JP2006299037A - Acrylic resin film manufacturing method and laminate including the acrylic resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably express desired matte properties in mass production of acrylic resin film-like products having excellent surface hardness and heat resistance.
SOLUTION: A method for producing a film by extruding a pellet obtained by adding 0.1 to 40 parts by mass of a matting agent to 100 parts by mass of the following acrylic resin composition (A), comprising the following (A-2 ), Particles having a mass average particle diameter of 10 μm to 2 mm are used.
Composition (A)
5.5 to 80 parts by mass of the following rubber-containing polymer (A-1) and 20 to 94.5 parts by mass of a thermoplastic polymer (A-2) obtained by using an alkyl methacrylate as a main component [(A- 1) + (A-2) = 100 parts by mass]
Rubber-containing polymer (A-1)
In the presence of an elastic copolymer (a-1) as an inner layer mainly composed of an acrylic acid alkyl ester, a hard polymer (a-2) is formed as an outer layer obtained by graft polymerization using an alkyl methacrylate as a main component. Multi-layer structure rubber-containing polymer [selection figure] None

Description

  The present invention relates to a method for producing a matte acrylic resin film, and a laminate having the film on the surface.

  An in-mold molding method is available as a surface decoration method that imparts design properties to a molded product at low cost. This method involves printing on the surface of a sheet or film of polyester resin, polycarbonate resin, acrylic resin, etc. and molding it into a desired shape by a vacuum molding method or the like, or without injection molding as it is It is the method of arrange | positioning in and injecting resin used as a base material. According to this in-mold molding method, the sheet or film and the substrate can be integrated with high productivity, or only the printing part can be transferred.

  In recent years, it has been required to add a design and decoration such as a high-class feeling and a deep feeling, with the surface of a printed acrylic resin film being matt. Such a request can be realized by printing on a matte acrylic resin film.

  Patent Document 1 (Japanese Patent Laid-Open No. 10-237261) uses a rubber-containing polymer whose particle size is controlled within a specific range in an acrylic resin composition, and further, as a matting agent, inorganic particles, organic crosslinked particles In addition, it is disclosed that a matte acrylic resin film with suppressed matting can be produced by adding a hydroxyl group-containing linear polymer or the like.

  Furthermore, when printing on a matte acrylic resin film, the surface gloss difference between the front and back surfaces of the film is reduced by using an acrylic resin composition having a specific heat distortion temperature for the purpose of providing a film that suppresses printing omission. It is disclosed in Patent Document 2 (Japanese Patent Application Laid-Open No. 2002-361712).

  In recent years, a member having a film layer as a surface layer, which has been formed by an insert molding method or an in-mold molding method, has been used for vehicles. By containing a specific amount of a rubber-containing polymer having a specific average particle diameter, a film having excellent surface hardness, heat resistance, moldability and matting properties can be obtained (for example, see Patent Documents 1 and 2).

  However, these acrylic resin films are made by combining an acrylic resin as a matrix polymer, a rubber-containing polymer, and a matting material, and the shape of the rubber-containing polymer and matting material is defined. However, the shape of the acrylic resin as the matrix polymer is not particularly specified at the time of charging, and when a commercially available pellet-shaped acrylic resin is used, there is a problem in expressing stable matting properties. There was a case.

Specifically, when trying to obtain an acrylic resin film, there is a difference in surface gloss between the film obtained at the initial stage of production and the film obtained at the later stage, and the desired surface gloss is stable. A matte film cannot be obtained, and the industrial utility value is lowered because it is not particularly suitable for mass production.
Japanese Patent Laid-Open No. 10-237261 JP 2002-361712 A

  An object of the present invention is to provide a production method capable of stably expressing desired matte properties in mass production of an acrylic resin film having excellent surface hardness and heat resistance. An object of this invention is to provide the laminated body which laminated | stacked these on the base material.

  As a result of intensive studies to solve the above problems, the present inventors have found that a matte film having a stable surface glossiness can be obtained by defining the shape of a matrix polymer that has not been considered in the past. .

