treatment was performed under reflux in an acetone solvent, and the treated solution was separated by centrifugation, dried, then measured for the mass of acetone-insoluble matter (post-extraction mass), and calculated according to the following formula.

Gel content (%) = mass after extraction (g) / mass before extraction (g) × 100
(3) Tg (Tg) of rubber-containing polymers (I) and (II):
It calculated from the formula of FOX using the value described in the polymer handbook [Polymer HandBook (J. Brandrup, Interscience, 1989)].

(4) Reduced viscosity of thermoplastic polymer (III):
0.1 g of the polymer was dissolved in 100 mL of chloroform and measured at 25 ° C.

(5) Hydroxyl value of binder resin:
It measured according to JIS K0070.

(6) Mass average molecular weight of binder resin:
Using Shimadzu LC-6A system (manufactured by Shimadzu Corporation), three KF-805L (manufactured by Showa Denko KK) connected as a GPC column, THF as a solvent, and measurement in terms of polystyrene. .

(7) Total light transmittance, haze value of acrylic resin film, haze value after heating:
It measured according to the test method of JISK7136. In addition, for the haze value after heating the acrylic resin film, the acrylic resin film was heated to 160 ° C. and then allowed to cool to room temperature.

(8) HDT (thermal deformation temperature) of acrylic resin film:
The pellets of the resin composition were formed into heat deformation temperature measurement specimens based on ASTM D648 by injection molding and annealed at 60 ° C. for 4 hours. And this test piece was used and measured according to ASTM D648 with a low load (0.45 MPa).

(9) Bending resistance to whitening of acrylic resin film The whitening state when the acrylic resin film formed into a film thickness of 125 μm is bent 180 ° at a relatively high speed in an atmosphere of 20 ° C. is shown. The display is as follows.

    ○: No whitening was observed.

    Δ: Slightly whitening.

    X: Whitening occurs.

(10) The thickness of the matte layer of the matte acrylic resin film:
A sample obtained by cutting a matte acrylic resin film to a thickness of 70 nm in the cross-sectional direction is observed with a transmission electron microscope (J100S, manufactured by JEOL Ltd.), the thickness is measured at five locations, and they are averaged. Thus, the thickness of the matte layer was obtained. The thickness of the matte layer was measured by observing a portion where the matting material was not present, that is, a portion consisting only of the binder resin.

(11) Surface gloss of matte acrylic resin film:
Using a gloss meter (manufactured by Murakami Color Research Laboratory Co., Ltd., GM-26D type (trade name)), the surface gloss at 60 ° of the matte surface was measured.

(12) Thickness of the photocurable resin layer of the photocurable acrylic resin film:
A sample obtained by cutting a photo-curable acrylic resin film to a thickness of 70 nm in the cross-sectional direction was observed with a transmission electron microscope (J100S, manufactured by JEOL Ltd.), and the thickness was measured at five locations. Thus, the thickness of the photocurable resin layer was obtained.

(13) Formation of laminated sheet made of acrylic resin film and vacuum forming:
The acrylic resin film was provided with a wood grain pattern as a pattern layer by gravure printing. Further, an ABS sheet having a thickness of 1 mm having an adhesive layer was laminated by thermal lamination so that the adhesive layer and the woodgrain pattern layer were in contact with each other, thereby obtaining a laminated sheet of an acrylic resin film. Molding was performed using this laminated sheet.

  Specifically, the obtained laminated sheet is placed in a mold having a vacuum drawing function so that the acrylic resin film side becomes the cavity side, and after heating with a heater until the laminated sheet reaches 190 ° C., Vacuum forming was performed.

(14) Laminated acrylic resin film laminated sheet and vacuum forming:
The matte acrylic resin film was provided with a silver metallic pattern as a pattern layer on the acrylic resin film side (the side opposite to the matte layer) by gravure printing. Further, a 1 mm thick ABS sheet having an adhesive layer is laminated on the matte acrylic resin film by thermal lamination so that the adhesive layer and the silver metallic pattern layer are in contact with each other, thereby obtaining a laminate sheet of the matte acrylic resin film. It was.

  The laminated sheet was placed in a mold having a vacuuming function so that the matte acrylic resin film side became the cavity side, heated with a heater until the laminated sheet reached 190 ° C., and then vacuum-formed.

(15) Vacuum forming of photocurable acrylic resin film:
The photocurable acrylic resin film was provided with a jet black pattern as a pattern layer on the acrylic resin film side (the side opposite to the photocurable resin layer) by gravure printing.

  This photo-curable acrylic resin film is placed in a mold with a vacuum drawing function so that the photo-curable resin layer side becomes the cavity side, heated with a heater until the laminated sheet reaches 190 ° C, and then vacuum-formed Went.

(16) Trimming processability of laminated sheet made of acrylic resin film or matte acrylic resin film, and photo-curable acrylic resin film:
Unnecessary part of laminated sheet or photo-curable acrylic resin film made of acrylic resin film or matte acrylic resin film vacuum-formed in (12) to (15) above (part not bonded to base resin in final laminate) A laminated sheet end made of an acrylic resin film or a matte acrylic resin film when trimmed from the acrylic resin film or the matte acrylic resin film or the photocurable resin layer side using a Thomson punching die, and photocuring The state of the end portion of the conductive acrylic resin film was observed and evaluated as follows.

    ○: Neither crack nor crack.

    X: Two or more cracks and cracks occur in 50 molded products.

