JP2006143785A - Acrylic resin film and laminated molded product laminated therewith - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acrylic resin film having surface hardness, scratch resistance and heat resistance enough to be usable in insert molding and in-mold molding, also having good printability and extremely good surface appearance, and enabling the good surface appearance to be maintained through secondary processings including in-mold molding. <P>SOLUTION: The acrylic resin film comprises 100 pts.mass of an acrylic resin composition comprising a rubber-containing polymer(I) and/or a methacrylic alkyl ester-based thermoplastic polymer(II) and 1-15 pts.mass of organic crosslinked particles or inorganic particles having a mass-average size Dw of larger than 1μm but not larger than 20μm and containing no particles with a size of 10×Dwμm or larger. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an acrylic resin film and a laminated molded product obtained by laminating the acrylic resin film.

As typical molding methods for imparting design properties to resin molded products, 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 for printing or the like is previously formed into a three-dimensional shape by vacuum forming or the like, and an unnecessary film or sheet portion is removed. This is a method of obtaining a molded product by transferring it into an injection mold and integrating the resin as a base material by injection molding. On the other hand, the in-mold molding method is a method in which a sheet or film of polyester resin, polycarbonate resin, acrylic resin or the like that has been decorated for printing or the like is placed in an injection mold, vacuum molded, and then placed in the same mold. In this method, an integrated molded product is obtained by injection molding a resin as a base material.
In particular, according to the in-mold molding method, the sheet or film and the base material can be integrated with high productivity, or only the printing part can be transferred. A member having an acrylic resin film layer on the surface layer thus obtained is used as a component material for a vehicle.

In recent years, it has been required to add a design and decoration such as a high-class feeling and a deep feeling by making the surface of an acrylic resin film subjected to high-luminance printing such as metallic to a matte state.
Conventional matting methods for thermoplastic resins can be broadly divided into (1) a patterning process and a matting process, and (2) a method of adding an inorganic or organic matting material. However, although the method (1) generally has the advantage that the physical properties are hardly lowered, the productivity is poor and the processing cost increases and the matting effect is insufficient. In many cases, the film is heated by secondary processing. There is a problem that the luster is restored in use and the matting effect disappears. Further, the method (2) can control the degree of matting without significantly reducing the productivity, and can be applied to a secondary processing application. However, the method (2) has a serious problem that the physical properties are lowered. .

Under such circumstances, various resin compositions having a matting effect containing a matting material are being actively developed to solve the above problems, and the physical properties such as impact resistance, high elongation, and transparency are small. It is being advanced. For example, methacrylic resin fine particles having a crosslinked structure (for example, see Patent Documents 1 and 2), inorganic fine particles such as resin fine particles having a crosslinked structure, mica fine particles and talc fine particles (for example, see Patent Document 3), rubbery alkyl acrylate A film-like or sheet-like resin composition containing a polymer (for example, see Patent Document 4), polymer particles (for example, see Patent Document 5) or inorganic particles and / or organic crosslinked particles (for example, see Patent Document 6) Etc. are being developed.
On the other hand, after melt-extruding a resin composition containing various matting materials, it is sandwiched between a mirror roll and a rubber roll or a textured roll so that only one of the films is rough and the other is smooth. A matte film having printability has also been developed (see, for example, Patent Documents 7 to 9).

  However, according to the experiments conducted by the present inventors, the various resin compositions described above have many concave defects on the film surface, the surface appearance is remarkably deteriorated, and when the printing process is performed, the film surface As a decorative film or sheet, it is difficult to obtain a good print layer, such as large irregularities, difficult to get printing ink into the recesses, and printing defects on the film, such as printing patterns becoming unclear Those with sufficient characteristics were not obtained. Moreover, when the matte film was created by the method described in Patent Documents 8 and 9, it was sandwiched between a mirror roll and a rubber roll or a textured roll, so that the indented defect on the film surface once became inconspicuous. When the film was heated in the secondary processing step such as molding, the concave surface defect was developed again. In particular, when high-luminance printing such as silver metallic tone is performed on the smooth surface side, this surface defect is very conspicuous, and it has not been possible to obtain a decorative film and a laminated molded product. Therefore, development of a resin material for obtaining a decorative film having a good surface appearance or a laminate thereof is desired.

JP-A-3-237134 Japanese Patent No. 3295134 JP-A-6-73200 Japanese Patent No. 2530687 JP 2000-191708 A Japanese Patent Laid-Open No. 10-237261 JP 2002-103371 A JP 2002-254495 A JP 2002-361712 A

  The object of the present invention is to have surface hardness, scratch resistance, and heat resistance that can be used for insert molding and in-mold molding, have good printability, and have a very good surface appearance. Furthermore, the object is to develop an acrylic resin film in which this good surface appearance can be maintained through secondary processing such as in-mold molding, and a laminated molded product obtained by laminating this film.

  As a result of intensive studies to solve the above problems, the present inventors have found that organic crosslinked particles having a specific particle diameter in a specific rubber-containing polymer or a thermoplastic polymer mainly composed of an alkyl methacrylate ester Or, by incorporating inorganic particles, we develop acrylic resin films that have surface hardness, scratch resistance, heat resistance, good printability and good surface appearance, and laminated molded products that are laminated with these films. Succeeded in doing.

That is, the present invention provides an acrylic resin film described in the following 1) to 6) and an acrylic resin laminated molded product obtained by laminating the acrylic resin film on a base material.
1) Mass average particles with respect to 100 parts by mass of an acrylic resin composition comprising a rubber-containing polymer (I) and / or a thermoplastic polymer (II) mainly composed of an alkyl methacrylate as shown below. An acrylic resin film containing 1 to 15 parts by mass of organic crosslinked particles or inorganic particles having a diameter Dw of more than 1 μm and not more than 20 μm and not containing particles having a particle diameter of 10 × Dw μm or more.
Rubber-containing polymer (I):
In the presence of an innermost layer polymer (IA) having a structure of one layer or two or more layers obtained with an alkyl acrylate ester as a main component, a monomer having an alkyl methacrylate ester as a main component is graft-polymerized. A rubber-containing polymer having a multilayer structure of two or more layers having a mass average particle diameter of 0.01 to 0.5 μm formed by molding an outermost layer polymer (IC) having a structure of one layer or two or more layers .
2) Mass average particle diameter Dw with respect to 100 parts by mass of the acrylic resin composition comprising the rubber-containing polymer (I) and / or the thermoplastic polymer (II) mainly composed of an alkyl methacrylate as a main component. 1 to 15 parts by mass of organic crosslinked particles made of the crosslinked acrylic polymer (III) shown below which does not contain particles having a particle diameter of more than 1 μm and not more than 20 μm and a particle diameter of 10 × Dw μm or more. Acrylic resin film.
Crosslinked acrylic polymer (III):
Cross-linked methacrylic particles composed of a polymerizable monomer mainly composed of an alkyl methacrylate and a polyfunctional monomer, or
Core-shell structure polymer particles comprising a rubber-like polymer core mainly composed of an acrylic acid alkyl ester and a glassy polymer shell mainly composed of an alkyl methacrylate.

3) The said 1) or 2 description which contains 0.1-1 mass part of silica particles whose mass mean particle diameter is 100 nm or less further with respect to 100 mass parts of acrylic resin compositions of said 1) description. Acrylic resin film.
4) The acrylic resin film as described in the above items 1) to 3), wherein the resin composition is produced by melt extrusion and sandwiching between a mirror roll and a rubber roll to form a film.
5) The acrylic resin film according to the above item 4), wherein the contact surface with the rubber roll is printed during the production of the acrylic resin film.
6) An acrylic resin laminate molded article obtained by laminating the acrylic resin film described in 1) to 5) above on a substrate.

  According to the present invention, 100 parts by mass of an acrylic resin composition comprising a specific rubber-containing polymer (I) and / or a thermoplastic polymer (II) whose main component is an alkyl methacrylate, and mass average particles. By adopting an acrylic resin film consisting of 1 to 15 parts by mass of organic crosslinked particles or inorganic particles having a diameter Dw of more than 1 μm and not more than 20 μm and not containing particles having a particle diameter of 10 × Dw μm or more. Can be used for insert molding and in-mold molding, has surface hardness, scratch resistance, heat resistance, good printability, and very good surface appearance. It is possible to provide an acrylic resin film that can maintain a good surface appearance through secondary processing such as in-mold molding and a laminated molded product obtained by laminating this film.

  In the present invention, the rubber-containing polymer (I) is a methacrylic acid alkyl ester in the presence of an innermost layer polymer (IA) having a structure of one layer or two or more layers obtained mainly from an acrylic acid alkyl ester. A rubber-containing polymer having a multilayer structure of two or more layers formed by graft polymerization of a monomer having a main component as a main component to form an outermost layer polymer (IC) having a structure of one layer or two or more layers. Therefore, the rubber-containing polymer (I ′) or (I ″) shown below will be described.

<< Rubber-containing polymer (I ') >>
Examples of the alkyl acrylate used in the innermost layer polymer (I′-A) include various known alkyl acrylates. Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. Of these, n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferable. This alkyl acrylate is used as a main component of the monomers constituting the innermost layer polymer (I′-A). The amount of acrylic acid alkyl ester used is preferably 35 to 99.9% by mass in the total monomers. When the amount used is 35% by mass or more, the moldability of the film is good. Furthermore, the preferable usage-amount is 50 mass% or more. When the innermost layer polymer (I′-A) has a structure of two or more layers, the ranges of these usage amounts are the use of the acrylic acid alkyl ester as a whole of the innermost layer polymer (I′-A). It shows the amount. For example, when making innermost layer polymer (I'-A) into a hard core structure, the usage-amount of the acrylic acid alkylester of the 1st layer (core part) can also be made into less than 35 mass%.
As the monomer constituting the innermost layer polymer (I′-A), together with the alkyl acrylate ester, other vinyl monomers copolymerizable therewith can be used. When other vinyl monomers are used, the amount used is preferably 64.9% by mass or less based on the total monomers. Other vinyl monomers include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methacrylic acid alkyl esters such as cyclohexyl methacrylate, lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, and acrylic acid. Acrylic monomers such as methacrylic acid, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile and the like are preferable. These can be used alone or in combination of two or more.

A polyfunctional monomer is preferably used as a part of the monomer constituting the innermost layer polymer (I′-A). As the polyfunctional monomer, for example, alkylene glycol dimethacrylate such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and propylene glycol dimethacrylate is preferably used. In addition, polyvinyl benzene such as divinylbenzene and trivinylbenzene, triallyl cyanurate, triallyl isocyanurate, and the like can also be used. These can be used alone or in combination of two or more. The amount of the polyfunctional monomer used is preferably 0.1 to 10% by mass in the total monomers.
The rubber-containing polymer (I ′) is obtained by graft-polymerizing a monomer having an alkyl methacrylate ester as a main component in the presence of the innermost layer polymer (I′-A). -C) is a rubber-containing polymer having a multilayer structure of two or more layers.
In the graft polymerization for obtaining the outermost layer polymer (I′-C), methacrylic acid alkyl ester is used as a main component. Specifically, the amount of methacrylic acid alkyl ester used is preferably 50% by mass or more based on the total amount of monomers used for graft polymerization. Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and the like. Of these, methyl methacrylate is preferred.

As a monomer used for graft polymerization for obtaining the outermost layer polymer (I′-C), together with an alkyl methacrylate, other vinyl monomers copolymerizable therewith can also be used. When other vinyl monomers are used, the amount used is preferably 50% by mass or less based on the total monomers. Examples of other vinyl monomers include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and cyclohexyl acrylate. Preferred are acrylic monomers such as lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid and methacrylic acid, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile and the like. These 1 type can be used individually or in combination of 2 or more types.
Each of these monomers is graft polymerized in one or more stages in the presence of the innermost layer polymer (I′-A) to form the outermost layer polymer (I′-C), and rubber. The containing polymer (I ′) is obtained. The amount of the outermost layer polymer (I′-C) in the rubber-containing polymer (I ′) is preferably 10 to 400 parts by mass with respect to 100 parts by mass of the innermost layer polymer (I′-A). Preferably it is 20-200 mass parts.
The mass average particle diameter of the rubber-containing polymer (I ′) is 0.01 to 0.5 μm. 0.08 to 0.3 μm is more preferable. In particular, from the viewpoint of film formability, the particle diameter is preferably 0.08 μm or more. The mass average particle diameter can be measured by a dynamic light scattering method using a light scattering photometer DLS-700 (trade name: manufactured by Otsuka Electronics Co., Ltd.).

Next, a method for producing the rubber-containing polymer (I ′) will be described.
As the method for producing the rubber-containing polymer (I ′), the sequential multi-stage polymerization method by the emulsion polymerization method is the most suitable polymerization method, but is not particularly limited thereto. For example, after the emulsion polymerization, the outermost layer It can also be carried out by an emulsion suspension polymerization method in which the polymer (I′-C) is converted to a suspension polymerization system at the time of polymerization.
As an emulsifier used in emulsion polymerization, 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, sodium N-lauroylsarcosate, alkenyl succinate dipotassium, sulfate esters such as sodium lauryl sulfate , 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. Among these, phosphate ester salts such as sodium polyoxyethylene alkyl ether sodium phosphate are particularly preferable.

The surfactants are: Eleminol NC-718 (manufactured by Sanyo Chemical Industries), Phosphanol LS-529, Phosphanol RS-610NA, Phosphanol RS-620NA, Phosphanol RS-630NA, Phospha Nord RS-640NA, Phosphanol RS-650NA, Phosphanol RS-660NA (manufactured by Toho Chemical Industry Co., Ltd.), Latemul P-0404, Latemulu P-0405, Latemulu P-0406, Latemulu P-0407 ( As mentioned above, it is commercially available as Kao Corporation.
On the other hand, the polymerization initiator used in forming the innermost layer polymer (I′-A) and the outermost layer polymer (I′-C) constituting the preferred rubber-containing polymer (I ′) of the present invention is known. As the addition method, a method of adding to one or both of the aqueous phase and the monomer phase can be used. As a preferred polymerization initiator, a peroxide, an azo initiator, or a redox initiator combined with an oxidizing agent / reducing agent is used. In particular, a redox initiator is preferable, and a sulfoxylate initiator in which ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, longalite, and hydroperoxide are combined is preferable.