That is, the above object of the present invention can be solved by the following present invention.
[1] Extruding pellets containing acrylic resin composition (B) as a constituent component by adding 0.1 to 40 parts by mass of matting agent to 100 parts by mass of acrylic resin composition (A) shown below A method for producing an acrylic resin film to be molded, wherein a thermoplastic polymer having a mass average particle diameter of 10 μm to 2 mm is used as the following thermoplastic polymer (A-2).
Acrylic resin composition (A)
5.5 to 80 parts by mass of the following rubber-containing polymer (A-1) and 20 to 94.5 parts by mass of a thermoplastic polymer (A-2) obtained by using an alkyl methacrylate as a main component [component Acrylic resin composition comprising (A-1) and 100 parts by mass of component (A-2)] Rubber-containing polymer (A-1)
In the presence of an elastic copolymer (a-1) as an inner layer having a structure of one layer or two or more layers obtained with alkyl acrylate as a main component, a monomer having alkyl methacrylate as a main component in the presence of A rubber-containing polymer having a multilayer structure of two or more layers formed by graft polymerization to form a hard polymer (a-2) as an outer layer having a structure of one layer or two or more layers

[2] The method for producing an acrylic resin film according to [1], wherein the matting agent is a polymer (C) or (D) containing a hydroxyl group having a mass average particle diameter of 1 to 500 μm shown below.
Polymer containing hydroxyl group (C)
1 to 80 parts by mass of an acrylic acid hydroxyalkyl ester or methacrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms, 10 to 99 parts by mass of an alkyl methacrylate having an alkyl group having 1 to 13 carbon atoms, and carbon The polymer containing the hydroxyl group obtained by superposing | polymerizing the monomer composition which consists of 100 mass parts in total of 0-79 mass parts of acrylic acid alkylesters which have a C1-C8 alkyl group.
Polymer (D) containing hydroxyl group
5 to 80 parts by mass of an acrylic acid hydroxyalkyl ester or methacrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms, 10 to 94 parts by mass of an alkyl methacrylate having an alkyl group having 1 to 13 carbon atoms, and aromatic vinyl The polymer containing the hydroxyl group obtained by superposing | polymerizing the monomer composition which consists of a total of 100 mass parts of 1-80 mass parts of monomers.

[3] The method for producing an acrylic resin film according to the above [1], wherein the matting agent is a crosslinked polymer (E) having a mass average particle diameter of 0.5 to 50 μm and mainly composed of alkyl methacrylate.

[4] A laminate formed by laminating the acrylic resin film obtained by the method described in [1] to [3] on a substrate.

  As in the present invention, the heat obtained by using 5.5 to 80 parts by mass of the rubber-containing polymer (A-1) and a methacrylic acid alkyl ester as a main component, comprising granules having a mass average particle diameter of 10 μm to 2 mm. With respect to 100 parts by mass of the acrylic resin composition (A) comprising 20 to 94.5 parts by mass of the plastic polymer (A-2) [total 100 parts by mass of the component (A-1) and the component (A-2)] When an acrylic resin film composed of 0.1 to 40 parts by mass of a matting agent and having an acrylic resin composition (B) as a constituent component is employed, a matting material is added to a conventional acrylic resin composition. Can provide an acrylic resin film-like material having surface hardness and heat resistance that are difficult to realize, and a laminated body obtained by laminating these on a base material.

  As resin which comprises the acrylic resin film of this invention, it is an acrylic resin composition (B) formed by adding 0.1-40 mass parts of matting agents with respect to 100 mass parts of acrylic resin compositions (A). is there.

  First, the acrylic resin composition (A) will be described. The acrylic resin composition (A) is composed of 5.5 to 80 parts by mass of a rubber-containing polymer (A-1) and a methacrylic acid alkyl ester composed mainly of granules having a mass average particle diameter of 10 μm to 2 mm. The resin composition comprising 20 to 94.5 parts by mass of the obtained thermoplastic polymer (A-2) [total 100 parts by mass of the component (A-1) and the component (A-2)].

  The rubber-containing polymer (A-1) used for the acrylic resin composition (A) is an elastic copolymer (a- as an inner layer having a structure of one layer or two layers or more obtained from an alkyl acrylate ester as a main component. In the presence of 1), a monomer having an alkyl methacrylate as a main component is graft-polymerized to form a hard polymer (a-2) as an outer layer having a structure of one layer or two or more layers. A rubber-containing polymer having a multilayer structure of two or more layers.