(17) Insert moldability of acrylic resin film, matte acrylic resin film, photocurable acrylic resin film:
A laminated sheet made of an acrylic resin film or a matte acrylic resin film after trimming unnecessary portions in (16) above, and a photocurable acrylic resin film on the bottom of the mold on the cavity side and in the center gate Placed 3cm in the horizontal direction from the bottom of the mold with a recess of 1cm ² and depth of 1mm, so that the acrylic resin film (matte acrylic resin film, photocurable resin layer) side is the cavity side did.

  Next, an ABS resin (made by UMG ABS Co., Ltd., trade name “Diapet ABS Bulk Sum TM25”) as a base material is injection molded on the ABS sheet side of the laminated sheet (the acrylic resin film side of the photocurable acrylic resin film). Then, a laminate was obtained by insert molding.

  The shape of the laminated body is a box shape with a length of 150 mm × width of 120 mm × thickness of 2 mm and a depth of 10 mm. The gate position of the mold is one in the middle of the laminated body, and 40 mm above and below the central gate (stacked body longitudinal direction). The gate shape is a pinpoint gate having a diameter of 1 mm. The corner corner R connecting the bottom surface and the side surface on the cavity side of the mold is about 3. That is, the corner R of the laminate edge portion on the side where the acrylic resin film is laminated is about 3. The corner R was measured with RADIUS GAGE manufactured by FUJI TOOL.

  The injection molding was performed using a J85 ELII type injection molding machine (trade name) manufactured by Nippon Steel Works, Ltd. under the conditions of a cylinder temperature of 250 ° C., an injection speed of 30%, an injection pressure of 43%, and a mold temperature of 60 ° C.

The state of the 1 cm ² formed on the obtained laminate, a convex portion having a height of 1 mm, or the vicinity of the corner of the laminate edge was observed, and the following evaluation was performed.

(Regarding whitening of convex parts and corners)
○: No film whitening.

    Δ: The film has weak whitening.

    X: There is strong whitening of the film.

(18) In-mold moldability of acrylic resin film, matte acrylic resin film, photocurable acrylic resin film:
In the above (12) to (15), an acrylic resin film having a woodgrain pattern layer, a matte acrylic resin film having a silver metallic pattern layer, and a photocurable acrylic resin film having a jet black pattern layer are used. Then, in-mold molding was performed using the following apparatus.

J85ELII type injection molding machine using a mold that has a evacuation function and has a recess of 1 cm ² and a depth of 1 mm at a position 3 cm laterally from the bottom of the mold on the cavity side and the center gate. In-mold molding was performed with an in-mold molding apparatus that combines (manufactured by Nippon Steel Works, trade name) and hot pack system (trade name, manufactured by Nissha Printing Co., Ltd.).

  The shape of the laminated body is a box shape with a length of 150 mm × width of 120 mm × thickness of 2 mm and a depth of 10 mm. The gate position of the mold is one in the middle of the laminated body, and 40 mm above and below the central gate (stacked body longitudinal direction). The gate shape is a pinpoint gate having a diameter of 1 mm. The corner corner R connecting the bottom surface and the side surface on the cavity side of the mold is about 3. That is, the corner R of the laminate on which the acrylic resin film is laminated is about 3. The corner R was measured with RADIUS GAGE manufactured by FUJI TOOL.

  Vacuum forming of acrylic resin film, matte acrylic resin film or photo-curable acrylic resin film is performed under the conditions of heater set temperature of about 330 ° C, heating time of 12 seconds, distance between heater and film at the film side (each picture Vacuum forming was performed in such a direction that the other side of the layer was in contact with the mold.

  Further, in the injection molding performed in the same mold, the base resin was injected from the non-matte layer under the conditions of a cylinder temperature of 250 ° C., an injection speed of 30%, an injection pressure of 43%, and a mold temperature of 60 ° C. As the base resin, heat-resistant ABS resin (trade name “Bulksa TM25B” manufactured by UMG ABS Co., Ltd.) was used.

The state in the vicinity of the corner of the 1 cm ² convex portion having a height of 1 mm formed on the obtained laminate or the edge of the laminate was observed, and the following evaluation was performed.

(Regarding whitening of convex parts and corners)
○: No film whitening.

    Δ: The film has weak whitening.

    X: There is strong whitening of the film.

(19) Acrylic resin film, matte acrylic resin film, photocurable acrylic resin film Pencil hardness of these laminates:
It measured according to JIS K5400. In the case of a matte acrylic resin film, the pencil hardness of the matte layer surface was measured.

(20) Abrasion resistance of the laminate of the photocurable acrylic resin film:
The value of the haze after the Taber abrasion test (the test was carried out with a load of 500 g on one side, a wear wheel of CS-10F (trade name), rotation speed of 60 rpm, 100 times of tests and 500 times) was measured. And the numerical value represented by [the haze value after the test] − [the haze value before the test] was shown as wear resistance (%).

[Production of rubber-containing polymer (I)]
After charging 10.8 parts of deionized water into a vessel equipped with a stirrer, MMA 0.3 part, n-BA 4.5 part, 1,3-BD 0.2 part, AMA 0.05 part and CHP 0 A monomer component consisting of 0.025 parts was added and stirred and mixed at room temperature. Next, 1.3 parts of an emulsifier (manufactured by Toho Chemical Co., Ltd., trade name “Phosphanol RS610NA”) was charged into the container while stirring, and stirring was continued for 20 minutes to prepare an emulsion.