A monomer component that gives the innermost layer polymer (I′-A) described above mixed with a surfactant is supplied to the reactor and polymerized, and then the outermost layer polymer (I′-C). In the method of polymerizing by supplying a monomer component to give a reactor, the aqueous solution containing ferrous sulfate, ethylenediaminetetraacetic acid disodium salt and Rongalite is heated to the polymerization temperature, and then the prepared emulsion is reacted. A method of supplying a monomer component to give an outermost layer polymer (I′-C) containing a polymerization initiator such as a peroxide to a reactor and polymerizing the monomer component is a method of the present invention. The most preferable method for obtaining the rubber-containing polymer (I ′).
In addition, although superposition | polymerization temperature changes with kinds and quantity of a polymerization initiator, Preferably it is 40-120 degreeC, More preferably, it is 60-95 degreeC.

The polymer latex containing the rubber-containing polymer (I ′) obtained by the above method is treated using a filtration device provided with a filter medium as necessary. This filtration treatment is for removing the scale from the latex generated during the polymerization, or for removing impurities contained in the polymerization raw material and during the polymerization. In order to obtain the rubber-containing polymer (I ′), This is the preferred method.
The rubber-containing polymer (I ′) can be produced by recovering from the polymer latex produced by the above-described method. Examples of a method for recovering the rubber-containing polymer (I ′) from the polymer latex include salting out or acid precipitation coagulation, spray drying, freeze drying, and the like. Among these, when 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 having a strong affinity for water such as magnesium or sodium is used as a salting-out agent, unless the residual metal content is reduced as much as possible, the finally obtained rubber-containing polymer (I ′ When an acrylic resin film having a part of a raw material is immersed in boiling water, a whitening phenomenon occurs, which is a serious problem in practical use. In addition, when calcium-based and sulfuric acid-based coagulation is performed, a relatively good tendency is shown. In any case, in order to give excellent water whitening resistance, it is necessary to make the residual metal amount 800 ppm or less, The smaller the amount, the better.

<< Rubber-containing polymer (I ") >>
The rubber-containing polymer (I ″) comprises, in order from the inside, the innermost layer polymer (I ″ -A), the intermediate layer polymer (I ″ -B), and the outermost layer polymer (I ″ -C). Has a multilayer structure.
Hereinafter, the structure of the above-mentioned rubber-containing polymer (I ″) will be sequentially described.
1) Innermost layer polymer (I ″ -A)
The innermost layer polymer (I ″ -A) constitutes the central portion of the polymer having the multilayer structure, and includes an acrylic acid alkyl ester (I ″ -A1), a methacrylic acid alkyl ester (I ′ '-A2), other monomers having a double bond copolymerizable therewith (I ″ -A3), multifunctional monomers (I ″ -A4) and graft crossing agents (I ″) -A5) is a polymer obtained by polymerizing monomer components. In this monomer component, component (I ″ -A1) and component (I ″ -A5) are essential components, and component (I ″ -A2), component (I ″ -A3) and The component (I ″ -A4) is an optional component.

The alkyl acrylate ester of the component (I ″ -A1) may be 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 of the above component (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.

In addition, the other component (I ″ -A3) which has a copolymerizable double bond is an acrylic monomer such as lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid or methacrylic acid. Styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile, and the like. These can be used individually or in mixture of 2 or more types.
The polyfunctional monomer (I ″ -A4), which is an optional component, is defined as a monomer having two or more copolymerizable double bonds in one molecule. Specific examples thereof include alkylene glycol dimethacrylates such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and propylene glycol dimethacrylate. In addition, polyvinyl benzene such as divinylbenzene and trivinylbenzene, triallyl cyanurate, triallyl isocyanurate, and the like can also be used. 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 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. For example, when the hot strength or the like is strictly required, it may be arbitrarily performed depending on the purpose of addition.

  On the other hand, it is different from the graft crossing agent (I ″ -A5) which is an essential component contained in the monomer component for constituting the innermost layer polymer (I ″ -A). A monomer having two or more 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, the above polyfunctional monomers such as triallyl cyanurate and triallyl isocyanurate are also effective as grafting agents. Further, the graft crossing agent (I ″ -A5) is polymerized mainly because the conjugated unsaturated bond of the ester reacts much faster than the allyl group, methallyl group or crotyl group. During this time, a significant portion of the allyl, methallyl or crotyl groups work effectively during the polymerization of the next layer of polymer, providing a graft bond between adjacent two layers. This polymerization reaction may be performed in the presence of a chain transfer agent.

The total content of the acrylic acid alkyl ester (I ″ -A1) and the methacrylic acid alkyl ester (I ″ -A2) in the innermost layer polymer (I ″ -A) is 80 to 99.9. Mass% is preferred. Moreover, as for content of acrylic acid alkylester (I ''-A1), 50-99.9 mass% is preferable. From the viewpoint of molding whitening resistance of the resulting acrylic resin film, decorative acrylic resin film and laminate, it is more preferably 55% by mass or more, and still more preferably 60% by mass or more. Further, the upper limit content is more preferably 79.9% by mass or less, and further preferably 69.9% by mass or less, from the viewpoint of the surface hardness of the obtained acrylic resin film, decorative acrylic resin film and laminate. .
On the other hand, the content of the methacrylic acid alkyl ester (I ″ -A2) is preferably 0 to 49.9% by mass. From the viewpoint of the surface hardness of the obtained acrylic resin film, decorated acrylic resin film and laminate, it is more preferably 20% by mass or more, and further preferably 30% by mass or more. Further, from the viewpoint of molding whitening resistance, the upper limit is more preferably 44.9% by mass or less, and further preferably 39.9% by mass or less.

Further, the content of the other monomer (I ″ -A3) having a copolymerizable double bond is preferably 0 to 20% by mass. More preferably, it is 15 mass% or less.
Further, the content of the polyfunctional monomer (I ″ -A4) is preferably 0 to 10% by mass. More preferably, it is 0.1 mass% or more and 6 mass% or less.
The content of the graft crossing agent (I ″ -A5) is preferably 0.1 to 10% by mass. By containing 0.1% by mass or more, the rubber-containing polymer (I ″) obtained can be molded without deteriorating optical properties such as transparency. On the other hand, a content of 10% by mass or less is preferable because sufficient flexibility and toughness can be imparted to the rubber-containing polymer (I ″). More preferably, it is 0.5 mass% or more and 2 mass% or less.

The Tg of the innermost layer polymer (I ″ -A) alone is less than the Tg of the below-mentioned intermediate layer polymer (I ″ -B) alone from the viewpoint of obtaining a product excellent in impact resistance and molding whitening resistance. It is preferable that More preferably, it is less than 25 degreeC, More preferably, it is 10 degreeC or less, Most preferably, it is 0 degreeC or less. Tg can be calculated from the FOX equation using values described in Polymer Handbook (Polymer HandBook (J. Brandrup, Interscience, 1989)).
The content of the innermost layer polymer (I ″ -A) in the rubber-containing polymer (I ″) is preferably 15 to 50% by mass. In the case of 15% by mass or more, it is possible to impart molding whitening resistance to the resulting acrylic resin film, decorative acrylic resin film, and laminate, and further, film forming properties when the acrylic resin is formed into a film, The toughness that is possible for insert molding and in-mold molding of the acrylic resin film and the decorative acrylic resin film to be produced can be made compatible. More preferably, it is 20 mass% or more. Moreover, when the upper limit of content is 50 mass% or less, since the surface hardness and heat resistance required for a vehicle use are obtained, it is preferable. More preferably, it is 35 mass% or less.

The innermost layer polymer (I ″ -A) may be a single layer or multiple layers, but preferably consists of two layers. It is preferable that these two layers have different monomer composition ratios.
When the innermost layer polymer (I ″ -A) is composed of two layers, the Tg of the inner layer (I ″ -A ₁ ) and the Tg of the outer layer (I ″ -A ₂ ) may be the same. From the viewpoints of molding whitening resistance, impact resistance and surface hardness of the resulting acrylic resin film, decorative acrylic resin film and laminate, the Tg of the inner layer (I ″ -A ₁ ) is the outer layer (I ″). more lower than the Tg of -A ₂₎ is preferred. Specifically, from the viewpoint of molding whitening resistance and impact resistance of the resulting acrylic resin film, decorative acrylic resin film, and laminate, the Tg of the inner layer (I ″ -A ₁ ) is less than −30 ° C. The Tg of the outer layer (I ″ -A ₂ ) is preferably 10 ° C. or less. In particular, from the viewpoint of surface hardness, the Tg of the outer layer (I ″ -A ₂ ) is preferably −15 ° C. or higher. The content of the inner layer (I ″ -A ₁ ) in the innermost layer polymer (I ″ -A) at this time is preferably 1% by mass or more and 20% by mass or less, and the outer layer (I ″ -A) The content of ₂ ) is preferably 80% by mass or more and 99% by mass or less.

2) Intermediate layer polymer (I ″ -B)
In the presence of the innermost layer polymer (I ″ -A), the intermediate layer polymer (I ″ -B) is an acrylic acid alkyl ester (I ″ -B1), a methacrylic acid alkyl ester (I ″ -B). -B2), other monomers having a double bond copolymerizable therewith (I "-B3), multifunctional monomers (I" -B4) and graft crossing agents (I "- B5) is a polymer obtained by polymerizing a monomer component. A polymer having a higher Tg of the polymer in the monomer component here than the Tg of the innermost layer polymer is preferable. In this monomer component, the component (I ″ -B1), the component (I ″ -B2) and the component (I ″ -B5) are essential components, and the component (I ″ -B3) and The component (I ″ -B4) is an optional component.
The alkyl ester of acrylic acid (I ″ -B1) may be either an alkyl group having 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, preferred are methyl acrylate and n-butyl acrylate.

The methacrylic acid alkyl ester (I ″ -B2) may be 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.
Other monomers having a copolymerizable double bond of component (I ″ -B3) are acrylic monomers such as lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid and methacrylic acid, styrene Alkyl-substituted styrene, acrylonitrile, methacrylonitrile and the like can be used. These can be used individually or in mixture of 2 or more types.
The polyfunctional monomer of the component (I ″ -B4) is an alkylene such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, etc. Glycol dimethacrylate is preferably used. In addition, polyvinyl benzene such as divinylbenzene and trivinylbenzene, triallyl cyanurate, triallyl isocyanurate, and the like can also be used. Of these, 1,3-butylene glycol dimethacrylate is preferred. These can be used individually or in mixture of 2 or more types. Even when the polyfunctional monomer does not act at all, as long as the grafting agent is present, a fairly stable rubber-containing polymer (I ″) is obtained. For example, when the hot strength or the like is strictly required, it may be arbitrarily performed depending on the purpose of addition.

Examples of the graft crossing agent (I ″ -B5) 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. Among these, methacrylic acid allyl ester has an excellent effect. In addition, the above polyfunctional monomers such as triallyl cyanurate and triallyl isocyanurate are also effective as grafting agents. The graft crossing agent (I ″ -B5) is chemically bonded mainly by the conjugated unsaturated bond of the ester reacting much earlier than the allyl group, methallyl group or crotyl group. During this time, a substantial portion of the allyl, methallyl or crotyl group works effectively during the polymerization of the next layer polymer and provides a graft bond between adjacent two layers.
In addition, you may perform superposition | polymerization here in presence of a chain transfer agent.

The total content of the acrylic acid alkyl ester (I ″ -B1) and the methacrylic acid alkyl ester (I ″ -B2) for constituting the intermediate layer polymer (I ″ -B) was 19.8. -90 mass% is preferable. And as for content of one acrylic acid alkylester (I ''-B1), 9.9-90 mass% is preferable. More preferably, it is 19.9% by mass or more, and more preferably 29.9% by mass or more from the viewpoint of imparting properties such as molding whitening resistance, surface hardness, and heat resistance. Further, the more preferable upper limit content is 60% by mass or less, and further preferably 50% by mass or less.
Further, the content of the methacrylic acid alkyl ester (I ″ -B2) is preferably 9.9 to 90% by mass. From the viewpoint of imparting characteristics such as molding whitening resistance, surface hardness, and heat resistance, it is more preferably 39.9% by mass or more, and most preferably 49.9% by mass or more. Further, the more preferable upper limit content is 80% by mass or less, and more preferably 70% by mass or less.

The content of the other monomer (I ″ -B3) having a copolymerizable double bond is preferably 0 to 20% by mass. More preferably, it is 15 mass% or less.
Further, the content of the polyfunctional monomer (I ″ -B4) is preferably 0 to 10% by mass. More preferably, it is 6 mass% or less.
And as for content of a graft crossing agent (I ''-B5), 0.1-10 mass% is preferable. When the content is 0.1% by mass or more, the resulting rubber-containing polymer (I ″) can be molded without deteriorating the optical properties. A content of 5% by mass or less is preferable because sufficient flexibility and toughness can be imparted to the rubber-containing polymer (I ″). More preferably, it is 0.5 mass% or more and 2 mass% or less.
Here, the composition of the intermediate layer polymer (I ″ -B) is preferably different from the composition of the innermost layer polymer (I ″ -A). When the composition of the polymer is different, the impact resistance and molding whitening resistance of the resulting acrylic resin film, decorative acrylic resin film and laminate can be satisfied at the same time.
In the present invention, “different composition” refers to alkyl acrylates, methacrylic acid alkyl esters, other monomers having copolymerizable double bonds, and polyfunctional monomers forming each polymer. And the type and / or amount of the grafting agent is different.