  Examples of the alkyl acrylate ester used for the elastic copolymer (a-1) include conventionally known various alkyl acrylate esters. In particular, butyl acrylate, 2-ethylhexyl acrylate, and the like are preferable. This alkyl acrylate is used as a main component of the monomers constituting the elastic copolymer (a-1). Specifically, the usage amount of the acrylic acid alkyl ester is preferably 35 to 99.9% by mass in all monomers. When the amount used is 35% by mass or more, the moldability of the film becomes good. A more preferable usage amount is 50% by mass or more. Each range of these usage-amounts shows the usage-amount of the alkyl acrylate ester as a whole of an elastic copolymer (a-1), when an elastic copolymer (a-1) has a structure of two or more layers. Is. For example, when making an elastic copolymer (a-1) 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 elastic copolymer (a-1), together with the alkyl acrylate ester, other vinyl monomers copolymerizable therewith can also be used. When other vinyl monomers are used, the amount used is preferably 64.9% by mass or less based on the total monomers. As other vinyl monomers, for example, methacrylic acid alkyl esters such as methyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, styrene, acrylonitrile and the like are preferable. These can be used individually by 1 type or in combination of 2 or more types.

  A crosslinkable monomer is preferably used as a part of the monomer constituting the elastic copolymer (a-1). Examples of the crosslinkable monomer include ethylene glycol dimethacrylate, butanediol dimethacrylate, allyl acrylate, allyl methacrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, diallyl maleate , Trimethylolpropane triacrylate, and allyl cinnamate. These can be used individually by 1 type or in combination of 2 or more types. The amount of the crosslinkable monomer used is preferably 0.1 to 10% by mass in the total monomers.

  The rubber-containing polymer (A-1) is obtained by graft polymerization of a monomer mainly composed of an alkyl methacrylate in the presence of the elastic copolymer (a-1) described above. -2) is a rubber-containing polymer having a multilayer structure of two or more layers. That is, the elastic copolymer (a-1) constitutes the inner layer, and the hard polymer (a-2) constitutes the outer layer.

  In the graft polymerization for obtaining the hard polymer (a-2), 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, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and the like.

  As the monomer used for the graft polymerization for obtaining the hard polymer (a-2), other vinyl monomers copolymerizable therewith can be used together with the alkyl methacrylate. When other vinyl monomers are used, the amount used is preferably 50% by mass or less based on the total monomers. As other vinyl monomers, for example, acrylic acid alkyl esters such as methyl acrylate, butyl acrylate, cyclohexyl acrylate, styrene, acrylonitrile and the like are preferable. These can be used individually by 1 type or in combination of 2 or more types.

  These monomers are graft polymerized in one or more stages in the presence of the elastic copolymer (a-1) to form a hard polymer (a-2) as an outer layer, and a rubber-containing polymer. (A-1) is obtained. The amount of the hard polymer (a-2) in the rubber-containing polymer (A-1) is preferably 10 to 400 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the elastic copolymer (a-1). 20 to 200 parts by mass.

  The particle size of the rubber-containing polymer (A-1) is preferably from 0.01 to 0.5 μm, more preferably from 0.08 to 0.3 μm. In particular, from the viewpoint of film formability, the particle diameter is preferably 0.08 μm or more.

  As a production method of the rubber-containing polymer (A-1), that is, a polymerization method for forming the elastic copolymer (a-1) and a polymerization method for forming the hard polymer (a-2), For example, a conventionally known emulsion polymerization method can be used. Although the optimum value of the polymerization temperature varies depending on the type and amount of the polymerization initiator used, it is usually preferably 40 ° C or higher, more preferably 60 ° C or higher, preferably 95 ° C or lower, and more preferably 120 ° C or lower.

  Various conventionally known polymerization initiators can be used. The polymerization initiator may be added to one or both of the aqueous phase and the monomer phase.

  Examples of the emulsifier used in the emulsion polymerization include anionic, cationic and nonionic surfactants, and anionic surfactants are particularly preferable. Anionic surfactants include, for example, carboxylate surfactants such as potassium oleate, sodium stearate, sodium myristate, sodium N-lauroyl sarcosinate, dipotassium alkenyl succinate; sulfuric acid such as sodium lauryl sulfate Ester salt surfactants; sulfonate surfactants such as sodium dioctyl sulfosuccinate, sodium dodecylbenzenesulfonate, sodium alkyldiphenyl ether disulfonate; phosphate ester-based interfaces such as sodium polyoxyethylene alkylphenyl ether phosphate Active agents; and the like.