  Next, 139.2 parts of deionized water was charged into a polymerization vessel equipped with a condenser, and the temperature was raised to 75 ° C. Further, a mixture prepared by adding 0.20 part of sodium formaldehyde sulfoxylate, 0.0001 part of ferrous sulfate and 0.0003 part of EDTA to 5 parts of ion-exchanged water was put into the polymerization vessel at once. Next, while stirring under nitrogen, the prepared emulsion was added dropwise to the polymerization vessel over 8 minutes, and then the reaction was continued for 15 minutes to complete the first stage polymerization of the monomer mixture (IA). (IA-1). Subsequently, a monomer component consisting of 9.6 parts of MMA, 14.4 parts of n-BA, 1.0 part of 1,3-BD, and 0.25 part of AMA, together with 0.016 part of CHP, is added over 90 minutes. After dropping into the polymerization vessel, the reaction was continued for 60 minutes to complete the second stage polymerization of the monomer mixture (IA) to obtain a polymer. The Tg obtained from the FOX formula of the polymer obtained from the monomer mixture used in the first stage is -48 ° C, and the FOX formula of the polymer obtained from the monomer mixture used in the second stage polymerization. Tg calculated | required from -10 degreeC.

  Subsequently, a monomer component consisting of 6 parts of MMA, 4 parts of MA and 0.075 part of AMA was dropped into the polymerization vessel over 45 minutes together with 0.0125 part of CHP, and then the reaction was continued for 60 minutes to conduct polymerization. went. Tg calculated | required from the formula of FOX of the polymer obtained from a monomer mixture (IB) was 60 degreeC.

  Subsequently, a monomer component (1-C) consisting of 57 parts of MMA, 3 parts of MA, 0.264 part of n-OM and 0.075 part of t-BH was dropped into the polymerization vessel over 140 minutes, and then 60 minutes. The reaction was continued to obtain a polymer latex of the rubber-containing polymer (I). The Tg determined from the FOX formula of the polymer obtained from the (IC) monomer mixture was 99 ° C. The mass average particle diameter of the rubber-containing polymer (I) measured after polymerization was 0.11 μm.

  The polymer latex of the rubber-containing polymer (I) thus obtained was filtered using a vibration type filtration device equipped with a SUS mesh (average opening: 62 μm) as a filter medium, and then 3.5 parts of calcium acetate was added. Salting out was carried out in an aqueous solution containing, recovered by washing with water, and then dried to obtain a powdery rubber-containing polymer (I). The gel content of the rubber-containing polymer (I) was 70% by mass. The rubber content of the rubber-containing polymer (I) was 30% by mass.

  Also, 214.3 g of the obtained rubber-containing polymer (I) was added to 1500 mL of acetone filtered through a nylon mesh having an opening of 25 μm and stirred for 3 hours to prepare an acetone dispersion of the rubber-containing polymer (I). did. Next, the dispersion was filtered through a nylon mesh having a mesh size of 32 μm, and the nylon mesh was washed with chloroform for 15 minutes to wash the captured matter on the mesh with chloroform. Next, the captured substance after ultrasonic cleaning is put into 150 mL of acetone filtered through a nylon mesh having an opening of 25 μm together with the nylon mesh, and this liquid is subjected to ultrasonic treatment for 15 minutes. A 150 mL acetone dispersion of the trapped material was prepared. Next, 70 mL of this dispersion was measured at 25 ° C. with an automatic liquid particle counter (model: KL-01) manufactured by Rion Co., Ltd., and the number of particles having a diameter of 55 μm or more was determined. It was a piece.

[Production of rubber-containing polymer (II) [rubber-containing polymer (IIa1)]]
The following (a) is charged into a reaction vessel, and the following raw materials (b) shown below are continuously added over 200 minutes at 80 ° C. in a nitrogen atmosphere while stirring. Latex was obtained.

  The following (c) shown below is added to the latex of this polymer, and the following raw materials (d) shown below are continuously added over 100 minutes at 80 ° C. under a nitrogen atmosphere while stirring. A polymer was formed by continuous polymerization at 60 ° C. for 60 minutes to obtain a latex of a rubber-containing polymer (IIa1). The rubber-containing polymer (IIa1) had an average particle size of 0.12 μm.

  The latex of the rubber-containing polymer (IIa1) was subjected to coagulation, aggregation and solidification using calcium acetate, filtered, washed with water and dried to obtain a rubber-containing polymer (IIa1). The gel content of the rubber-containing polymer (IIa1) was 84% by mass. The rubber content of the rubber-containing polymer (IIa1) was 62.5% by mass.

  In addition, Tg calculated | required from the formula of FOX of the polymer obtained from the monomer mixture of (b) was -29 degreeC.

(I)
310 parts of deionized water Partially neutralized mixture of sodium hydroxide of 40% by mass of mono (polyoxyethylene nonylphenyl ether) phosphoric acid and 60% by mass of di (polyoxyethylene nonylphenyl ether) phosphoric acid 0.5 parts Carbonic acid Sodium 0.1 parts Sodium formaldehyde sulfoxylate 0.5 parts Ferrous sulfate 0.00024 parts Disodium ethylenediaminetetraacetate 0.0072 parts (b)
n-BA 81.0 parts St 19.0 parts AMA 1.0 parts tBH 0.25 parts Mono (polyoxyethylene nonylphenyl ether) phosphoric acid 40% by mass and di (polyoxyethylene nonylphenyl ether) phosphoric acid 60% by mass 1.1 part neutralized product of a mixture of sodium hydroxide of 0.1% (c)
Deionized water 10 parts Sodium formaldehyde sulfoxylate 0.15 parts (d)
MMA 57.0 parts MA 3.0 parts nOM 0.2 parts tBH 0.1 part.