A polymer having a Tg of 25 to 100 ° C. is preferred when only the monomer component constituting the intermediate layer polymer (I ″ -B) is polymerized. When Tg is 25 ° C. or higher, the surface hardness and heat resistance are at levels required for vehicle use. More preferably, it is 40 degreeC or more, More preferably, it is 50 degreeC or more. Moreover, when Tg is 100 ° C. or less, the molding whitening resistance is good, and the film forming property when the acrylic resin is formed into a film is good. More preferably, it is 80 degrees C or less, More preferably, it is 70 degrees C or less.
Thus, by providing the intermediate layer polymer (I ″ -B) having a specific composition and Tg, a rubber-containing polymer (I ″) or resin suitable for satisfying the required physical properties has been designed. A product having properties such as molding whitening resistance, surface hardness, heat resistance, etc., which were difficult to realize due to lack of leverage, can be obtained.
The content of the intermediate layer polymer (I ″ -B) in the rubber-containing polymer (I ″) is preferably 5 to 35% by mass. Within this range, the function of the intermediate layer polymer (I ″ -B), which is important for achieving both molding whitening resistance, surface hardness, heat resistance, etc., can be expressed, and the resulting film Other physical properties such as film forming properties when an acrylic resin is formed into a film, and imparting toughness that is possible for insert molding and in-mold molding of the resulting acrylic resin film and decorative acrylic resin film. This is preferable because it is possible. More preferably, it is 20 mass% or less.

3) Outermost layer polymer (I ″ -C)
In the presence of the polymer formed up to the intermediate layer, the outermost layer polymer (I ″ -C) is a methacrylic acid alkyl ester (I ″ -C1), an acrylic acid alkyl ester (I ″ -C2). , And other monomer components having a double bond copolymerizable therewith (I ″ -C3) as a constituent component. The outermost layer polymer (I ″ -C) can be obtained by polymerization in at least one stage, and can have a structure of one layer or two or more layers. In this monomer component, the component (I ″ -C1) is an essential component, and the component (I ″ -C2) and the component (I ″ -C3) are optional components.
The alkyl ester of methacrylic acid (I ″ -C1) may have 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.

In addition, the alkyl ester of acrylic acid (I ″ -C2) 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, preferred are methyl acrylate and n-butyl acrylate.
In addition, other monomers having a copolymerizable double bond of (I ″ -C3) are acrylic monomers such as lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, methacrylic acid, styrene, Alkyl substituted styrene, acrylonitrile, methacrylonitrile and the like can be used. These can be used individually or in mixture of 2 or more types.

The content of the alkyl methacrylate (I ″ -C1) in the monomer component for constituting the outermost layer polymer (I ″ -C) is preferably 51 to 100% by mass. From the viewpoint of surface hardness, heat resistance, and the like of the obtained acrylic resin film, it is more preferably 80% by mass or more, further preferably 90% by mass or more, and most preferably 93% by mass or more and 99% by mass or less.
Further, the content of the acrylic acid alkyl ester (I ″ -C2) is preferably 0 to 20% by mass. More preferably, it is 1 mass% or more. Further, it is more preferably 10% by mass or less, and most preferably 7% by mass or less.
Furthermore, the content of the monomer (I ″ -C3) having a copolymerizable double bond is preferably 0 to 49% by mass. More preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less.

The molecular weight of the outermost layer polymer (I ″ -C) can be adjusted by using a chain transfer agent during the polymerization of the outermost layer polymer (I ″ -C). This chain transfer agent is selected from those usually used for radical polymerization. Specific examples include alkyl mercaptans having 2 to 20 carbon atoms, mercapto acids, thiophenol, carbon tetrachloride and the like, and these can be used alone or in combination of two or more. The content of the chain transfer agent is 100% of monomers ((I ″ -C1) to (I ″ -C3)) included in the monomer component for constituting the polymer (I ″ -C). 0.01-5 mass% is preferable with respect to the mass%. More preferably, it is 0.2 mass% or more, More preferably, it is 0.4 mass% or more.
Further, it is preferable that the polymer having only the monomer component for constituting the outermost layer polymer (I ″ -C) has a Tg of 60 ° C. or higher. When Tg is 60 ° C. or higher, a film having surface hardness and heat resistance suitable for vehicle use can be obtained. More preferably, it is 80 degreeC or more, More preferably, it is 90 degreeC or more. Further, from the viewpoint of coagulability and handleability of the resulting rubber-containing polymer (I ″), the upper limit temperature is preferably 105 ° C. or less.

The content of the outermost layer polymer (I ″ -C) in the rubber-containing polymer (I ″) is preferably 10 to 80% by mass. From the viewpoint of surface hardness and heat resistance, it is preferably 15% by mass or more, more preferably 45% by mass or more. In addition, when the content is 80% by mass or less, the resulting acrylic resin film, the decorated acrylic resin film and the laminate can be molded whitening-resistant, and the resulting acrylic resin film and the decorated acrylic resin film can be in-mold molded Toughness can be imparted. More preferably, it is 70 mass% or less.
The rubber-containing polymer (I ″) of the present invention is composed of the polymer layers (I ″ -A), (I ″ -B) and (I ″ -C) described above. However, in the resulting acrylic resin film, decorative acrylic resin film, and laminate, the rubber-containing polymer (I ″) has a gel content of 50% or more in order to obtain further excellent molding whitening resistance. It is preferable. More preferably, it is 60% or more. In this case, the gel content (%) means that a predetermined amount (mass before extraction: W ₀ (g)) of the rubber-containing polymer (I ″) is extracted under reflux in an acetone solvent, and then centrifuged to remove acetone. After removing the soluble component and drying the remaining acetone-insoluble component, the mass (mass after extraction: W ₁ (g)) was measured and calculated by the following formula.
Gel content ratio = mass after extraction W ₁ / mass before extraction W ₀ × 100

In terms of the molding whitening resistance of the resulting acrylic resin film, decorative acrylic resin film and laminate, the higher the gel content, the more advantageous, but from the viewpoint of easy moldability, a certain amount of free polymer or more. The gel content is preferably 80% or less.
The mass average particle diameter of the rubber-containing polymer (I ″) is 0.01 to 0.5 μm. Preferably, it is in the range of 0.05 to 0.3 μm. From the viewpoint of mechanical properties of the obtained acrylic resin film, it is more preferably 0.07 μm or more, and most preferably 0.09 μm or more. Moreover, from a viewpoint of the shaping | molding whitening resistance of the obtained acrylic resin film, a decorative acrylic resin film, and a laminated body, More preferably, it is 0.15 micrometer or less, Most preferably, it is 0.13 micrometer or less. The mass average particle diameter can be measured by a dynamic light scattering method using a light scattering photometer DLS-700 (trade name: manufactured by Otsuka Electronics Co., Ltd.).

Next, a method for producing the rubber-containing polymer (I ″) will be described.
As the method for producing the rubber-containing polymer (I ″), the sequential multi-stage polymerization method by the emulsion polymerization method is the most suitable polymerization method, but is not particularly limited thereto. It can also be produced by an emulsion suspension polymerization method in which the outer layer polymer (I ″ -C) is converted to a suspension polymerization system during the polymerization.
When the rubber-containing polymer (I ″) is produced by an emulsion polymerization method, a monomer component that gives the innermost layer polymer (I ″ -A) in the rubber-containing polymer (I ″) is added. Then, an emulsion prepared by mixing with water and a surfactant in advance is supplied to the reactor and polymerized to give an intermediate layer polymer (I ″ -B) and an outermost layer polymer (I ″ -C). A method in which the monomer components are sequentially fed to the reactor and polymerized is preferable.
By polymerizing by the above-described polymerization method, the number of particles having a diameter of 55 μm or more present in the dispersion liquid, especially when dispersed in acetone, is 0 to 50 per 100 g of the rubber-containing polymer (I ″). A rubber-containing polymer (I ″) can be easily obtained. The 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 a low printing pressure that easily causes printing omission. Even when solid gravure printing such as metallic tone, jet black tone, etc. is applied, there are few print omissions and high level printability.

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, sodium N-lauroylsarcosate, alkenyl succinate dipotassium, sulfate esters such as sodium lauryl sulfate , 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. Among these, phosphate ester salts such as sodium polyoxyethylene alkyl ether sodium phosphate are particularly preferable.
As the surfactant, Eleminol NC-718 (trade name: Sanyo Chemical Industries, Ltd.), Phosphanol LS-529, Phosphanol RS-610NA, Phosphanol RS-620NA, Phosphanol RS-630NA , Phosphanol RS-640NA, Phosphanol RS-650NA, Phosphanol RS-660NA (trade name: manufactured by Toho Chemical Industry Co., Ltd.), Latemul P-0404, Latemul P-0405, Laterum P-0406 Laterum P-0407 (trade name: manufactured by Kao Corporation) and the like are commercially available.

In addition, as a method for preparing an emulsion, 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, For example, a method in which water is added after a surfactant is charged into the monomer component. Among these, the method of charging the surfactant after charging the monomer component into water and the method of charging the monomer component after charging the surfactant into water give the rubber-containing polymer (I ″). It is preferable as a method.
As a mixing device for preparing an emulsion prepared by mixing the monomer component giving the innermost layer polymer (I ″ -A) with water and a surfactant, a stirrer and a homogenizer equipped with a stirring blade, Various forced emulsification devices such as homomixers, membrane emulsification devices and the like can be mentioned.
The emulsified liquid to be prepared may be either a W / O type in which water droplets are dispersed in the monomer component oil, or an O / W type dispersion type in which oil droplets of the monomer component are dispersed in water. However, it is particularly preferable that the diameter of the oil droplets in the dispersed phase is 100 μm or less in the O / W type in which the oil droplets of the monomer component are dispersed in water.

The innermost layer polymer (I ″ -A), the intermediate layer polymer (I ″ -B) and the outermost layer polymer (I ″ -C) constituting the rubber-containing polymer (I ″) are formed. A known polymerization initiator can be used as the polymerization initiator used at the time. The addition method may be any of the method of adding to one or both of the aqueous phase and the monomer phase. As the polymerization initiator, a peroxide, an azo initiator, a redox initiator combined with an oxidizing agent / reducing agent, or the like is used. Among these, a redox initiator is preferable, and a sulfoxylate initiator combined with ferrous sulfate, disodium ethylenediaminetetraacetate, longalite, and hydroperoxide is particularly preferable.
An emulsion prepared by mixing the monomer component giving the innermost layer polymer (I ″ -A) with water and a surfactant is supplied to the reactor and polymerized, and then the intermediate layer polymer (I '' -B) and the monomer component giving the outermost layer polymer (I ''-C) are sequentially fed to the reactor, and in the polymerization method, ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, After raising the aqueous solution containing Rongalite to the polymerization temperature, the prepared emulsion is supplied to the reactor for polymerization, and then the intermediate layer polymer (I ″ -B) containing a polymerization initiator such as peroxide and the like The method of sequentially supplying the monomer component giving the outermost layer polymer (I ″ -C) to the reactor and polymerizing is the most preferable method for obtaining the rubber-containing polymer (I ″) of the present invention.
In addition, although superposition | polymerization temperature changes with kinds and quantity of a polymerization initiator, Preferably it is 40-120 degreeC, More preferably, it is 60-95 degreeC.

The polymer latex containing the rubber-containing polymer (I ″) obtained by the above method is treated by a filtration apparatus provided with a filter medium as necessary. This filtration treatment is intended to remove scales generated during polymerization from latex, or to remove impurities contained in the polymerization raw material and from the outside during polymerization. Rubber-containing polymer (I ″) Is a more preferred method for obtaining
In addition, as a filtration apparatus used at that time, a cylindrical filter medium is arranged on the inner side surface of the GAF filter system of ISP Filters PTE Ltd. using a bag-shaped mesh filter or a cylindrical filter chamber, A centrifugal filtration device in which a stirring blade is disposed in the filter medium, or a vibration type filter 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 from the polymer latex produced by the above-described method. Examples of a method for recovering the rubber-containing polymer (I ″) include methods such as salting out, acid precipitation coagulation, spray drying, and freeze drying.
Among these methods, when a salting-out treatment is performed 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 having a strong affinity for water such as magnesium or sodium is used as a salting-out agent, unless the residual metal content is reduced as much as possible, the finally obtained rubber-containing polymer (I ′ When an acrylic resin film made from ') is immersed in boiling water, whitening occurs, which is a serious problem in practical use. In addition, when calcium-based and sulfuric acid-based coagulation is performed, a relatively good tendency is shown, but in any case, in order to give excellent water whitening resistance, it is important that the residual metal amount is 800 ppm or less, The smaller the amount, the better.

<< Thermoplastic polymer (II) >>
The thermoplastic polymer (II) has a methacrylic acid alkyl ester of 50 to 100% by mass, an acrylic acid alkyl ester of 0 to 50% by mass, and a monomer having a double bond copolymerizable therewith of 0 to 49% by mass. % Of a polymer having a reduced viscosity (0.1 g of the polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) of 0.15 L / g or less. It is preferably a coalescence.
When the reduced viscosity of the thermoplastic polymer (II) is 0.15 L / g or less, moderate elongation occurs at the time of melting when the acrylic resin is processed into a film, and the film-forming property is improved. More preferably, it is 0.1 L / g or less. Further, the lower limit of the reduced viscosity is preferably 0.05 L / g or more. If it is 0.05 L / g or more, the problem of film breakage at the time of film formation of an acrylic resin film due to brittleness and at the time of printing on the film becomes difficult to occur.
Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate. Of these, methyl methacrylate is most preferred. This methacrylic acid alkyl ester is preferably in the range of 50 to 100% by mass in the monomer component for obtaining the thermoplastic polymer (II). More preferably, it is the range of 85-99.9 mass%, More preferably, it is the range of 92-99.9 mass%. By setting this range, for example, vehicle members and the like are easily exposed to high temperatures and easily touched by hands and objects, but are necessary when a laminate having an acrylic resin as the outermost layer is applied to the vehicle member. It can exhibit heat resistance and high hardness.