  The polymer latex obtained by emulsion polymerization may be filtered through a filter having an opening of 100 μm or less, and then coagulated by a known coagulation method such as an acid coagulation method, a salt coagulation method, a freeze coagulation method, or a spray drying method. . In the acid coagulation method, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and organic acids such as acetic acid can be used. In the salt coagulation method, inorganic salts such as sodium sulfate, magnesium sulfate, aluminum sulfate and calcium chloride, and organic salts such as calcium acetate and magnesium acetate can be used. The rubber-containing polymer (A-1) is obtained by further washing, dehydrating and drying the solidified polymer.

  The thermoplastic polymer (A-2) composed of granules having a mass average particle diameter of 10 μm to 2 mm used for the acrylic resin composition (A) is a polymer obtained by using an alkyl methacrylate as a main component. Various known ones can be used.

  Examples of the thermoplastic polymer (A-2) include 50 to 99.9 parts by weight of a methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms, 0.1 to 50 parts by weight of an acrylic acid alkyl ester, and a combination thereof. It is obtained by polymerizing a total of 100 parts by mass of 0 to 49.9 parts by mass of other polymerizable vinyl monomers, and reduced viscosity (0.1 g of polymer is dissolved in 100 ml of chloroform and measured at 25 ° C. ) Of 0.1 L / g or less is preferable from the viewpoint of film forming property.

  As the methacrylic acid alkyl ester used for obtaining the thermoplastic polymer (A-2), for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like are preferable, and methyl methacrylate is most preferable.

  As a monomer used for obtaining the thermoplastic polymer (A-2), other copolymerizable vinyl monomers can be used together with the alkyl methacrylate. As used in the preferred polymers listed above, the other vinyl monomer is preferably an alkyl acrylate. Specific examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, butyl acrylate, and the like. The amount of acrylic acid alkyl ester used is preferably 0.1 to 50 parts by mass. Also, vinyl monomers other than alkyl acrylate can be used as other copolymerizable vinyl monomers, and the amount of vinyl monomers used is preferably 49.9% by mass or less. Specific examples thereof include aromatic vinyl compounds such as styrene, vinyl cyanide monomers such as acrylonitrile, unsaturated dicarboxylic anhydrides such as maleic anhydride and itaconic anhydride, N-phenylmaleimide, and N-cyclohexylmaleimide. Etc.

  From the viewpoint of the glossy spots of the resulting matte acrylic resin film, the thermoplastic polymer (A-2) must have a mass average particle diameter of 10 μm to 2 mm for stable surface gloss. It is. Preferably it is the range of 100 micrometers-700 micrometers. If it is 100 micrometers or more, the handleability of a thermoplastic polymer (A-2) will become favorable, and the supply to the screw of a thermoplastic polymer (A-2) will be stabilized at the time of extrusion molding. If it is 700 micrometers or less, surface glossiness will express more stably. In addition, a granule is, for example, a spherical particle obtained by suspension polymerization, which will be described later, or a powdery material obtained by latex obtained by emulsion polymerization by the aforementioned coagulation method. Moreover, it is preferable from a viewpoint of stable matte expression that the thermoplastic polymer (A-2) does not contain coarse particles exceeding 2 mm.

  The manufacturing method of a thermoplastic polymer (A-2) is not specifically limited, For example, various polymerization methods, such as suspension polymerization, emulsion polymerization, and block polymerization, can be used. From the viewpoint of obtaining a spherical or amorphous thermoplastic polymer (A-2) having a mass average particle diameter of 1 μm to 2 mm, it is preferable to perform polymerization by suspension polymerization. During the polymerization, a chain transfer agent, other polymerization aids, and the like may be used. Various chain transfer agents can be used, and mercaptans are particularly preferred. In order to adjust the particle size, it can be carried out by the amount of dispersant added during polymerization or by the number of stirring revolutions.

  It is preferable that the reduced viscosity of the thermoplastic polymer (A-2) is 0.1 L / g or less because appropriate elongation occurs when the film raw material resin is melted and the film-forming property is improved. Further, the reduced viscosity is preferably 0.05 L / g or more from the viewpoint that the film does not become brittle, so that it is difficult to cause film breakage during film formation and printing.

  The acrylic resin composition (A) is a rubber-containing polymer (A-1) 5.5 to 80 parts by mass, and a thermoplastic polymer (A-2) 20 to 94 obtained by using a methacrylic acid alkyl ester as a main component. It is necessary for stable matting to be a resin composition comprising 0.5 parts by mass [total 100 parts by mass of component (A-1) and component (A-2)]. From the viewpoint of more stable matte appearance, surface hardness, and heat resistance, the thermoplastic polymer (A-2) is preferably 40 parts by mass or more, and more preferably 60 parts by mass or more.