[Production of rubber-containing polymer (II) [rubber-containing polymer (IIa2)]]
Under a nitrogen atmosphere, 244 parts of deionized water was placed in a reaction vessel equipped with a reflux condenser, and the temperature was raised to 80 ° C. Then, (a) shown below was added, and while stirring, 1/15 of the monomer mixture (IIa2-A-1) was charged and held for 15 minutes. Subsequently, the remaining monomer mixture (IIa2-A-1) was continuously added at an increase rate of 8% / hour of the monomer component [monomer mixture (IIa2-A-1)] with respect to water. Thereafter, it was held for 60 minutes to obtain a latex. Tg calculated | required from the formula of FOX of the polymer obtained from the monomer mixture (IIa2-A-1) was 4 degreeC.

  Subsequently, 0.6 parts of sodium formaldehyde sulfoxylate was added to the latex and held for 15 minutes. And stirring at 80 degreeC under nitrogen atmosphere, the monomer mixture (IIa2-A-2) shown below is an increase in the monomer component [monomer mixture (IIa2-A-2)] with respect to water. After continuously adding at a rate of 4% / hour, the mixture was held for 120 minutes to obtain a latex. In addition, Tg calculated | required from the formula of FOX of the polymer obtained from a monomer mixture (IIa2-A-2) was -38 degreeC.

  Subsequently, 0.4 parts of sodium formaldehyde sulfoxylate was added to the latex and held for 15 minutes. Then, while stirring at 80 ° C. in a nitrogen atmosphere, the monomer mixture (IIa2-C) shown below was continuously added at an increase rate of 10% / hour of the monomer component [(IIa2-C)] with respect to water. After the addition, the mixture was held for 60 minutes to obtain a polymer latex of a rubber-containing polymer (IIa2). In addition, Tg calculated | required from the formula of FOX of the polymer obtained from a monomer mixture (IIa2-C) was 99 degreeC.

  The rubber-containing polymer (IIa2) obtained had a weight average particle size of 0.28 μm.

  The polymer latex of the obtained rubber-containing polymer (IIa2) was subjected to coagulation, aggregation and solidification using calcium acetate, filtered, washed with water, and dried to obtain a rubber-containing polymer (IIa2). . The gel content of the rubber-containing polymer (IIa2) was 90% by mass. The rubber content of the rubber-containing polymer (IIa2) was 62.5% by mass.

(I) sodium formaldehyde sulfoxylate 0.6 part,
0.00012 parts of ferrous sulfate,
0.0003 parts EDTA,

Monomer mixture (IIa2-A-1)
18 parts of MMA,
20 parts of n-BA,
St 2 parts,
0.4 part AMA,
1,3-BD 0.14 parts,
0.18 parts t-BH,
1.0 part of a partially neutralized product of a mixture of sodium hydroxide of 40% by mass of mono (polyoxyethylene nonylphenyl ether) phosphoric acid and 60% by mass of di (polyoxyethylene nonylphenyl ether) phosphoric acid,

Monomer mixture (IIa2-A-2)
n-BA 50.0 parts,
10.0 parts of St,
0.4 part AMA,
1,3-BD 0.14 parts,
0.2 part of t-HH,
1.0 part of a partially neutralized product of a mixture of sodium hydroxide of 40% by mass of mono (polyoxyethylene nonylphenyl ether) phosphoric acid and 60% by mass of di (polyoxyethylene nonylphenyl ether) phosphoric acid,

Monomer mixture (IIa2-C)
MMA 57.0 parts,
3.0 parts of MA,
n-OM 0.3 part,
0.06 parts t-BH.

[Production of rubber-containing polymer (II) [rubber-containing polymer (IIb)]
After charging 8.5 parts of deionized water into a vessel equipped with a stirrer, MMA 0.3 part, n-BA 4.5 part, 1,3-BD 0.2 part, AMA 0.05 part and CHP 0 A monomer mixture (IIb-A-1) consisting of 0.025 parts was added and stirred and mixed at room temperature. Next, 1.3 parts of an emulsifier (manufactured by Toho Chemical Co., Ltd., trade name “Phosphanol RS610NA”) was charged into the container while stirring, and stirring was continued for 20 minutes to prepare an emulsion.

  Next, 186.5 parts of deionized water was put into a polymerization vessel equipped with a cooler, and the temperature was raised to 70 ° C. Further, a mixture prepared by adding 0.20 part of sodium formaldehyde sulfoxylate, 0.0001 part of ferrous sulfate and 0.0003 part of EDTA to 5 parts of ion-exchanged water was put into the polymerization vessel at once. Next, the prepared emulsion was dropped into the polymerization vessel over 8 minutes while stirring under nitrogen, and then the reaction was continued for 15 minutes to complete the polymerization. Subsequently, a monomer mixture (IIb-A-2) consisting of 1.5 parts of MMA, 22.5 parts of n-BA, 1.0 part of 1,3-BD and 0.25 part of AMA was added to CHP 0. Together with 016 parts, the solution was dropped into the polymerization vessel over 90 minutes, and then the reaction was continued for 60 minutes to complete the polymerization.

  The Tg determined from the FOX formula of the polymer obtained from the monomer mixture (IIb-A-1) is −48 ° C., and the polymer FOX obtained from the monomer mixture (IIb-A-2) The Tg determined from the formula was -48 ° C.

  Subsequently, a monomer mixture (IIb-B) consisting of 6 parts of MMA, 4 parts of n-BA and 0.075 part of AMA was dropped into the polymerization vessel over 45 minutes together with 0.0125 part of CHP, and then for 60 minutes. The reaction was continued. The Tg determined from the FOX formula of the polymer obtained from the monomer mixture (IIb-B) was 20 ° C.