Moreover, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, etc. are mentioned as alkyl acrylate ester used for the said monomer component as needed. It is preferable to use the acrylic acid alkyl ester in the monomer component in the range of 0 to 50% by mass. More preferably, it is the range of 0.1-40 mass%, More preferably, it is the range of 0.1-15 mass%, Most preferably, it is the range of 0.1-8 mass%. By setting this range, for example, vehicle members and the like are easily exposed to high temperatures and easily touched by hands and objects, but are necessary when a laminate having an acrylic resin as the outermost layer is applied to the vehicle member. It can exhibit heat resistance and high hardness.
Furthermore, examples of the monomer having a copolymerizable double bond used as necessary for the monomer component include styrenes such as styrene and α-methylstyrene, N-phenylmaleimide and N-cyclohexyl. And maleimides such as maleimide, maleic acid, maleic anhydride and acrylonitrile. The amount used is preferably in the range of 0 to 49% by mass in the monomer component.
The polymerization method of the thermoplastic polymer (II) is not particularly limited, and can be performed by suspension polymerization, emulsion polymerization, bulk polymerization, or the like. A chain transfer agent may be used to bring the reduced viscosity of the polymer into a predetermined range. As the chain transfer agent, known ones can be used, and mercaptans are particularly preferable. The amount used may be determined appropriately depending on the type or composition of the monomer.

By changing the ratio of the rubber-containing polymer (I) and the thermoplastic polymer (II) used in the acrylic resin film of the present invention, the heat resistance and hardness of the film can be easily adjusted. For example, sufficient heat resistance can be exhibited when applied to a laminate having an acrylic resin film as the outermost layer, such as a vehicle member, which is easily exposed to high temperatures and easily touched by hands and objects.
The compounding ratio of the rubber-containing polymer (I) and the thermoplastic polymer (II) is based on a total of 100 parts by mass of the rubber-containing polymer (I) and the thermoplastic polymer (II). 1) to 99 parts by mass and 1 to 99 parts by mass of the thermoplastic polymer (II).
When using the rubber-containing polymer (I ′), from the viewpoint of heat resistance and surface hardness, when the total of the rubber-containing polymer (I ′) and the thermoplastic polymer (II) is 100 parts by mass, the thermoplasticity The polymer (II) is more preferably 60 parts by mass or more, and still more preferably 70 parts by mass or more. For example, a vehicle member or the like is a member that is easily exposed to high temperatures and is easily touched by a hand or an object. In this case, heat resistance and high hardness that can withstand it can be exhibited.

The content of the rubber-containing polymer (I ′) is preferably 40 parts by mass or less, preferably 30 parts by mass or less, when the total of the rubber-containing polymer (I ′) and the thermoplastic polymer (II) is 100 parts by mass. More preferred. For example, when the laminated body which laminated | stacked the acrylic resin film or decorative acrylic resin film of this invention on the base material is applied to a vehicle member, the heat resistance which can endure it, and high hardness can be exhibited.
Moreover, when using rubber-containing polymer (I ''), from the viewpoint of molding whitening resistance of the resulting acrylic resin film, decorative acrylic resin film and laminate, the rubber-containing polymer (I '') and The rubber-containing polymer (I ″) is preferably 50 parts by mass or more and more preferably 65 parts by mass or more with respect to 100 parts by mass in total with the thermoplastic polymer (II).
The thermoplastic polymer (II) is preferably 50 parts by mass or less, more preferably 35 parts by mass or less from the viewpoint of resistance to molding whitening. Moreover, 5 mass parts or more are preferable from a viewpoint of heat resistance and hardness, and 20 mass parts or more are preferable. By doing so, when applying the laminated body which laminated | stacked the acrylic resin film of this invention on the base material to a vehicle member, it can exhibit the heat resistance and high hardness which can endure it, and the acrylic resin obtained The laminated molded product which does not impair the whitening resistance of the film, the decorative acrylic resin film and the laminate can be provided.

Of the rubber-containing polymer (I), the thermoplastic polymer (II), the organic crosslinked particles or the inorganic particles which are the main raw materials of the acrylic resin film of the present invention, the rubber-containing polymer (I) and the organic crosslinked particles The shape of the inorganic particles is powdery. On the other hand, when the thermoplastic polymer (II) to be used is melt-extruded in advance and shaped into a pellet shape, the raw materials are mixed and then put into the extruder hopper, the shape of the shape is within the hopper. The classification is caused by the difference, and the problem that the difference in film quality such as matte property becomes extremely large during production.
For this reason, the shape of the thermoplastic polymer (II) is preferably a bead or powder. That is, the rubber-containing polymer (I), the thermoplastic polymer (II), the organic crosslinked particles or the inorganic particles used as the main raw material of the acrylic resin film of the present invention are all in the form of powder or beads. Preferably there is. When the main raw material for film is in the form of powder or beads, after mixing the raw material for film, it is possible to stabilize the film quality such as matte properties without causing classification in the extruder hopper. Become.

The gel content of the acrylic resin composition constituting the acrylic resin film of the present invention is the film forming property when the acrylic resin composition is formed into a film, and the resulting acrylic resin film, decorated acrylic resin film, and From the viewpoint of molding whitening resistance of the laminate, it is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 40% by mass or more. Moreover, from a viewpoint of the film forming property at the time of shape | molding an acrylic resin composition in a film form, 80 mass% or less is preferable, 75 mass% or less is more preferable, and 70 mass% or less is further more preferable.
The organic crosslinked particles or inorganic particles used in the present invention do not contain particles having a mass average particle diameter Dw of more than 1 μm and 20 μm or less and a particle diameter of 10 × Dw μm or more.
When the Dw of the organic crosslinked particles or inorganic particles to be used exceeds 1 μm, it is preferable because a good matte property can be imparted to the film with an appropriate addition amount. Further, when the Dw of the organic crosslinked particles or inorganic particles is 20 μm or less, it is preferable because the physical property degradation such as impact resistance is small. More preferably, it is 15 micrometers or less, More preferably, it is 10 micrometers or less, Most preferably, it is 8 micrometers or less.

In addition, when the organic crosslinked particles or the inorganic particles do not contain coarse particles having a particle diameter of 10 × Dw μm or more, the generation of defects having a recessed film surface is eliminated, and a film having a very good surface appearance can be obtained. In particular, even when high brightness printing such as a silver metallic tone in which the surface defects are very conspicuous, a decorative film having a good surface appearance can be obtained, which is preferable. In addition, in the case of a film obtained by sandwiching between a mirror roll and a rubber roll during film production, it is good without developing concave surface defects when the film is heated in a secondary processing step such as in-mold molding. A laminated molded product can be obtained while maintaining a good surface appearance.
As for the presence or absence of coarse particles that cause defects that appear to be concave on the film surface that can be confirmed when the resin composition is formed into a film, a conventionally known method such as a particle counter or a laser light scattering method is used. In this case, it is difficult to detect, and it can be confirmed for the first time by observing the mass of the matting material blended in a predetermined film area with a scanning electron microscope. That is, even if a very small amount of coarse particles are present in the organic crosslinked particles or inorganic particles blended in the predetermined film area, a specific (10 × Dw μm) mass-average particle diameter region is mass by laser light scattering method. There are cases where it is evaluated as 0% in terms of conversion. In such a case, when the film is formed into a film, defects with a concave surface are generated, resulting in a film having a poor surface appearance and low industrial utility value. End up.

The content of the organic crosslinked particles or inorganic particles is appropriately adjusted within the above range depending on the surface gloss of the target film. For example, when the addition amount is 1 part by mass or more with respect to 100 parts by mass of the acrylic resin composition, an excellent matting effect is exhibited. Further, from the viewpoint of obtaining good matting properties, 2 parts by mass or more is more preferable, and 5 parts by mass or more is most preferable with respect to 100 parts by mass of the acrylic resin composition. On the other hand, in the case of 15 parts by mass or less, good film forming properties are obtained, and further, from the viewpoint of good film mechanical properties that enable insert molding and in-mold molding properties. More preferably, it is 10 parts by mass or less. The surface gloss of the film can be obtained by using a gloss meter (manufactured by Murakami Color Research Laboratory, model GM-26D) and measuring the surface that was in contact with the mirror roll at the time of film formation at an angle of 60 °.
For the organic crosslinked particles of the present invention, generally known organic crosslinked particles such as a crosslinked styrene polymer and a crosslinked acrylic polymer are used. Further, generally known inorganic particles such as silica, alumina, calcium carbonate, mica, mica and talc are used for the inorganic particles of the present invention. Among these, although it does not specifically limit, it is preferable that it is crosslinked acrylic polymer (III). When a cross-linked acrylic polymer is used, it is possible to suppress a decrease in transparency of the film, and it is preferable because it does not impair the design properties when the film is printed. The crosslinked acrylic polymer (III) refers to an acrylic polymer having a crosslinked structure. Specifically, a cross-linked methacrylic monomer composed of a polyfunctional monomer having two or more copolymerizable double bonds in one molecule similar to a polymerizable monomer mainly composed of methacrylic acid alkyl ester. Core-shell structure polymer particles composed of particles, a core of a rubbery polymer mainly composed of alkyl acrylate, and a glassy polymer shell mainly composed of alkyl methacrylate. Hereinafter, the crosslinked methacrylic particles and the core-shell structure polymer particles will be described.

<Crosslinked methacrylic particles>
The cross-linked methacrylic particles are composed of a polyfunctional monomer having two or more copolymerizable double bonds in one molecule as much as a polymerizable monomer mainly composed of methacrylic acid alkyl ester. The alkyl methacrylate used for the crosslinked methacrylic particles refers to those having methyl methacrylate as a main component, but in addition, alkyl groups such as ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate and the like. Is a straight chain or branched chain alkyl alkyl ester, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate or the like. Or branched acrylic alkyl ester, lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid such as acrylic acid, methacrylic acid, etc., styrene, alkyl substituted styrene, acrylonitrile, methacrylonitrile, etc. The other monomers having a double bond can be used in combination.
Polyfunctional monomers having two or more copolymerizable double bonds in one molecule are ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol diester. Dimethacrylate compounds such as methacrylate and propylene glycol dimethacrylate, trimethacrylate compounds such as trimethylolpropane trimethacrylate and trimethylolethane trimethacrylate, polyvinylbenzene such as divinylbenzene and trivinylbenzene, triallyl cyanurate, triallyl isocyanurate, etc. Can be used.
The proportion of the methacrylic acid alkyl ester constituting the crosslinked methacrylic particles is preferably 50 to 99.5% by mass, and the proportion of the polyfunctional monomer is preferably 0.5 to 50% by mass.

Next, a method for producing crosslinked methacrylic particles will be described.
As a method for producing the crosslinked methacrylic particles, a polymerization method by suspension polymerization is preferred. A known method can be adopted as the concentration of the polymerizable monomer in the suspension and the method for preparing the suspension. To obtain the crosslinked acrylic particles of the present invention, first, a dispersion stabilizer is used. An O / W emulsion having a desired droplet size is prepared by mixing water in which water is dissolved or suspended and a polymerizable monomer containing a polymerization initiator, and applying mechanical shear to the mixture. It is then preferred to polymerize.
In order to stabilize the suspension, it is preferable to add a dispersion stabilizer to the suspension as necessary. Specifically, water-soluble polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, and methyl cellulose, anionic surfactants such as sodium oleate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkylsulfonate, laurylamine Known substances such as cationic surfactants such as acetate and lauryltrimethylammonium chloride, and nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene alkylphenyl ether can be used.

As the polymerization initiator, an oil-soluble peroxide-based or azo-based initiator usually used for suspension polymerization can be used. Specifically, peroxides such as benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, 2,2′-azobisisobutyronitrile, 2,2 Examples include azo initiators such as' -azobis (2,4-dimethylvaleronitrile). The polymerization temperature varies depending on the type and amount of the polymerization initiator used, but is usually 50 to 95 ° C.
The method for removing the crosslinked methacrylic particles from the suspension is not particularly limited, although a method of filtering, a method of using a separator such as a centrifugal separator, or spray drying is simple. The crosslinked methacrylic particles after being taken out from the suspension may be washed and dried as necessary, but the drying temperature and the drying method are not particularly limited.
It is preferable to remove specific coarse particles by classifying the crosslinked methacrylic particles obtained by drying. The classification method is not particularly limited, but an air classifier is preferred from the balance of the classification ability and the processing amount.

<Core-shell structure polymer particles>
The core-shell structure polymer particles are composed of a rubber-like polymer core mainly composed of an acrylic acid alkyl ester and a shell mainly composed of a methacrylic acid alkyl ester.
The rubber-like polymer that is the core consists of an alkyl acrylate ester as the main component, another monomer having a copolymerizable double bond, and two copolymerizable double bonds in one molecule. It consists of a polyfunctional monomer having the above and a graft crossing agent having two or more different copolymerizable double bonds in one molecule.
In the alkyl acrylate ester, alkyl groups such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate are linear or branched. Is.
In addition, other monomers having the above double bond are methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methacrylic acid alkyl esters such as cyclohexyl methacrylate, lower alkoxy acrylate, cyanoethyl acrylate, Acrylic monomers such as acrylamide, acrylic acid and methacrylic acid, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile and the like are preferable. These can be used individually by 1 type or in combination of 2 or more types.