  Next, the acrylic resin composition (B) will be described. The acrylic resin composition (B) is formed by adding 0.1 to 40 parts by mass of a matting agent to 100 parts by mass of the acrylic resin composition (A) described above.

  As a matting agent used for an acrylic resin composition (B), various matting agents known conventionally are mentioned regardless of an organic type and an inorganic type. In particular, from the viewpoints of matteness, moldability, and appearance, the polymers (C) and (D) containing a hydroxyl group having a mass average particle diameter of 1 to 500 μm and a mass average particle diameter of 0.5 to 50 μm shown below. It is preferable to use a crosslinked polymer (E) mainly composed of alkyl methacrylate as a matting agent.

  The polymer (C) containing a hydroxyl group is a methacrylic acid having 1 to 80 parts by weight of an acrylic acid hydroxyalkyl ester or methacrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms and an alkyl group having 1 to 13 carbon atoms. It is a polymer obtained by polymerizing monomers consisting of 10 to 99 parts by mass of an alkyl ester and 100 parts by mass in total of 0 to 79 parts by mass of an alkyl acrylate ester having an alkyl group having 1 to 8 carbon atoms.

  Examples of the (meth) acrylic acid hydroxyalkyl ester having a C1-C8 alkyl group used for the polymer (C) containing a hydroxyl group include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and methacrylic acid. Examples include 2,3-dihydroxypropyl, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and the like. Of these, 2-hydroxyethyl methacrylate is preferable. The usage-amount of this (meth) acrylic-acid hydroxyalkyl ester is the range of 1-80 mass parts. If the amount used is 1 part by mass or more, the matting effect is sufficient, and if it is 80 parts by mass or less, the dispersibility of the particles becomes good and the film-forming property becomes good. From the point of matteness and film forming property, the amount used is preferably 5 to 50 parts by mass, and more preferably 20 to 50 parts by mass.

  On the other hand, in vehicle interior use, there is a possibility that fragrances, hair styling agents, and the like adhere to interior parts, and therefore, it is common for interior members to have chemical resistance. In order to make the film exhibit resistance to these chemicals, the amount of (meth) acrylic acid hydroxyalkyl ester used is preferably 5 to 25 parts by mass. From the viewpoint of achieving both matte properties and chemical resistance, 10 to 20 parts by mass is preferable.

  As the alkyl methacrylate having an alkyl group having 1 to 13 carbon atoms used for the polymer (C) containing a hydroxyl group, for example, lower methacrylate alkyl esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate are preferable. Of these, methyl methacrylate is most suitable. The amount of the methacrylic acid alkyl ester used is 10 to 99 parts by mass, and more preferably 30 to 90 parts by mass.

  Specifically, the alkyl acrylate ester having an alkyl group having 1 to 8 carbon atoms used for the polymer (C) containing a hydroxyl group is methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, or the like. The lower acrylic acid alkyl esters are preferred. The amount of the alkyl acrylate used is 0 to 79 parts by mass, preferably 0.5 to 40 parts by mass, and more preferably 5 to 25 parts by mass.

  On the other hand, from the viewpoint of chemical resistance, the glass transition temperature of the polymer (C) containing a hydroxyl group is preferably 80 ° C. or higher, and more preferably 90 ° C. or higher. In this case, it is necessary to use the alkyl acrylate ester in the range of more than 0 parts by mass and 5 parts by mass or less, and preferably in the range of more than 0 parts by mass and 2 parts by mass.

  The polymer (D) containing a hydroxyl group is a methacrylic acid having 5 to 80 parts by mass of a hydroxyalkyl ester of acrylic acid or hydroxyalkyl ester of methacrylic acid having an alkyl group having 1 to 8 carbon atoms and an alkyl group having 1 to 13 carbon atoms. It is a polymer obtained by polymerizing a monomer composition consisting of 10 to 94 parts by mass of an alkyl ester and 100 parts by mass in total of 1 to 80 parts by mass of an aromatic vinyl monomer.