  Subsequently, a monomer mixture (IIb-C) consisting of 55.2 parts of MMA, 4.8 parts of MA, 0.19 part of n-OM and 0.08 part of t-BH was dropped into the polymerization vessel over 140 minutes. Thereafter, the reaction was continued for 60 minutes to obtain a polymer latex of the rubber-containing polymer (IIb). Tg calculated | required from the formula of FOX of the polymer obtained from a monomer mixture (IIb-C) was 84 degreeC. The mass average particle diameter of the rubber-containing polymer (IIb) measured after polymerization was 0.12 μm.

  The polymer latex of the obtained rubber-containing polymer (IIb) was filtered using a vibration type filtration device equipped with a SUS mesh (average opening: 62 μm) as a filter medium, and then 3.0 parts of calcium acetate was added. Salting out was carried out in an aqueous solution containing, recovered by washing with water, and then dried to obtain a powdery rubber-containing polymer (IIb). The gel content of the rubber-containing polymer (IIb) was 60% by mass. The rubber content of the rubber-containing polymer (IIb) was 40% by mass.

  Further, 214.3 g of the obtained rubber-containing polymer (IIb) was added to 1500 mL of acetone filtered through a nylon mesh having an opening of 25 μm and stirred for 3 hours to prepare an acetone dispersion of the rubber-containing polymer (IIb). did. Next, the dispersion was filtered through a nylon mesh having a mesh size of 32 μm, and the nylon mesh was washed with chloroform for 15 minutes to wash the captured matter on the mesh with chloroform. Next, the captured substance after ultrasonic cleaning is put into 150 mL of acetone filtered through a nylon mesh having an opening of 25 μm together with the nylon mesh, and this liquid is subjected to ultrasonic treatment for 15 minutes. A 150 mL acetone dispersion of the trapped material was prepared. Next, 70 mL of this dispersion was measured at 25 ° C. with an automatic liquid particle counter (model: KL-01) manufactured by Rion Co., Ltd., and the number of particles having a diameter of 55 μm or more was determined. It was a piece.

[Production of thermoplastic resin (z-1) having radically polymerizable unsaturated group in side chain]
50 parts of methyl ethyl ketone was placed in a 1 L four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, and the temperature was raised to 80 ° C. Under a nitrogen atmosphere, a mixture of 79.9 parts of methyl methacrylate, 20.1 parts of glycidyl methacrylate and 0.5 parts of azobisisobutyronitrile was added dropwise over 3 hours. Thereafter, a mixture of 80 parts of methyl ethyl ketone (boiling point 79.6 ° C.) and 0.2 part of azobisisobutyronitrile was added and polymerized. After 4 hours, 74.4 parts of methyl ethyl ketone, 0.5 part of hydroquinone monomethyl ether, 2.5 parts of triphenylphosphine and 10.1 parts of acrylic acid were added and stirred at 80 ° C. for 30 hours while blowing air. Then, after cooling, the reaction product was taken out from the flask, and a solution of a thermoplastic resin (z-1) having a radical polymerizable unsaturated group in the side chain was obtained.

  The polymerization rate of the monomer in the thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain is 99.5% or more, the polymer solid content is about 35% by mass, and the number average molecular weight is about 3%. The Tg was about 105 ° C., and the average double bond equivalent was 788 g / mol.

[Production of colloidal silica (inorganic fine particles (a-3))]
In a flask equipped with a stirrer, a condenser and a thermometer, IPA-ST (isopropanol-dispersed colloidal silica sol (manufactured by Nissan Chemical Industries, Ltd.), silica particle size = 15 nm) 1 part, KBM503 (γ- Add 0.1 part of methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight = 248) and 0.3 part of water, raise the temperature of the hot water bath to 75 ° C. with stirring, and increase the temperature to 2 at that temperature. By reacting for a period of time, colloidal silica dispersed in isopropanol and having a surface treated with a silane compound was obtained. Subsequently, isopropanol was distilled off and toluene (boiling point 110.6 ° C.) was repeatedly added. By completely replacing isopropanol with toluene, the colloidal was dispersed in toluene and the surface was treated with a silane compound. Silica was obtained.

[Production of photocurable resin solution]
100 parts by weight of thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain, 3 parts of 1-hydroxycyclohexyl phenyl ketone (photopolymerization initiator (z-2)) A photocurable resin solution composed of 66 parts of colloidal silica (inorganic fine particles (a-3)) was prepared by stirring with a propeller mixer.

[Example 1]
75 parts of rubber-containing polymer (I), 15 parts of rubber-containing polymer (IIb) as rubber-containing polymer (II) and thermoplastic polymer (III) [MMA / MA copolymer (MMA / MA = 99/1) (Mass ratio), reduced viscosity ηsp / c = 0.06 L / g)] 10 parts, Ciba Specialty Chemicals Co., Ltd. as a compounding agent, trade name “Tinubin 234” 1.4 parts, manufactured by Asahi Denka Kogyo Co., Ltd. After adding 0.1 part of the product name “Adekastab AO-50” and 0.3 part of the product name “Adekastab LA-67” manufactured by Asahi Denka Kogyo Co., Ltd., the mixture was mixed using a Henschel mixer. This mixture was supplied to a degassing extruder heated to 230 ° C. (PCM-30 (trade name) manufactured by Ikekai Tekko Co., Ltd.), kneaded, extruded while removing foreign matter with a 300 mesh screen mesh, and pellets Got.