Examples of the polyfunctional monomer include ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, propylene glycol dimethacrylate and other dimethacrylate compounds, trimethylolpropane trimethacrylate. Trimethacrylate compounds such as trimethylolethane trimethacrylate, polyvinylbenzene such as divinylbenzene and trivinylbenzene, triallyl cyanurate, triallyl isocyanurate and the like can be used.
Further, as the graft crossing agent, acrylic acid, methacrylic acid, maleic acid, fumaric acid allyl ester, or the like can be used.
The content of the acrylic acid alkyl ester in the monomer component for constituting the rubber-like polymer as the core is preferably 50 to 99.9% by mass. The other monomer having a double bond capable of copolymerization is 0 to 49.9% by mass, the polyfunctional monomer is 0 to 20% by mass, and the grafting agent is 0.1 to 20% by mass. preferable.

The glassy polymer that becomes the shell is composed of alkyl methacrylate ester as the main component, other monomers having a copolymerizable double bond, and two copolymerizable double bonds in one molecule. It consists of a polyfunctional monomer having the above.
The alkyl methacrylate ester contained in the monomer component for constituting the glassy polymer to be the shell is methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, An alkyl group such as cyclohexyl methacrylate is linear or branched.
Other monomers having a copolymerizable double bond include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and acrylic acid. Acrylic acid alkyl esters such as cyclohexyl, lower alkoxy acrylates, cyanoethyl acrylates, acrylamides, acrylic monomers such as acrylic acid and methacrylic acid, styrene, alkyl-substituted styrenes, acrylonitrile, methacrylonitrile and the like are preferable. These 1 type can be used individually or in combination of 2 or more types.

The polyfunctional monomer having two or more copolymerizable double bonds in one molecule includes ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol. Dimethacrylate compounds such as dimethacrylate and propylene glycol dimethacrylate, and trimethacrylate compounds such as trimethylolpropane trimethacrylate and trimethylolethane trimethacrylate can be used.
As for content of the alkyl methacrylate in the monomer component for comprising the glassy polymer used as a shell, 50-100 mass% is preferable. The other monomer having a copolymerizable double bond is preferably 0 to 50% by mass, and the polyfunctional monomer is preferably 0 to 20% by mass.
Further, the content of the rubber-like polymer serving as the core in the core-shell structure polymer particles is preferably 30 to 95% by mass. On the other hand, the content of the glassy polymer to be a shell is preferably 5 to 70% by mass.

Next, the manufacturing method of a core-shell structure polymer particle is demonstrated.
As a method for producing the core-shell structure polymer particles, a polymerization method by suspension polymerization is preferable. As the concentration of the polymerizable monomer in the suspension and the method for preparing the suspension, a known method can be adopted. A mixture of water in which an agent is dissolved or suspended and a polymerizable monomer that forms a rubber-like polymer as a core containing a polymerization initiator, and mechanical shear is applied to the mixture to form desired droplets. It is preferred to prepare an O / W emulsion having a diameter and then polymerize.
In order to stabilize the suspension, it is preferable to add a dispersion stabilizer to the suspension as necessary. Specifically, water-soluble polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, methylcellulose, anionic surfactants such as sodium oleate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium dialkylsulfosuccinate, laurylamine acetate, Known ones such as cationic surfactants such as lauryltrimethylammonium chloride and nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene alkylphenyl ether can be used.

As the polymerization initiator, an oil-soluble peroxide-based or azo-based initiator usually used for suspension polymerization can be used. Specifically, peroxides such as benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, 2,2′-azobisisobutyronitrile, 2,2 Examples include azo initiators such as' -azobis (2,4-dimethylvaleronitrile).
The polymerization temperature varies depending on the type and amount of the polymerization initiator used, but is preferably 50 to 95 ° C.
The rubber-like polymer that becomes the core is reacted, and the monomer mixture that becomes the glassy polymer that becomes the shell is added to the obtained rubber-like polymer particle suspension. As an addition method, a method of preparing a suspension together with the above-mentioned dispersion stabilizer and supplying it all at once or over a predetermined time is preferable.
As a method for taking out the core-shell structure polymer particles from the suspension, a method of filtering, a method using a separator such as a centrifugal separator, or spray drying is simple, but not particularly limited. The core-shell structure polymer particles taken out from the suspension may be washed and dried as necessary, but the drying temperature and the drying method are not particularly limited.
It is preferable to remove specific coarse particles by classifying the core-shell structure polymer particles obtained by drying. The classification method is not particularly limited, but an air classifier is preferred from the balance of the classification ability and the processing amount.

Although not particularly limited, it is preferable to add 0.1 to 1 part by mass of silica particles having a mass average particle diameter of 100 nm or less with respect to 100 parts by mass of the acrylic resin composition that is a constituent of the acrylic resin film of the present invention. .
When 0.1 parts by mass or more of silica particles having a mass average particle diameter of 100 nm or less are added to the acrylic resin composition, the main raw materials for acrylic resin film are all in the form of powder or beads for the purpose of stabilizing the film quality This is preferable because it can prevent the raw material powder from consolidating easily, improve the fluidity in the extruder hopper, and realize satisfactory supply to the extruder. More preferably, it is 0.2 parts by mass. Moreover, it is preferable to add 1 part by mass or less of the silica particles because the degree of deterioration of optical properties such as transparency and mechanical properties such as elongation at break is small. More preferably, it is 0.8 mass part, More preferably, it is 0.5 mass part.
In the acrylic resin composition constituting the acrylic resin film of the present invention, separately from the above-mentioned thermoplastic polymer (II), the reduced viscosity of the polymer as an additive (0.1 g of polymer is dissolved in 100 mL of chloroform, 25 Thermoplastic polymer (IV) exceeding 0.15 g / L can be used.

<Thermoplastic resin (IV)>
The thermoplastic polymer (IV) to be blended with the above polymer as required contains 50 to 100% by mass of methyl methacrylate and 0 to 50 other monomers having a double bond copolymerizable therewith. It is a polymer obtained by polymerizing a monomer component having a mass%, and is preferably a thermoplastic polymer having a reduced viscosity of the polymer exceeding 0.15 L / g.
When the thermoplastic polymer (IV) is used, the film forming property when the acrylic resin is formed into a film is improved, so that it is particularly useful when a high level of thickness accuracy and film forming speed are required. In particular, when the reduced viscosity of the thermoplastic polymer (IV) is in a range exceeding 0.15 L / g, a film with good thickness accuracy can be obtained. This reduced viscosity usually exceeds 0.15 L / g and is 2 L / g or less, preferably 1.2 L / g or less.
Other monomers having a double bond copolymerizable with methyl methacrylate used as necessary for the monomer component for obtaining the thermoplastic polymer (IV) include alkyl acrylates, methacrylates. Examples include acid alkyl esters, aromatic vinyl compounds, and vinyl cyanide compounds.
The thermoplastic polymer (IV) is obtained by polymerizing these monomer components. The polymerization method is preferably an emulsion polymerization method, and the polymer can be recovered in a powder form by a usual emulsion polymerization method and post-treatment method.
The amount of the thermoplastic polymer (IV) used is preferably 0 to 10 parts by mass when the total of the rubber-containing polymer (I) and the thermoplastic polymer (II) is 100 parts by mass. By using the thermoplastic polymer (IV), the film-forming property when the acrylic resin is formed into a film is improved. On the other hand, by controlling the viscosity to 10 parts by mass or less, the viscosity of the acrylic resin is suppressed. It is possible to prevent the film formability from being lowered when the resin is formed into a film.

In addition, the acrylic resin composition constituting the acrylic resin film of the present invention can be prepared by adding a general compounding agent such as a stabilizer, a lubricant, a processing aid, a matting agent, a light diffusing agent, a plasticizer, Impact aids, foaming agents, fillers, colorants, antibacterial agents, fungicides, mold release agents, antistatic agents, light stabilizers, ultraviolet absorbers and the like can be included.
From the viewpoint of reducing the appearance defects that appear to be recessed in the vicinity of the gate when in-mold molding is performed using a decorative acrylic resin film that has been given designability and high-intensity printing of metallic tone, You may contain a light-diffusion agent in the resin composition which comprises the acrylic resin film of invention. An acrylic resin film containing a light diffusing agent is sandwiched between a mirror-finished SUS plate heated to 130 ° C., subjected to hot press molding under a condition of 3 MPa, and the surface is mirror-finished so that the internal haze (JIS) K7136; whiteness measurement method C method described in “Measurement based on“ how to obtain haze of plastic-transparent material ”” is 2 to 75% and whiteness (JIS L1015; “chemical fiber staple test method”) (Measurement based on (Hunter method)) is preferably 30% or less.
As the light diffusing agent to be used, various conventionally known light diffusing agents can be mentioned regardless of organic or inorganic. A light-diffusion agent can be used individually or in mixture of 2 or more types. The light diffusing agent to be used is preferably about 2 to 30 μm from the viewpoint of preventing the decorative portion of the laminate from becoming too cloudy and from the viewpoint of film forming properties of the acrylic resin film, for example, a silicone resin or a styrene resin. Styrene-acrylic resin, acrylic resin, benzoguanamine-formaldehyde condensate, benzoguanamine-melamine-formaldehyde condensate, melamine-formaldehyde condensate, mica, talc, calcium carbonate, silica and the like.

  From the viewpoint of protecting the substrate, it is preferable to add an ultraviolet absorber to the resin composition constituting the acrylic resin film of the present invention in order to impart weather resistance. The molecular weight of the ultraviolet absorber is preferably 300 or more, and more preferably 400 or more. If this molecular weight is 300 or more, it is difficult to volatilize when vacuum forming or pressure forming is performed in an injection mold, and mold contamination is difficult to occur. The type of the UV absorber is not particularly limited, but a benzotriazole UV absorber having a molecular weight of 400 or more and a triazine UV absorber having a molecular weight of 400 or more are particularly preferable. As the former commercial product, for example, Tinuvin 234 (trade name: manufactured by Ciba Specialty Chemicals), Adeka Stub LA-31 (trade name: manufactured by Asahi Denka Kogyo Co., Ltd.), and the latter commercial product, for example, Tinuvin 1577 (Trade name: manufactured by Ciba Specialty Chemicals).

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.
A method in which the resin composition, which is a raw material for the acrylic resin film of the present invention, is formed into a film shape by a melt extrusion method such as a T-die method, and then is sandwiched between a mirror roll and a rubber roll to form a film. By sandwiching between the mirror roll and the rubber roll, surface protrusions due to foreign matters that cause printing omission can be remarkably reduced, and printing omission can be remarkably reduced when printing is performed on the obtained film. Various conventionally known rolls can be used as the rubber roll. From the viewpoint of heat resistance, the rubber roll is preferably made of silicone rubber.

In particular, it is preferable to sandwich the acrylic resin film with a silicone rubber roll whose surface is mirror-finished by polishing or the like (hereinafter also simply referred to as “silicone mirror rubber roll”). Specifically, for example, IT68S silicone mirror roll (hardness = A87, surface roughness R _MAX = 2 μm, manufactured by Mochida Corporation). In the case of the acrylic resin film of the present invention, by sandwiching one surface with a mirror surface roll and the other surface with a silicone mirror surface rubber roll, the silicone rubber roll contact surface may be a smooth surface and the mirror surface contact surface may be a matte surface. In particular, like the film of the present invention, it is possible to manufacture while maintaining the original surface roughness of the film raw material having a fine uneven shape with a maximum height of 5 μm or less on the film surface, that is, the matte degree. Become. As a known example, when a silicone rubber roll containing sand (specifically, a silicone rubber roll to which 50% by mass of sand having an average particle size of 40 μm is added) as described in JP-A-2002-361712 is used. The surface roughness of the film after being produced is more strongly affected by the surface roughness of the silicone rubber roll containing sand than the original surface roughness of the film raw material. For this reason, when manufacturing the film of this invention characterized by the fine uneven | corrugated shape of a film surface, use of the well-known sandy silicone rubber roll is not suitable.

In the calendering method, the film can be formed by replacing one side of the two mirror-finished rolls between which the film is finally sandwiched with a rubber roll. Or after forming into a film shape once by a well-known method, an acrylic resin film can be heated again more than a glass transition temperature, and it can also pinch | interpose with a mirror surface roll and a rubber roll, and can also manufacture.
As the mirror surface roll, a roll having a surface roughness of 0.5 S or less obtained by performing chrome plating on a known mirror surface roll is preferable. During film production, the mirror roll is preferably temperature-controlled within a range of 20 to 140 ° C. The temperature range is preferably 50 to 120 ° C, more preferably 60 to 100 ° C. When the mirror roll is in this temperature range, the mirror roll contact surface is a matte surface, and the silicone rubber roll contact surface is a smooth surface while maintaining film-forming properties such as good peelability of the acrylic resin film from the mirror roll. A film with good appearance can be obtained.
Moreover, when melt-extruding a resin composition, it is preferable to extrude while filtering the resin composition in a molten state with a screen mesh of 80 mesh or more.

The acrylic resin film of the present invention preferably has a pencil hardness (measured based on JIS K5400) of 2B or higher (higher hardness including 2B). Further, HB or more is preferable, and F or more is most preferable. When an acrylic resin film having a pencil hardness of 2B or more is used, the acrylic resin film and the decorative acrylic resin film are not easily damaged during the process of insert molding or in-mold molding, and the resistance of the laminated molded product obtained by laminating them is further improved. Abrasion is also good.
For example, when used for a vehicle, the pencil hardness of the acrylic resin film of the present invention is preferably HB or higher. Acrylic resin film with a pencil hardness of HB or higher, decorative acrylic resin film, and laminated molded products laminated with these are suitable for various vehicle members such as door waist garnish, front control panel, power window switch panel, airbag cover, etc. Can be used for It is very useful industrially from the viewpoint of expanding applications. Furthermore, if the pencil hardness is F or more, the scratches are not noticeable even when scratched with a cloth with a rough surface such as gauze, and have practical scratch resistance equivalent to that of a molded product using an acrylic resin film with a pencil hardness of 2H. Since it can be imparted, the industrial utility value is extremely high.