  As the (meth) acrylic acid hydroxyalkyl ester having a C1-C8 alkyl group used for the polymer (D) containing a hydroxyl group, the same one as in the case of the polymer (C) containing a hydroxyl group may be used. it can. The usage-amount of acrylic-acid hydroxyalkyl ester is the range of 5-80 mass parts. When the amount used is 5 parts by mass or more, the matting effect is sufficient, and when it is 80 parts by mass or less, the dispersibility of the particles is good and the film-forming property is good. From the viewpoint of matting properties, film-forming properties, and chemical resistance, the amount used is preferably 5 to 50 parts by mass, and more preferably 10 to 20 parts by mass.

  As the methacrylic acid alkyl ester having a C1-C13 alkyl group used for the polymer (D) containing a hydroxyl group, the same one as in the case of the polymer (C) containing a hydroxyl group can be used. The amount of the methacrylic acid alkyl ester used is 10 to 94 parts by mass, and more preferably 50 to 90 parts by mass.

  Specific examples of the aromatic vinyl monomer used for the polymer (D) containing a hydroxyl group may include styrene and α-methylstyrene. Of these, styrene is preferred. By using an aromatic vinyl monomer, the chemical resistance of the film-like product can be improved. The usage-amount of an aromatic vinyl monomer is 1-80 mass parts, 5-40 mass parts is preferable and 5-20 mass parts is more preferable.

  From the viewpoint of chemical resistance, the glass transition temperature of the polymer (D) containing a hydroxyl group is preferably 80 ° C. or higher, and more preferably 90 ° C. or higher.

  The intrinsic viscosity of the polymer (C) or (D) having a hydroxyl group is preferably adjusted in the range of 0.05 to 0.3 L / g from the viewpoint of matte appearance and appearance. More preferably, it is in the range of 0.06 to 0.15 L / g. In order to adjust the molecular weight, it is preferable to use a polymerization regulator such as mercaptan. As the mercaptan, for example, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and the like can be used. However, it is not limited to these, and various conventionally known mercaptans can be used.

  The size of the polymer (C) or (D) having a hydroxyl group is preferably a bead shape having a mass average particle diameter of 1 to 500 μm from the viewpoint of matteness.

  Although the manufacturing method of the polymer (C) or (D) which has a hydroxyl group is not specifically limited, Suspension polymerization, emulsion polymerization, etc. are preferable. As the initiator for suspension polymerization, various conventionally known initiators can be used, and specific examples include organic peroxides and azo compounds. Various conventionally known suspension stabilizers can be used. Specifically, organic colloidal polymer materials, inorganic colloidal polymer materials, inorganic fine particles, combinations of these with surfactants, etc. Is mentioned. Suspension polymerization is usually carried out by suspending monomers with an initiator in the presence of a suspension stabilizer. In addition, suspension polymerization can be performed by using a polymer soluble in the monomer dissolved in the monomer.

  The addition amount of the matting agent is 0.1 to 40 parts by mass with respect to 100 parts by mass of the acrylic resin composition (A). A sufficient matting effect is exhibited with an addition amount of 0.1 parts by mass or more. Further, it is preferable to add 2 parts by mass or more in order to obtain good matting properties.

  In particular, when the polymer (C) or (D) having a hydroxyl group is used as a matting agent, physical properties such as film elongation are hardly deteriorated. Therefore, the film can be used satisfactorily without incurring film breakage or the like even in in-mold forming such as vacuum forming of the film in advance.

  The crosslinked polymer (E) composed mainly of alkyl methacrylate is composed of beads having a mass average particle diameter of 0.5 to 50 μm, and is equivalent to a polymerizable monomer mainly composed of alkyl methacrylate. It consists of a polyfunctional monomer having two or more copolymerizable double bonds in one molecule.

  The methacrylic acid alkyl ester used in the cross-linked polymer (E) having methacrylic acid alkyl ester as a main component refers to those having methyl methacrylate as a main component, but in addition, ethyl methacrylate, propyl methacrylate, methacrylic acid. n-Butyl, methacrylic acid cyclohexyl and other alkyl groups having a linear, branched or cyclic alkyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate , Alkyl group such as n-octyl acrylate is linear or branched alkyl acrylate, lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, methacrylic acid and other acrylic monomers, styrene, alkyl substitution styrene, Acrylonitrile, it can be used in combination with other monomers having a copolymerizable double bond, such as methacrylonitrile.

  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 polymer (E) mainly composed of the methacrylic acid alkyl ester is preferably from 50 to 99.5% by mass, and the proportion of the polyfunctional monomer is from 0.5 to 50 mass% is preferable.