  The pellets produced by the above method were dried at 80 ° C. all day and night, and a cylinder temperature of 180 to 240 ° C. was used using a 40 mmφ non-vent screw extruder (L / D = 26) equipped with a 300 mm wide T-die. Then, extruding while removing foreign matter with a 500 mesh screen mesh, passing the molten acrylic resin film extruded under the conditions of T-die temperature of 240 ° C. and T-die slit width of 0.3 mm between two metal cooling rolls Then, after sandwiching the resin without any bank (resin reservoir) and transferring the surface without rolling, an acrylic resin film having a thickness of 100 μm was formed by winding it around a paper roll with a winder. The obtained acrylic resin film was evaluated. The results are shown in Table 1.

[Examples 2 to 4]
In Example 1, it carried out like Example 1 except mix | blending rubber-containing polymer (I), rubber-containing polymer (IIb), and thermoplastic polymer (III) as shown in Table 1.

[Examples 5 to 7]
In Example 1, it carried out like Example 1 except mix | blending rubber-containing polymer (I), rubber-containing polymer (IIa), and thermoplastic polymer (III) as shown in Table 1.

[Example 8]
In Example 1, it carried out like Example 1 except mix | blending rubber-containing polymer (I) and rubber-containing polymer (II) as shown in Table 1.

[Example 9]
In Example 1, an acrylic resin film having a film thickness of 75 μm was formed. On the other hand, 27.4 parts of a hydroxyl group-containing acrylic resin (hydroxyl value 80 mg KOH / g, Tg 90 ° C., weight average molecular weight of about 80,000), which is a copolymer of 85% by mass of MMA, 12% by mass of HEMA and 3% by mass of n-BA, and polyisocyanate 6.8 parts of hexamethylene diisocyanate (isocyanurate type) trimer, 7 parts of amorphous silica having a mass average particle diameter of 5 to 6 μm, and amorphous silica having a mass average particle diameter of 0.1 μm as a suspending agent. 5 parts and 1 part of wax S-363 (trade name, manufactured by SHAMROCK, melting point 142 ° C.) made of polyethylene and polypropylene having a mass average particle diameter of 5 μm, 22.3 parts of MEK, 49.6 parts of MIBK, and 45.8 parts of butyl acetate A paint was obtained by dispersing in a solvent comprising In addition, when this paint was measured with the Iwata cup viscometer immediately before coating, the flow-down time was 15 seconds and the liquid temperature was 21 ° C. After adjusting the viscosity, the coating solution was filtered using CPII-10 manufactured by Chisso Filter Co., Ltd.

Next, both surfaces of the 75 μm acrylic resin film formed in advance are bonded to an adhesive tape (manufactured by Kaneron Chemical Industry Co., Ltd., adhesive strength; SUS # 430 plate with a 5 kg rubber roll, and 180 ° in a 20 ° C. environment. After passing through the step of removing foreign matter present on both surfaces of the film by contacting with two rolls wound with a peeling load of 30 g / 25 mm when peeled at a tensile speed of 300 mm / min in the direction, On one side of the film, a 200-line oblique gravure roll with an inch width (the oblique line angle is about 45 ° with respect to the roll axis direction, the plate opening width is 116 μm, the plate bottom width is 13 μm, the plate depth is 33 μm, and the cell capacity is 16.9 cm. ³ / m ² , diameter 120 mm), using a ceramic doctor blade, the gravure coater applied the paint at a coating speed of 20 m / min. The solvent was volatilized under an atmosphere of 0 ° C. to obtain a matte acrylic resin film. The appearance of the resulting matte acrylic resin film was free of faint or noticeable prints due to a decrease in the transfer amount, and a good matte layer could be formed. The matte acrylic resin film was wound around a paper tube and aged at 40 ° C. for 2 days to cure the matte layer.

  The thickness of the matte layer was 1 μm. Further, the obtained matte acrylic resin film had a good appearance with a reflection of a fluorescent lamp and no grain. This acrylic resin film was evaluated and the results are shown in Table 2.

[Examples 10 to 16]
In Examples 2-8, it implemented similarly to Example 9 except having used the acrylic resin film formed into a film with a film thickness of 75 micrometers, respectively.

[Comparative Example 1]
90 parts of rubber-containing polymer (IIb) and thermoplastic polymer (III) [MMA / MA copolymer (MMA / MA = 99/1 (mass ratio), reduced viscosity ηsp / c = 0.06 L / g)] 10 parts as a compounding agent manufactured by Ciba Specialty Chemicals Co., Ltd., 1.4 parts of the trade name “Tinubin 234”, manufactured by Asahi Denka Kogyo Co., Ltd., 0.1 part of the trade name “ADK STAB AO-50” and Asahi Denka Kogyo Co., Ltd. ), Product name "ADK STAB LA-67" 0.3 part was added, and then mixed using a Henschel mixer. This mixture was supplied to a degassing extruder heated to 230 ° C. (PCM-30 (trade name) manufactured by Ikekai Tekko Co., Ltd.), kneaded, extruded while removing foreign matter with a 300 mesh screen mesh, and pellets Got.

  The pellets produced by the above method were dried at 80 ° C. all day and night, and a cylinder temperature of 180 to 240 ° C. was used using a 40 mmφ non-vent screw extruder (L / D = 26) equipped with a 300 mm wide T-die. Then, extruding while removing foreign matter with a 500 mesh screen mesh, passing the molten acrylic resin film extruded under the conditions of T-die temperature of 240 ° C. and T-die slit width of 0.3 mm between two metal cooling rolls Then, after sandwiching the resin without any bank (resin reservoir) and transferring the surface without rolling, an acrylic resin film having a thickness of 100 μm was formed by winding it around a paper roll with a winder. The obtained acrylic resin film was evaluated. The results are shown in Table 1.