  The acrylic resin film of the present invention preferably has a heat distortion temperature (measured based on ASTM D648) of 80 ° C. or higher. In the case of an acrylic resin film having a heat distortion temperature of 80 ° C. or higher, the melt viscosity of the resin composition for the film becomes moderately high when the film is formed, the releasability from the mirror roll becomes good, and the film is wound around the mirror roll. It can prevent problems such as sticking. Further, for example, in a vehicle application, the acrylic resin film, the decorative acrylic resin film of the present invention, and a laminated molded product including these can be used for a part that receives direct sunlight in a vehicle, such as a front control panel. From the viewpoint of further expanding the application, the heat distortion temperature is preferably 90 ° C. or higher. Moreover, it is preferable that the heat distortion temperature of the acrylic resin film of this invention is 130 degrees C or less. In the case of an acrylic resin film having a heat deformation temperature of 130 ° C. or lower, the followability to the rubber roll becomes good when the film is formed, the film surface in contact with the rubber roll exhibits good smoothness, and printing omission is reduced. . The measurement of the heat distortion temperature is carried out using a heat deformation temperature measurement specimen obtained by molding raw material pellets of an acrylic resin film by injection molding and annealing at 60 ° C. for 4 hours. Usually, it is the same as the thermal deformation temperature of the acrylic resin film.

  It is particularly useful to use the acrylic resin film of the present invention after printing by an appropriate printing method as necessary in order to impart design properties to various substrates. In this case, it is preferable that the acrylic resin film is subjected to a one-side printing process and used as a film having a picture layer on one side. In the case of the acrylic resin film of the present invention, it is preferable to produce while maintaining the fine uneven shape of the original surface of the film. As the production method, a resin composition melt-extruded from a T-die is mirror-finished and polished. It is preferable to hold it with a rubber roll having a mirror-finished surface. Under the present circumstances, a rubber roll contact surface becomes a smooth surface among the acrylic resin films obtained. For this reason, it is preferable to arrange a pattern layer on the surface that was in contact with the rubber roll when the acrylic resin film was produced. Moreover, at the time of shaping | molding, it is preferable from a viewpoint of protection of a decorating surface (printing surface) and provision of a high-class feeling to arrange | position a printing surface to an adhesive surface with base-material resin. Examples of the printing method include a method of applying ink by a conventionally known printing method and coating method. Specifically, gravure printing method, flexographic printing method, silk screen printing method, offset printing method, roll coating method, gravure coating method, comma coating method and the like.

As the ink used in the printing layer, a known thermoplastic resin such as an acrylic resin, a polyvinyl resin, a polyester resin, a polyurethane resin, or a polyamide resin can be used as a binder. Moreover, the acrylic resin composition which consists of rubber-containing polymer (I) and / or thermoplastic polymer (II) of this invention can also be used as a thermoplastic resin binder. In particular, when an acrylic resin composition comprising the rubber-containing polymer (I ″) and the thermoplastic polymer (II) of the present invention is used as a thermoplastic resin binder, the printed layer disappears in the vicinity of the gate during in-mold molding described later. It is preferable because a printing layer that suppresses the above can be provided.
In the case of metallic tone printing, the ink contains a high brightness pigment as an essential component. For example, a known high-luminance pigment such as an aluminum pigment such as non-leafing aluminum paste (manufactured by Showa Aluminum Powder) or a pearl pigment such as iriodine (manufactured by Merck) is used. Moreover, a pigment or dye of an appropriate color can be contained as a colorant.
Further, as a method other than the printing method and the coating method, the metallic print layer can be formed by a known method such as a vacuum deposition method, a sputtering method, an ion plating method, or a plating method. Although a known metal can be used as the printing layer, it is preferable from the viewpoint of in-mold moldability to use aluminum, indium, or an alloy containing these with excellent malleability.

The number of missing prints on the surface on which the acrylic resin film is printed 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 laminated product of this film becomes better. The number of missing prints on the printed surface is more preferably 5 pieces / m ² or less.
When the number of missing prints is 10 pieces / m ² or less, even in the case of a metallic printed pattern in which missing prints are obvious as defects, the design properties and the surface appearance are not deteriorated. It is preferable because it does not decrease, and industrial utility value is extremely high.
Moreover, what colored the acrylic resin film of this invention can be used.
Further, in addition to the printing layer, it is preferable to provide an adhesive layer in order to enhance the adhesiveness with the resin as the base material. The adhesive layer may be provided on the printing layer, or may be provided on the film surface opposite to the printing layer. It is also possible to provide an adhesive layer on the surface of an acrylic resin film having no printed layer.

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 and 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, the sense of depth can be more sufficiently imparted to the obtained molded product together with the protection of the base material. As for the thickness of an acrylic resin film, 30 micrometers or more are more preferable. The thickness of the acrylic resin film is more preferably 200 μm or less.
In order to form a coating film having a sufficient thickness on a molded product by coating, it may be necessary to apply ten or more times of recoating. On the other hand, since the acrylic resin film itself becomes a coating film, the laminated molded product of the present invention can easily form a very thick coating film and has high industrial utility value.

The laminated molded product of the present invention is characterized in that the acrylic resin film or the decorated acrylic resin film of the present invention is laminated on a substrate. In particular, it is obtained by an in-mold molding method in which the acrylic resin film is subjected to vacuum molding or pressure molding in an injection mold, and then the resin as the base material is injection molded in the injection mold. It is preferable to use a laminated molded product. Also, a laminate obtained by an insert molding method in which preforming such as vacuum forming or pressure forming is performed, and the preform is inserted into another mold, and then a resin as a base material is injection molded to obtain a laminate molded product. It can also be a molded product. In the case of this insert molding method, it is preferable to use a laminated sheet or film obtained by laminating the acrylic resin film or the decorated acrylic resin film of the present invention on a thermoplastic resin layer. As the thermoplastic resin layer used for the laminated sheet or film, a known thermoplastic resin film or sheet can be used. For example, acrylic resin, ABS resin, AS resin, vinyl chloride resin, polystyrene resin, polycarbonate resin, polyester resin, polyolefin resin, and the like can be given. Among these, acrylic resin, ABS resin, vinyl chloride resin, and polyolefin resin are preferable from the viewpoint of printability and secondary moldability of the laminated film or sheet. The position of the printed layer in the laminated sheet or film in which the decorative acrylic resin film is laminated on the thermoplastic resin layer is not particularly limited, but from the viewpoint of imparting the desired design of the pattern to the laminated molded product, It is preferable to arrange between acrylic resin layers. Thereby, a decoration layer can be protected and the design property with the depth can be implement | achieved.
Furthermore, it is preferable to provide an adhesive layer in order to improve the adhesiveness with the resin as the base material. The adhesive layer may be provided on the thermoplastic resin layer, or may be provided on the film surface opposite to the thermoplastic resin layer.

It is preferable that resin used as the base material in the laminated molded product of the present invention is a resin that can be melt-bonded to an acrylic resin film or a decorative acrylic resin film. For example, ABS resin, AS resin, polystyrene resin, polycarbonate resin, vinyl chloride resin, acrylic resin, polyester resin, or resin containing these as main components can be given. From the viewpoint 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. However, it is possible to bond an acrylic resin film or a decorative acrylic resin film and a base material at the time of molding by using an adhesive layer even with a base material resin such as polyolefin resin that is not thermally fused.
When the laminated molded product of the present invention is molded into a two-dimensional shape, a known method such as thermal lamination can be used for a base material that can be heat-sealed. It is possible to bond to a base material that is not heat-sealed through an adhesive. Moreover, when shape | molding in a three-dimensional shape, well-known methods, such as an insert molding method and an in-mold molding method, can be used, and the in-mold molding method is preferable from the point of productivity. In the in-mold molding method, after the acrylic resin film or the decorated acrylic resin film is heated, vacuum molding is performed in a mold having a vacuum drawing function. This method is preferable from the viewpoints of workability and economy because the film can be molded and injection molded in one step.
When in-mold molding is performed using an acrylic resin film having a printing layer, the printing layer near the gate may disappear depending on the shape of the mold and the injection molding conditions. The gate is roughly classified into a non-restricted gate in which the resin path is not narrowed in the gate portion and a limited gate in which the resin path is narrowed. Typical examples of the latter include pinpoint gates, side gates, and submarine gates. Although these gate shapes reduce the residual stress near the gate, the temperature of the resin passing through the gate increases, or the injection resin pressure per unit area on the acrylic resin film surface near the gate increases. The printed layer on the acrylic resin film surface tends to disappear.

Among the acrylic resin films of the present invention, in particular, by using an acrylic resin film comprising an acrylic resin composition comprising a rubber-containing polymer (I ″) and a thermoplastic polymer (II), a conventional acrylic resin film is used. Compared with the case of using a resin film, the disappearance of the pattern can be reduced. In addition, it is preferable to perform insert molding using a laminated sheet or a film from the point which can suppress the loss | disappearance of a printing layer more by suppressing transmission of a calorie | heat amount by presence of a thermoplastic resin layer.
The heating temperature during in-mold molding is preferably equal to or higher than the temperature at which the acrylic resin film or the decorative acrylic resin film is softened. Specifically, although it depends on the thermal properties of the film or the shape of the molded product, it is usually 70 ° C. or higher. On the other hand, if the temperature is too high, the surface appearance tends to deteriorate or the releasability tends to deteriorate. Although this also depends on the thermal properties of the film or the shape of the molded product, it is usually preferably 170 ° C. or lower.
Furthermore, from the viewpoint of energy efficiency, it is preferable that the preheating temperature during vacuum forming is low. Specifically, 135 ° C. or lower is preferable. In addition, a film that can be molded even if the preheating temperature is low can shorten the preheating time instead of lowering the preheating temperature. In this case, it is possible to increase the cycle of vacuum forming, and the industrial utility value is high.

As a method for suppressing the problem of disappearance of the printed layer generated when performing in-mold molding from the molding conditions, the preheating temperature during vacuum molding may be increased. The purpose of this is to use a printing layer having a heat-crosslinking reactive component and apply heat more than in normal molding to firmly fix the printing layer on an acrylic resin film and then mold it. This method naturally reduces the molding cycle. Among the acrylic resin films of the present invention, in particular, when an acrylic resin film comprising an acrylic resin composition comprising a rubber-containing polymer (I ″) and a thermoplastic polymer (II) is used, such a method is used. A laminated molded product having a good appearance can be obtained without adopting, so that a high cycle of molding is possible and the industrial utility value is very high.
Thus, when a three-dimensional shape is imparted to the film by vacuum forming, the acrylic resin film or the decorative acrylic resin film is rich in elongation at high temperatures, which is very advantageous.
The laminated molded product obtained by laminating the acrylic resin film or the decorated acrylic resin film of the present invention on a base material can be subjected to surface treatment for imparting various functions as needed. For example, printing processes such as silk printing and ink jet printing, metal deposition or sputtering / wet plating process for imparting metal tone or preventing reflection, surface hardening process for improving surface hardness, water repellency process for preventing dirt, or Examples include photocatalyst layer forming treatment, dust adhesion prevention or antistatic treatment for the purpose of cutting electromagnetic waves, and antiglare treatment.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples. In the examples, “part” represents “part by mass”, and “%” represents “% by mass”. Abbreviations in the examples are as follows.
Methyl methacrylate MMA
Methyl acrylate MA
Ethyl acrylate EA
n-butyl acrylate n-BA
Styrene St
Ethylene glycol dimethacrylate ED
1,3-butylene glycol dimethacrylate 1,3-BD
Allyl methacrylate AMA
Cumene hydroperoxide CHP
Lauroyl peroxide LPO
t-Butyl hydroperoxide t-BH
2,2'-Azobisisobutyronitrile AIBN
n-octyl mercaptan n-OM
Ethylenediaminetetraacetic acid disodium EDTA

Rubber-containing polymer (I) [(I ′) and (I ″)], thermoplastic polymer (II), thermoplastic polymer (IV), crosslinked acrylic polymer (III) [(III-1) (III-4)], acrylic resin films and laminated molded products were measured for various physical properties by the following test methods.
1) Glass transition temperature of each polymer layer of rubber-containing polymer (I) The value described in Polymer Handbook (Polymer HandBook (J. Brandrup, Interscience, 1989)) was used to calculate from the FOX equation.
2) Gel content G (%) of rubber-containing polymer (I)
A predetermined amount of rubber-containing polymer (I) (mass before extraction: W ₀ (g)) is extracted under reflux in an acetone solvent, and acetone-soluble components are removed by centrifugation, and the remaining acetone-insoluble components are dried. Then, the mass (mass after extraction: W ₁ (g)) was measured and calculated by the following formula.
Gel content rate G = mass after extraction W ₁ / mass before extraction W ₀ × 100
3) Mass average particle diameter of rubber-containing polymer (I) The mass average particle diameter of the polymer latex of the rubber-containing polymer (I) obtained by emulsion polymerization was measured with a light scattering photometer (DLS, manufactured by Otsuka Electronics Co., Ltd.). -700 (trade name)) and measured by a dynamic light scattering method.

4) Mass average particle diameter of cross-linked acrylic polymer (III) [(III-1) to (III-4)] Measured using a laser diffraction / scattering particle size distribution analyzer (LA-910, manufactured by Horiba, Ltd.). did.
5) Reduced viscosity of thermoplastic polymer (II) and thermoplastic polymer (IV) Using an AVL-2C (trade name) automatic viscometer manufactured by San Denki Kogyo Co., Ltd., using chloroform as the solvent and measuring at 25 ° C did. In the measurement of the reduced viscosity, a sample prepared by dissolving 0.1 g of a sample in 100 mL of chloroform was used.
6) Surface gloss of film Using a gloss meter (manufactured by Murakami Color Research Laboratory, model GM-26D), the surface that was in contact with the mirror roll at the time of film formation was measured at an angle of 60 °.
7) Total light transmittance of film The obtained film was measured according to the test method of JIS K7361-1.