  Next, the manufacturing method of the crosslinked polymer (E) which has a methacrylic acid alkyl ester as a main component is demonstrated.

  As a method for producing a crosslinked polymer (E) containing a methacrylic acid alkyl ester as a main component, 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. However, the crosslinked polymer (E) containing the alkyl methacrylate of the present invention as a main component. In order to obtain a desired droplet, first, water in which a dispersion stabilizer is dissolved or suspended is mixed with a polymerizable monomer containing a polymerization initiator, and the mixture is subjected to mechanical shearing. 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 and methylcellulose, anionic surfactants such as sodium oleate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkylsulfonate, laurylamine Known ones 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, oil-soluble peroxide-based or azo-based initiators 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.

  As a method for taking out the crosslinked polymer (E) mainly composed of an alkyl methacrylate ester from the suspension, a method of filtering, a method using a separator such as a centrifuge, or spray drying is convenient, It is not limited. 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 polymer (E) mainly composed of an alkyl methacrylate ester 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.

  In this invention, it is also preferable to mix | blend and use 0.1-20 mass parts of thermoplastic polymers (F) shown below with respect to 100 mass parts of acrylic resin compositions (A).

  The thermoplastic polymer (F) is formed by polymerizing a total of 100 parts by mass of 50 to 100 parts by mass of methyl methacrylate and 0 to 50 parts by mass of other vinyl monomers copolymerizable therewith. It is a thermoplastic polymer having a reduced viscosity (0.1 g of polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) exceeding 0.2 L / g. By using this thermoplastic polymer (F), the film-forming property is improved, which is particularly effective when a high level of thickness accuracy and film-forming speed are required. Moreover, since the reduced viscosity of a thermoplastic polymer (F) exceeds 0.2 L / g, it becomes a film with favorable thickness accuracy. The reduced viscosity is usually more than 0.2 L / g and 2 L / g or less, preferably 1.2 L / g or less.

  Examples of other vinyl monomers copolymerizable with methyl methacrylate in the thermoplastic polymer (F) include alkyl acrylates, alkyl methacrylates other than methyl methacrylate, aromatic vinyl compounds, and vinyl cyanide. Compounds and the like.

  As a polymerization method for producing the thermoplastic polymer (F), an emulsion polymerization method is preferred. In the method for producing the thermoplastic polymer (F), for example, the polymer latex produced by the emulsion polymerization method is separated and collected by various coagulants, or the solid content is separated and collected by spray drying. obtain.

  In this invention, the preferable usage-amount of the thermoplastic polymer (F) used as needed is 0.1-20 mass with respect to 100 mass parts of acrylic resin composition (A) or an acrylic resin composition (B). Part. When the amount used is 0.1 parts by mass or more, the effect of improving the film forming property is exhibited. On the other hand, when the amount is 20 parts by mass or less, the viscosity of the resin composition becomes appropriate, and good film forming properties are obtained. It is done.

  The acrylic resin film of the present invention is a general compounding agent, for example, a stabilizer, a lubricant, a processing aid, a plasticizer, an impact resistance aid, a foaming agent, a filler, a colorant, an ultraviolet absorber, etc., if necessary. Can be included.

  In particular, in terms of protecting the substrate, it is preferable to add an ultraviolet absorber 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, trade name “Tinubin 234” of Ciba Specialty Chemicals Co., Ltd., the trade name “Adeka Stub LA-31” of Asahi Denka Kogyo Co., Ltd. The name “Tinubin 1577” and the like can be mentioned.

  Moreover, when using especially the polymer (C) or (D) containing a hydroxyl group, it is preferable to mix | blend a phosphorus compound in the ratio of 0.01-3 mass parts from a matte viewpoint. The addition amount of 0.01 parts by mass or more provides good matting properties, and the use of 3 parts by mass or less is preferable from the economical viewpoint. A more preferable blending amount is in the range of 0.1 to 1 part by mass.