[Comparative Examples 2 to 5]
Comparative Example 1 was carried out in the same manner as Comparative Example 1 except that the rubber-containing polymer (I), the rubber-containing polymer (II) and the thermoplastic polymer (III) were blended as shown in Table 1.

[Comparative Examples 6-8]
In Comparative Examples 1-3, it implemented like Example 9 except having used the acrylic resin film formed by film thickness 75micrometer, respectively.

[Example 17]
A metallic print pattern layer using an aluminum pigment was formed on the acrylic resin film obtained in Example 7 by gravure printing. Next, 666 parts of isophorone diisocyanate, 440 parts of tetrahydrofurfuryl acrylate, and 300 parts of polyethylene glycol diacrylate are mixed, and further stirred at 70 ° C. while adding 1200 parts of a ring-opening reaction product of trimethylolpropane and epsilon caprolactone. After confirming that the isocyanate groups were reduced, 350 parts of 2-hydroxyethyl acrylate was added and reacted at 70 ° C. to completely eliminate the isocyanate groups, thereby synthesizing urethane acrylate. Subsequently, 97: 3 parts by mass of this urethane acrylate and 2-hydroxy-2-methyl-phenylpropan-1-one were blended on the surface opposite to the metallic printed pattern layer of the acrylic resin film. A photocurable resin layer was formed by screen printing.

  Thereafter, the surface of the photocurable resin layer is first irradiated with short wavelength ultraviolet light having a wavelength of 254 nm ± 20 nm, and 3 seconds later, the entire photocurable resin layer is irradiated with long wavelength ultraviolet light having a wavelength of 350 nm ± 20 nm. Irradiated to produce a photocurable acrylic resin film.

A laminate obtained by insert molding or in-mold molding using this photocurable acrylic resin film can express a high degree of design such as a three-dimensional feeling (depth feeling).

  In the laminate of this example, whitening at the time of molding was suppressed, the design was not deteriorated, and the trimming processability at the time of production was excellent.

[Example 18]
In Example 3, an acrylic resin film having a film thickness of 200 μm was formed. The photocurable resin solution was applied onto the acrylic resin film with a comma roll coater with a coating width of 250 mm. Subsequently, the tunnel-type drying oven (width 800 mm, height 100 mm, length 8 m, divided into four drying zones (one zone length 2 m)) set to the temperature conditions shown in Table 6 below is suitable for the movement of the sheet. The solvent was volatilized by passing it through a method in which hot air was fed so as to form a flow at a speed of 10 m / min to form a photocurable resin layer. The photocurable resin layer had a thickness of 10 μm. The staying time in each drying zone at this time is shown in Table 4 below.

Subsequently, it was slit into a width of 200 mm and wound into a roll shape around an ABS core to a length of 20 m.

  The photocurable acrylic resin film was provided with a pattern layer (jet black), vacuum formed, trimmed unnecessary portions, and then insert molded.

Next, using an ultraviolet irradiation device, ultraviolet rays of about 700 mJ / cm ² were irradiated to cure the photocurable resin composition, and the surface properties of the laminate were evaluated. The results are shown in Table 3.

[Comparative Example 9]
In Comparative Example 2, the same procedure as in Example 18 was performed except that an acrylic resin film formed with a film thickness of 200 μm was used.

From Examples 1 to 8, rubber-containing polymer (I), rubber-containing polymer (II), thermoplastic polymer (III) as an optional component, rubber content is 25% by mass or more, gel content is An acrylic resin film employing an acrylic resin composition of less than 70% by mass has surface hardness, heat resistance, transparency, good insert molding or in-mold molding, and resistance to molding whitening. An acrylic resin film excellent in trimming processability and a laminate using the acrylic resin film are obtained. In particular, the acrylic resin film employing the rubber-containing polymer (IIb) as the rubber-containing polymer (II) had a good balance between trimming processability and molding whitening resistance during molding.

  Furthermore, from Examples 9-16, by using the acrylic resin film having the characteristics as in Examples 1-8, the matte layer containing the matting agent and the curable binder resin on one surface is the outermost layer. As with the acrylic resin film, the matte acrylic resin film for thermoforming provided as above has surface hardness, heat resistance, good insert molding or in-mold moldability, and resistance to molding whitening, and the molding The physical properties excellent in the trimming workability at the time are shown, and a laminate using this is obtained.

  Further, from Example 17, by using an acrylic resin film having the characteristics as in Example 7, even in a photocurable acrylic resin film having a photocurable resin layer on one surface, the acrylic resin film and Similarly, it exhibits physical properties excellent in whitening resistance to insert molding or in-mold molding, and trimming workability during the molding.

  Furthermore, from Example 18, by using the acrylic resin film having the characteristics as in Example 3, the thermoplastic resin (z-1) having a radically polymerizable unsaturated group in the side chain on one side and light Also in the photocurable acrylic resin film having a photocurable resin layer containing a polymerization initiator (z-2), as with the acrylic resin film, surface hardness, heat resistance, good insert molding or in-mold moldability, and By exhibiting excellent molding whitening resistance to the molding and excellent physical properties for trimming at the time of molding, in addition to curing the photocurable resin composition (Z) layer by irradiation with ultraviolet rays after molding. Excellent wear resistance.