8) HDT of the 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) Pencil hardness of film Measured according to JIS K5400.
10) Number of missing prints A gravure pattern was printed on the surface of the acrylic resin film that was in contact with the rubber roll, a 5 m ² visual inspection was performed, and the number of missing prints was measured and converted to 1 m ² .
11) Surface appearance of laminated molded product The surface appearance of the in-mold molded product was evaluated as follows.
○: There is no concave surface defect.
X: A concave surface defect exists and industrial utility value is low.

<1. Production of rubber-containing polymer (I ′)>
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, (15) shown below was added, and while stirring, 1/15 of the raw material (b) for the polymer (I′-A ₁ ) shown below was charged and held for 15 minutes. Next, the remaining raw material (b) was continuously added at an increase rate of 8% / hour of the monomer mixture [raw material (b)] with respect to water, and then held for 60 minutes to obtain a polymer (I′-A ₁ ) latex was obtained.
The Tg of the polymer (I′-A ₁ ) alone was 24 ° C.
Subsequently, 0.6 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 raw material (c) for the polymer (I′-A ₂ ) shown below was increased by 4% in the monomer mixture [raw material (c)] with respect to water. / Hour, and then continuously added for 120 minutes to polymerize the polymer (I′-A ₂ ), and the innermost layer polymer (I′-A) [(I′-A ₁ ) + (I′-A ₂ )] latex was obtained.
The Tg of the polymer (I′-A ₂ ) alone was −38 ° C.
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 raw material (d) for the outermost layer polymer (I′-C) shown below was increased by a monomer mixture [raw material (d)] with respect to water at an increase rate of 10 After continuously adding at% / hour, the mixture was held for 60 minutes, and the outermost layer polymer (I′-C) was polymerized to obtain a polymer latex of the rubber-containing polymer (I ′).
The Tg of the outermost layer polymer (I′-C) alone was 99 ° C.
The rubber-containing polymer (I ′) obtained had a weight average particle diameter of 0.28 μm.
The polymer latex of the obtained rubber-containing polymer (I ′) is subjected to coagulation, aggregation and solidification using calcium acetate, filtered, washed with water, and dried to obtain the rubber-containing polymer (I ′). Obtained. The gel content of the rubber-containing polymer (I ′) was 90%.

(I) sodium formaldehyde sulfoxylate 0.6 part,
0.00012 parts of ferrous sulfate,
0.0003 parts EDTA.
(B) MMA 22.0 parts,
n-BA 15.0 parts,
3.0 parts of St,
0.4 part AMA,
1,3-BD 0.14 parts,
0.18 parts t-BH,
40% mono (polyoxyethylene nonylphenyl ether) phosphoric acid
Di (polyoxyethylene nonylphenyl ether) phosphoric acid 60%
1.0 part of a partially neutralized mixture of sodium hydroxide.
(C) 50.0 parts of n-BA,
10.0 parts of St,
0.4 part AMA,
1,3-BD 0.14 parts,
0.2 part of t-BH,
40% mono (polyoxyethylene nonylphenyl ether) phosphoric acid
Di (polyoxyethylene nonylphenyl ether) phosphoric acid 60%
1.0 part of a partially neutralized mixture of sodium hydroxide.
(D) 57.0 parts of MMA,
3.0 parts of MA,
n-OM 0.3 part,
0.06 parts t-BH.

<2. Production of rubber-containing polymer (I ″)>
After charging 10.8 parts of deionized water into a vessel equipped with a stirrer, it consists of 0.3 part of MMA, 4.5 parts of n-BA, 0.2 part of 1,3-BD, 0.05 part of AMA and 0.025 part of CHP. The monomer mixture was added and stirred and mixed at room temperature. Next, 1.3 parts of an emulsifier (manufactured by Toho Chemical Industry 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 put into a polymerization vessel equipped with a cooler, 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. Subsequently, 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 of the polymer (I ″ -A ₁ ).
Subsequently, a monomer mixture 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 is dropped into the polymerization vessel over 90 minutes together with 0.016 part of CHP. Then, the reaction was continued for 60 minutes to complete the polymerization of the polymer (I ″ -A ₂ ) to obtain the innermost layer polymer (IA).
The Tg of the polymer (I ″ -A ₁ ) alone was −48 ° C., and the Tg of the polymer (I ″ -A ₂ ) alone was −10 ° C.

Subsequently, a monomer mixture 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 obtain an intermediate layer polymer ( I ″ -B) was formed.
The Tg of the intermediate layer polymer (I ″ -B) alone was 60 ° C.
Subsequently, a monomer mixture 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 the reaction was continued for 60 minutes. A polymer (I ″ -C) was formed to obtain a polymer latex of a rubber-containing polymer (I ″).
The Tg of the outermost layer polymer (I ″ -C) alone was 99 ° C.
The weight average particle diameter of the rubber-containing polymer (I ″) measured after the polymerization was 0.11 μm.
The polymer latex of the rubber-containing polymer (I ″) thus obtained was filtered using a vibration type filtration device in which a SUS mesh (average opening: 62 μm) was attached to the filter medium, and then calcium acetate 3.5 It was salted out in an aqueous solution containing parts, washed with water, recovered and dried to obtain a powdery rubber-containing polymer (I ″).
The gel content of the rubber-containing polymer (I ″) was 70%.

  Further, 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 obtain acetone of the rubber-containing polymer (I ″). A dispersion was prepared. Next, this dispersion was filtered through a nylon mesh having a mesh size of 32 μm, and then the nylon mesh was washed in 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, after which the nylon mesh is removed, 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. there were.

<3. Production of Crosslinked Acrylic Polymer (III-1 to III-3; Crosslinked Methacrylic Particles)>
A container equipped with a stirrer was charged with 600 parts of deionized water in which 0.5 part of polyoxyethylene alkyl sulfoammonium (Daiichi Kogyo Seiyaku Co., Ltd .: trade name “Hytenol N08”) was dissolved as a dispersion stabilizer. A monomer mixture consisting of 90 parts of MMA, 10 parts of trimethylolpropane trimethacrylate, 1.0 part of LPO, and 1 part of 3,4-dinitrobenzoic acid was added in advance. Thereafter, this mixed solution was treated with T.W. A homogenous suspension having a predetermined droplet diameter was prepared with a K homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Next, the temperature was raised to 75 ° C., and the polymerization reaction was carried out with stirring for 1 hour under a nitrogen atmosphere. Furthermore, the temperature was raised to 90 ° C., and the reaction was terminated while stirring for 4 hours under a nitrogen atmosphere. The suspension was cooled, filtered and dried to obtain polymer particles. The obtained polymer particles are classified by an air classifier (manufactured by Nissin Engineering Co., Ltd .; trade name “TC-15N”), and 10 × {mass average particle diameter (Dw) of the obtained polymer particles} μm or more The coarse particles were removed to obtain crosslinked PMMA particles. In addition, about 1.78 g of crosslinked PMMA (a mass when the amount of resin per 0.125 m ^{2 of} 125 μm film is 17.8 g and assuming that 10 mass% of the crosslinked PMMA is added), a scanning electron microscope (Hitachi, Ltd.) Observed using a product name “S570”), it was confirmed that there were no coarse particles of 10 × Dw μm or more.

<4. Production of Crosslinked Acrylic Polymer (III-4; Core-Shell Structure Polymer Particles)>
A container equipped with a stirrer was charged with 200 parts of deionized water in which 30 parts of a 5% polyvinyl alcohol aqueous solution was dissolved as a dispersion stabilizer. ) Was added. Thereafter, this mixed solution was treated with T.W. A uniform suspension having a droplet diameter of about 7 μm was prepared using a K homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Next, the temperature was raised to 70 ° C., and a polymerization reaction was carried out with stirring under a nitrogen atmosphere for 2 hours to obtain a rubber-like polymer particle suspension. Next, this rubber-like polymer particle suspension is cooled to 60 ° C., and the glassy polymer raw material (f) that becomes the shell is increased by 10% in the monomer mixture [raw material (f)] to water. After the continuous addition, the temperature was raised to 80 ° C. when polymerization started and an exothermic peak was observed, and the reaction was terminated with stirring for 3 hours. The suspension was cooled, filtered and dried to obtain polymer particles. The obtained core-shell structure polymer had a mass average particle diameter Dw of 8 μm. The obtained polymer particles are classified by an air classifier (manufactured by Nissin Engineering Co., Ltd .; trade name “TC-15N”), and coarse particles having a size of 10 × Dw (= 80) μm or more are removed to obtain core-shell structure polymer particles. Got. In addition, about 1.78 g of core-shell structure polymer (mass when the amount of resin per 0.125 m ^{2 of} 125 μm film is 17.8 g and 10 mass% of the core-shell structure polymer is added), scanning type Observation was performed using an electron microscope (manufactured by Hitachi, Ltd .; trade name “S570”), and it was confirmed that there were no coarse particles of 10 × Dw (= 80) μm or more.

(E) 61 parts of n-BA
1 part of AMA
1,3-BD 1 part
LPO 1 part (F) MMA 34 parts
EA 2 parts
ED 1 part
AIBN 0.4 parts
10 parts of 1% dioctyl sulfosuccinate sodium aqueous solution
10 parts of deionized water

<5. Production of thermoplastic polymer (IV)>
The reaction vessel was charged with 200 parts of ion-exchanged water substituted with nitrogen, 1 part of Latemul ASK (trade name; manufactured by Kao Corporation) and 0.15 part of potassium persulfate as emulsifiers. Subsequently, 40 parts of MMA, 2 parts of n-BA, and 0.004 part of n-OM were charged and stirred at 65 ° C. for 3 hours in a nitrogen atmosphere to complete the polymerization. Subsequently, a monomer mixture consisting of 44 parts of MMA and 14 parts of n-BA was added dropwise over 2 hours, and then maintained for 2 hours to complete the polymerization. The obtained latex was added to a 0.25% aqueous sulfuric acid solution, the polymer was acidified, dehydrated, washed with water, and dried to recover the polymer in powder form. The reduced viscosity of the obtained copolymer was 0.38 L / g.

[Example 1]
23 parts of the rubber-containing polymer (I ′) obtained above, thermoplastic polymer (II) (MMA / MA copolymer, MMA / MA = 99/1 (mass ratio), reduced viscosity 0.06 L / g, 67 parts of beads shape, 10 parts of crosslinked acrylic polymer (III-1) (mass average particle diameter Dw = 2 μm), 1.4 parts of tinuvin 234 (trade name: manufactured by Ciba Specialty Chemicals Co., Ltd.), ADK STAB AO -60 (trade name: manufactured by Asahi Denka Kogyo Co., Ltd.) 0.1 part, LA-67 (manufactured by Asahi Denka Kogyo Co., Ltd.) 0.3 part, JP333E (trade name: manufactured by Johoku Chemical Co., Ltd.) 0.3 part, Aerosil R972 (Product name: Nippon Aerosil Co., Ltd.) 0.3 part and thermoplastic polymer (IV) 6 part were mixed in a Henschel mixer. This mixture was supplied to a degassing extruder (manufactured by Ikekai Tekko Co., Ltd .; trade name “PCM-30”) heated to 230 ° C. and kneaded to obtain pellets. The obtained pellet had an HDT of 90 ° C.
The pellets were dried overnight at 80 ° C., and a cylinder temperature of 180 to 240 ° C. and a T die temperature of 240 ° C. were used using a 40 mmφ non-vent screw type extruder (L / D = 26) equipped with a 300 mm wide T die. Under the conditions, melt extrusion was performed through a 100-mesh metal filter and a T-die. The extruded resin was sandwiched between a mirror mirror roll for cooling adjusted to 75 ° C. (a chrome-plated roll having a surface roughness of 0.2S) and a silicone mirror rubber roll to form an acrylic resin film having a thickness of 125 μm. . The film had a pencil hardness of H.

On the silicone rubber roll contact surface side of the obtained acrylic resin film, 10 parts of gravure ink in which acrylic resin is dissolved in MEK and toluene (= 1/1 vol / vol) at a solid content of 25%, scaly aluminum pigment Using an ink containing 2 parts, silver metallic printing was performed by gravure printing. The thickness of the printing layer was 5 μm. No print loss occurred.
Next, using a heat-resistant ABS resin bulk sum TM25B (trade name: manufactured by UMGABS) and a printed acrylic resin film as a base resin, it has a vacuum drawing function, and a mold (molded product shape: length 150 mm) × Box shape with width 120mm × thickness 2mm, depth 10mm, gate position: one location at the center of the molded product, and one location at a position 40mm above and below the central gate (vertical direction of the molded product), gate shape: Using a pin-point gate with a diameter of 1 mm, an in-mold molding device (trade name; manufactured by Nippon Steel Works) and a hot pack system (produced by Nissha Printing Co., Ltd.) and in-mold molding ( Film vacuum forming conditions: heater temperature 260 ° C., heating time 15 seconds, distance between heater and film 15 mm, injection molding conditions: cylinder to nozzle temperature 50 ° C., injection speed 30%, injection pressure 43%, mold temperature 60 ° C., non-decorated surface was vacuum-formed in contact with the mold, and base resin was injected from the decorated surface side) A molded product was obtained.

[Example 2]
The blending ratio of the rubber-containing polymer (I ′), the thermoplastic polymer (II), and the crosslinked acrylic polymer (III-1) (mass average particle diameter Dw = 2 μm) is 23/70/7 (part / part). This was carried out in the same manner as in Example 1 except that The obtained pellet had an HDT of 91 ° C. Further, the pencil hardness of the obtained film was H.
[Example 3]
The blending ratio of the rubber-containing polymer (I), the thermoplastic polymer (II), and the crosslinked acrylic polymer (III-1) (mass average particle diameter Dw = 2 μm) was 23/72/5 (part / part / Example 1) was carried out in the same manner as in Example 1. The obtained pellet had an HDT of 91 ° C. Further, the pencil hardness of the obtained film was H.
[Examples 4 to 6]
In Examples 1 to 3, instead of the crosslinked acrylic polymer (III-1) (mass average particle diameter Dw = 2 μm), the crosslinked acrylic polymer (III-2) (mass average particle diameter Dw = 4 μm) was used. It implemented similarly to Examples 1-3, respectively except using. In addition, HDT of the obtained pellet was 90 degreeC (Example 4) and 91 degreeC (Examples 5 and 6), respectively. Moreover, the pencil hardness of the obtained film was all H.