As described above, the rubber-containing polymer (I), the rubber-containing polymer (II), and the thermoplastic polymer (III) as an optional component are contained, the rubber content is 25% by mass or more, and the gel content is 70% by mass. When the acrylic resin composition of the present invention of less than% is employed, it has excellent surface hardness, heat resistance and transparency that can be used for vehicles, and the molded product does not whiten when insert molding or in-mold molding is performed. In addition, an acrylic resin film excellent in trimming processability during molding, a matte acrylic resin film for thermoforming, a photocurable acrylic resin film, and a laminate using these films can be provided. It is possible to remarkably reduce the occurrence ratio of cracks / cracks in the process, and it is possible to set a wide processing condition width in the trimming process.

  As explained in detail above, the acrylic resin composition of the present invention, the acrylic resin film comprising the same, the matte acrylic resin film, and the laminate comprising these are particularly suitable for vehicle use and building material use. Specific examples include instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, dashboards and other automotive interior applications, weather strips, bumpers, bumper guards, side mud guards, body panels, Spoilers, front grills, strut mounts, wheel caps, center pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, etc., automotive exterior applications such as windows, headlamp covers, tail lamp covers, windshield parts, AV equipment and furniture products Applications such as front panels, buttons, emblems, surface cosmetics, housings for mobile phones, display windows, buttons, etc. Building interior materials such as surfaces, ceilings, floors, exterior walls such as siding, exterior materials for buildings such as fences, roofs, gates, and windbreak boards, surfaces of furniture such as window frames, doors, handrails, sills, and duck Cosmetic materials, various displays, lenses, mirrors, goggles, window glass and other optical components, trains, airplanes, ships and other vehicles other than automobiles, interior and exterior applications, bottles, cosmetic containers, various packaging such as accessories It can be suitably used for various other uses such as containers and materials, miscellaneous goods such as prizes and accessories.

Claims (10)

An acrylic resin composition containing the following rubber-containing polymer (I) and rubber-containing polymer (II), having a rubber content of 25% by mass to 50% by mass and a gel content of 40% by mass to less than 70% by mass. .
Rubber-containing polymer (I);
The following monomer mixture (IA), monomer mixture (IB) and monomer mixture (IC) are combined into monomer mixture (IA) and monomer mixture (IB). ) And the monomer mixture (IC) in this order.

Monomer mixture (IA)
(I-A1) Acrylic acid alkyl ester 50-99.9% by mass
(I-A2) Methacrylic acid alkyl ester 0 to 49.9% by mass
(I-A3) Other monomer having copolymerizable double bond 0 to 20% by mass
(I-A4) Polyfunctional monomer 0 to 10% by mass
(I-A5) Graft crossing agent 0.1 to 10% by mass
In addition, the glass transition temperature calculated | required by the formula of FOX of the polymer obtained from (I-A1)-(I-A3) is less than 25 degreeC.

Monomer mixture (IB)
(I-B1) Acrylic acid alkyl ester 9.9 to 90% by mass
(I-B2) Methacrylic acid alkyl ester 9.9 to 90% by mass
(I-B3) Other monomer having copolymerizable double bond 0 to 20% by mass
(I-B4) Polyfunctional monomer 0 to 10% by mass
(I-B5) Graft crossing agent 0.1 to 10% by mass
In addition, the glass transition temperature calculated | required by the formula of FOX of the polymer obtained from (I-B1)-(I-B3) is 25-100 degreeC.

Monomer mixture (IC)
(I-C1) Methacrylic acid alkyl ester 80-100% by mass
(I-C2) Acrylic acid alkyl ester 0 to 20% by mass
(I-C3) Other monomer having copolymerizable double bond 0 to 20% by mass

Rubber-containing polymer (II);
A monomer or monomer mixture comprising 35 to 100% by mass of an acrylic acid alkyl ester and 65 to 0% by mass of another vinyl monomer , and a crosslinkable monomer for 100 parts by mass of the monomer or monomer mixture. After polymerizing 0.1 to 10 parts by mass of a monomer, it is obtained by polymerizing a monomer or monomer mixture comprising 50 to 100% by mass of methacrylic acid alkyl ester and 50 to 0% by mass of other vinyl monomers. Obtained rubber-containing polymer.
In addition, the glass transition temperature calculated | required by the formula of FOX of the polymer obtained from the monomer or monomer mixture which consists of 35-100 mass% of acrylic acid alkylesters, and other vinyl monomers 65-0 mass% , It is less than 25 ° C.
2. The acrylic resin composition according to claim 1, further comprising the following thermoplastic polymer.

Thermoplastic polymer (III);
A thermoplastic polymer mainly composed of alkyl methacrylate.
  An acrylic resin film comprising the acrylic resin composition according to claim 1.   A matte acrylic resin film for thermoforming having a matte layer having a thickness of 0.1 to 5 µm containing the acrylic resin film according to claim 3 and a matting agent and a curable binder resin.   A photocurable acrylic resin film comprising the acrylic resin film according to claim 3 and a photocurable resin layer.   The photocurable resin layer according to claim 5 is a photocurable resin layer containing a thermoplastic resin (z-1) having a radically polymerizable unsaturated group in a side chain and a photopolymerization initiator (z-2). Photo-curable acrylic resin film.   An acrylic resin film having a pattern layer on at least one side of the acrylic resin film according to claim 3.   The matte acrylic resin film for thermoforming which has a pattern layer in the surface on the opposite side to the matte layer of the matte acrylic resin film for thermoforming of Claim 4.   The photocurable acrylic resin film which has a pattern layer in the surface on the opposite side to the photocurable resin layer of the photocurable acrylic resin film of Claim 5 or 6.   The laminated body formed by laminating | stacking the acrylic resin film in any one of Claims 3-9, the matte acrylic resin film for thermoforming, or a photocurable acrylic resin film.