[Examples 7 to 9]
In Examples 1 to 3, instead of the crosslinked acrylic polymer (III-1) (mass average particle diameter Dw = 2 μm), a crosslinked acrylic polymer (III-3) (mass average particle diameter Dw = 6 μm) was used. It implemented similarly to Examples 1-3, respectively except using. In addition, HDT of the obtained pellet was 90 degreeC (Example 4) and 91 degreeC (Examples 5 and 6), respectively. Moreover, the pencil hardness of the obtained film was all H.
[Example 10]
In Example 1, it implemented like Example 1 except having used bridge | crosslinking acrylic polymer (III-4) instead of bridge | crosslinking acrylic polymer (III-1). The obtained pellet had an HDT of 90 ° C. Further, the pencil hardness of the obtained film was H.

[Example 11]
In Example 1, instead of the cross-linked acrylic polymer (III-1), a micro mica “MK-100” (trade name: manufactured by Co-op Chemical) having a mass average particle diameter Dw = 5 μm was used as an air classifier (Nisshin). Made by Engineering Co., Ltd .: trade name “TC-15N”), and the same procedure as in Example 1 was used except that coarse particles of 10 × Dw (= 50) μm or more were used. The obtained pellet had an HDT of 90 ° C. Further, the pencil hardness of the obtained film was H.
In addition, about 1.78 g of micro mica (a mass when the amount of resin per 0.125 m ^{2 of a} 125 μm film is 17.8 g and assuming that 10 mass% of the micro mica is added), a scanning electron microscope (Hitachi Observed using a trade name “S570” manufactured by Seisakusho Co., Ltd.), it was confirmed that there were no coarse particles of 10 × Dw (= 50) μm or more.

[Example 12]
65 parts rubber-containing polymer (I ″), thermoplastic polymer (II) (MMA / MA copolymer, MMA / MA = 99/1 (mass ratio), reduced viscosity 0.06 L / g, bead shape) 25 parts, crosslinked acrylic polymer (III-1) (mass average particle diameter Dw = 2 μm) 10 parts, tinuvin 234 (trade name: manufactured by Ciba Specialty Chemicals) as a compounding agent, ADK STAB AO-60 ( Product name: Asahi Denka Kogyo Co., Ltd.) 0.1 part, LA-67 (trade name: Asahi Denka Kogyo Co., Ltd.) 0.3 part, JP333E (trade name: Johoku Chemical Industry Co., Ltd.) 0.3 part, Aerosil R972 (Product name: Nippon Aerosil Co., Ltd.) 0.3 parts and thermoplastic polymer (IV) 3 parts were mixed in a Henschel mixer. This mixture was supplied to a degassing extruder (manufactured by Ikekai Tekko Co., Ltd .; trade name “PCM-30”) heated to 230 ° C. and kneaded to obtain pellets. The same procedure as in Example 1 was performed except that pellets of this resin composition were used. The obtained pellet had an HDT of 88 ° C. Further, the pencil hardness of the obtained film was H.

[Example 13]
The blending ratio of the rubber-containing polymer (I ″), the thermoplastic polymer (II), and the crosslinked acrylic polymer (III-1) (mass average particle diameter Dw = 2 μm) is 65/28/7 (part / Part / part). The obtained pellet had an HDT of 89 ° C. Further, the pencil hardness of the obtained film was H.
[Example 14]
The blending ratio of the rubber-containing polymer (I ″), the thermoplastic polymer (II), and the crosslinked acrylic polymer (III-1) (mass average particle diameter Dw = 2 μm) is 65/30/5 (part / Part / part). The obtained pellet had an HDT of 89 ° C. Further, the pencil hardness of the obtained film was H.

[Example 15]
In Example 1, the film was formed in the same manner as in Example 1 except that the film was not sandwiched between the mirror roll and the silicone rubber roll during film formation, and the surface resulting from coarse particles of organic crosslinked particles or inorganic particles. Although no concave defects were generated, surface protrusions due to other foreign matters existed, printing omissions occurred frequently due to the surface protrusions, and the film could not be satisfactorily decorated.
[Example 16]
In Example 1, manufactured by Nippon Aerosil Co., Ltd., except that the trade name “Aerosil R972” was not added. Could not be produced.

[Comparative Example 1]
This was carried out in the same manner as in Example 1 except that Sekisui Plastics Co., Ltd .; trade name “MBX-8” (crosslinked PMMA, mass average particle diameter Dw = 8 μm) was used as the crosslinked acrylic polymer (III). The obtained pellet had an HDT of 90 ° C. Further, the pencil hardness of the obtained film was H.
In addition, about 1.78 g (mass on the assumption that the amount of resin per 0.125 m ^{2 of} 125 μm film is 17.8 g and 10 mass% of the crosslinked acrylic polymer is added), a scanning electron microscope ( Observed using a product name “S570” manufactured by Hitachi, Ltd., coarse particles of 10 × Dw (= 80) μm or more were present.
[Comparative Example 2]
As cross-linked acrylic polymer (III), manufactured by Soken Chemical Co., Ltd .; trade name “MR-2G” (cross-linked PMMA, mass average particle diameter Dw = 1 μm), rubber-containing polymer (I ′), thermoplastic polymer This was carried out in the same manner as in Comparative Example 1 except that a resin composition using (II) and the crosslinked acrylic polymer (III) at a compounding ratio shown in Table 1 was used.
At the time of film production, film breakage occurred frequently, resulting in poor film forming properties.
In addition, about 1.78 g (mass on the assumption that the amount of resin per 0.125 m ^{2 of} 125 μm film is 17.8 g and 10 mass% of the crosslinked acrylic polymer is added), a scanning electron microscope ( When observed using Hitachi Ltd. (trade name “S570”), coarse particles of 10 × Dw (= 10) μm or more were not present.

[Comparative Example 3]
The same procedure as in Example 1 was performed except that MR-7G (crosslinked PMMA, mass average particle diameter Dw = 5 μm (trade name) manufactured by Soken Chemical Co., Ltd.) was used as the crosslinked acrylic polymer (III). The obtained pellet had an HDT of 90 ° C. Further, the pencil hardness of the obtained film was H.
In addition, about 1.78 g (mass on the assumption that the amount of resin per 0.125 m ^{2 of} 125 μm film is 17.8 g and 10 mass% of the crosslinked acrylic polymer is added), a scanning electron microscope ( Observed using a product name “S570” manufactured by Hitachi, Ltd.), coarse particles of 10 × Dw (= 50) μm or more were present.
[Comparative Example 4]
In Example 1, the crosslinked acrylic polymer (III-1 ′) (mass average particle diameter 2 μm) obtained by producing in the same manner as the crosslinked acrylic polymer (III-1) except that it does not pass through the air classification process. When the same procedure as in Example 1 was carried out except that was used, a number of recessed defects were generated on the surface of the obtained acrylic resin film, and a film having a good appearance could not be produced.
In addition, about 1.78 g (mass on the assumption that the amount of resin per 0.125 m ^{2 of} 125 μm film is 17.8 g and 10 mass% of the crosslinked acrylic polymer is added), a scanning electron microscope ( Observed using a product name “S570” manufactured by Hitachi, Ltd., coarse particles of 10 × Dw (= 20) μm or more were present.
The evaluation results for the acrylic resin films, decorative films, and laminated molded products obtained in the examples and comparative examples are summarized in Table 1.

Organic crosslinked particles having a mass average particle diameter Dw of more than 1 μm and not more than 20 μm, and removing coarse particles of 10 × Dw μm or more by classification, and confirming the absence of coarse particles by scanning electron microscope observation or The acrylic resin films of Examples 1 to 14 having a resin composition to which inorganic particles are added as a constituent component have a good appearance with no concave defects on the surface. In addition, after printing on the film obtained by sandwiching between a mirror roll and a silicone rubber roll during film production, even if in-mold molding is performed, a good surface appearance is maintained without developing concave surface defects. A laminated molded product was obtained.
Moreover, although the acrylic resin film of Example 15 that did not sandwich the mirror roll and the silicone rubber roll at the time of film production did not cause surface-dented defects due to coarse particles of organic crosslinked particles or inorganic particles, There were surface protrusions due to other foreign matters, and when printing was performed due to this, printing omission occurred frequently, and a good decorative film could not be obtained.
Moreover, in Example 16 in which the acrylic resin composition did not contain silica particles having a mass average particle diameter of 100 nm or less, the acrylic resin composition pellets could not be stably produced. In the final film, there were no indented defects on the surface.

On the other hand, a commercially available crosslinked acrylic polymer in which coarse particles of 10 × Dw μm or more are present (manufactured by Sekisui Chemical Co., Ltd .; MBX-8 (trade name) [Comparative Example 1], manufactured by Soken Chemical Co., Ltd .; MR-7G) (Trade name) [Comparative Example 3]), and a crosslinked acrylic polymer (III-1 ′) [Comparative Example 4] which has not been subjected to a classification step to remove coarse particles of 10 × Dw μm or more, The acrylic resin films of Comparative Examples 1, 3, and 4 as constituent components had defects recessed on the surface, and became films with low industrial utility value from the viewpoint of design. Also, during film production, it was possible to make the defect inconspicuous by sandwiching it between a mirror roll and a silicone rubber roll, but after printing the obtained film, in-mold molding was performed, When the film was heated, the defects again appeared, a laminated molded product having a good surface appearance could not be obtained, and the industrial utility value was low.
Further, a resin composition obtained by adding 20 parts by mass of a commercially available crosslinked acrylic polymer having a mass average particle diameter Dw of 1 μm or less (manufactured by Soken Chemical Co., Ltd .; MR-2G (trade name, Dw = 1 μm)) is formed. The acrylic resin film of Comparative Example 2 as a component lacks mechanical properties, causes film breakage during film production, and fails to obtain a good film. In the case of an acrylic resin film comprising a resin composition obtained by adding 10 parts by mass of the cross-linked acrylic polymer as a constituent, the film surface gloss is as good as 59%, although the deterioration of film mechanical properties is reduced. It was not a film showing matte properties.

The acrylic resin film of the present invention has surface hardness, scratch resistance and heat resistance that can be used for insert molding and in-mold molding, has good printability, and has a very good surface appearance. In addition, this good surface appearance can be maintained through secondary processing such as in-mold molding.
Laminated molded products laminated with acrylic resin films of the present invention 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 guard, side mud guard, body panel, spoiler, front grill, strut mount, wheel cap, center pillar, door mirror, center ornament, side molding, door molding, wind molding, window, head lamp cover, tail lamp cover, windshield parts, etc. Automotive exterior applications, front panels for AV equipment and furniture products, buttons, emblems, surface cosmetics, housings for mobile phones, display windows, buttons Applications, furniture exterior materials, wall interiors, ceilings, floors and other architectural interior materials, siding exterior walls, roofs, roofs, gates, windbreak boards, and other architectural exterior materials, window frames, doors, Surface decoration materials for furniture such as handrails, sills and duck, various displays, lenses, mirrors, goggles, optical components such as window glass, interior and exterior applications for various vehicles other than automobiles such as trains, aircraft, ships, It can be suitably used for various packaging containers and materials such as bottles, cosmetic containers and accessory cases, and various other uses such as miscellaneous goods such as prizes and accessories.

Claims (6)

Mass average particle diameter Dw with respect to 100 parts by mass of acrylic resin composition comprising rubber-containing polymer (I) and / or thermoplastic polymer (II) mainly composed of alkyl methacrylate as shown below. An acrylic resin film containing 1 to 15 parts by mass of organic crosslinked particles or inorganic particles having a particle diameter of more than 1 μm and not more than 20 μm and not containing particles having a particle diameter of 10 × Dw μm or more.
Rubber-containing polymer (I):
In the presence of an innermost layer polymer (IA) having a structure of one layer or two or more layers obtained with an alkyl acrylate ester as a main component, a monomer having an alkyl methacrylate ester as a main component is graft-polymerized. A rubber-containing polymer having a multilayer structure of two or more layers having a mass average particle diameter of 0.01 to 0.5 μm formed by molding an outermost layer polymer (IC) having a structure of one layer or two or more layers . The mass average particle diameter Dw is 1 μm with respect to 100 parts by mass of the acrylic resin composition containing the rubber-containing polymer (I) and / or the thermoplastic polymer (II) mainly composed of an alkyl methacrylate as the main component. Acrylic resin containing 1 to 15 parts by mass of organic crosslinked particles made of the crosslinked acrylic polymer (III) shown below which does not contain particles having a particle diameter of 10 × Dw μm or more. the film.
Crosslinked acrylic polymer (III):
Cross-linked methacrylic particles composed of a polymerizable monomer mainly composed of an alkyl methacrylate and a polyfunctional monomer, or
Core-shell structure polymer particles comprising a rubber-like polymer core mainly composed of an acrylic acid alkyl ester and a glassy polymer shell mainly composed of an alkyl methacrylate.   The acrylic resin film according to claim 1 or 2, further comprising 0.1 to 1 part by mass of silica particles having a mass average particle diameter of 100 nm or less with respect to 100 parts by mass of the acrylic resin composition.   The acrylic resin film according to any one of claims 1 to 3, wherein the acrylic resin film is produced by melt-extruding the resin composition and forming a film by sandwiching it with a mirror roll and a rubber roll.   The acrylic resin film according to claim 4, wherein printing is performed on a contact surface with a rubber roll at the time of manufacturing the acrylic resin film. An acrylic resin laminated molded article obtained by laminating the acrylic resin film according to any one of claims 1 to 5 on a base material.