  Specific examples of phosphorus compounds include phosphite compounds such as alkyl phosphites, alkylaryl phosphites, aryl phosphites, nonylphenyl phosphites, alkylnonylphenyl phosphites; trialkyl phosphates, tripolyoxyethylene alkyl ether phosphates, Phosphate compounds such as dialkyl phosphates and metal salts thereof, dipolyoxyethylene alkyl ether phosphates and metal salts thereof, alkyl phosphates and metal salts thereof, polyoxyethylene alkyl ether phosphates and metal salts thereof; dialkyl alkyl phosphonates, alkyl alkyl phosphonates and And phosphonate compounds such as metal salts thereof. Of these, phosphite compounds are preferred from the standpoint of matte appearance. Furthermore, among the phosphite compounds, those having no bulky substituent around the phosphite group are more preferable from the viewpoint of matte appearance. In addition, trialkyl phosphite is particularly preferable from the viewpoint of stable matte development and roll contamination during film formation.

  The present invention is preferably obtained by forming the above-mentioned various acrylic resins into a desired film shape. In this acrylic resin, the content of the gel insoluble in chloroform is preferably 5 to 75% by mass. When the gel content is 5% by mass or more, since the content of the rubber-containing polymer in the acrylic resin is substantially 5% by mass or more, the film does not become brittle, so that the film forming property is improved. Moreover, if it is 75 mass% or less, moderate melt tension will be obtained at the time of film forming, and film forming property will become favorable. The gel content is more preferably 10 to 60% by mass.

  The acrylic resin composition (B) of the present invention preferably has a heat distortion temperature (measured based on ASTM D648) of 80 ° C. or higher. When the heat distortion temperature is 80 ° C. or higher, since the surface of the acrylic resin film is not whitened or clouded when exposed at a high temperature for a long time, the industrial utility value is high. In addition, when the acrylic resin composition (B) has a heat deformation temperature of 80 ° C. or higher in a vehicle application, a molded product using the acrylic resin film is a part that receives direct sunlight in the vehicle, such as a front control panel. Can also be used. From the viewpoint of further expanding the application, the thermal deformation temperature is more preferably 90 ° C. or higher. The measurement of the heat distortion temperature is performed using a heat distortion temperature measurement specimen obtained by molding the raw material pellet of the acrylic resin composition (B) by injection molding and then annealing at 60 ° C. for 4 hours. The heat deformation temperature is usually the same as the heat deformation temperature of the acrylic resin film.

  As a method for producing the acrylic resin film of the present invention, various conventionally known methods can be used. In particular, a method of forming a film by forming an acrylic resin composition into a film shape by a melt extrusion method such as a T-die method and then sandwiching it between a mirror surface roll and a rubber roll or a textured roll is preferable. In particular, the method of sandwiching between a mirror roll and a rubber roll is more preferable in that a film having a relatively thin film thickness of about 50 μm can be produced as compared with a method of sandwiching between a mirror roll and a textured roll. In addition, in the calendering method, the film can be formed by changing one side of two mirror-finished rolls between which the film is finally sandwiched to a rubber roll or a roll with grain. 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 point transfer temperature, and it can also pinch | interpose with a mirror surface roll, a rubber roll, or a wrinkled roll, and can also manufacture.

  Various conventionally known rolls can be used as the mirror roll. In particular, a roll having a surface roughness of 0.5 S or less subjected to chrome plating is preferable.

  During film production, if the temperature of the mirror roll is high, the followability to the rubber roll or wrinkled roll will be good, and good matting will be exhibited on the film surface in contact with the rubber roll or wrinkled roll. The mirror surface transfer property to the acrylic resin film becomes good, the smoothness of the surface in contact with the mirror surface roll is increased, and the printing omission is reduced. However, if the temperature is too high, the peelability of the acrylic resin film from the mirror roll may be poor or the acrylic resin film may be wound. On the other hand, when the temperature of the mirror roll is too low, the mirror transfer property of the mirror roll to the acrylic resin film becomes poor, and the effect of reducing printing loss is insufficient, or the film is likely to wrinkle. Although it depends on the glass point transition temperature of the acrylic resin, it is necessary to adjust the temperature of the cooling roll within a range of 20 to 140 ° C. The temperature range is preferably 50 to 120 ° C, more preferably 60 to 100 ° C.

  Various conventionally known rolls can be used as the rubber roll. In particular, silicone rubber is preferable from the viewpoint of heat resistance. In order to obtain good matting properties, silicone rubber containing sand is preferable. The acrylic resin film has a different matte appearance depending on the application, and therefore the particle size and amount of sand added to the silicone rubber vary depending on the application. Specifically, for example, a silicone rubber roll to which 50% by mass of sand having an average particle size of 40 μm is added can be used. In addition, a textured roll can be used instead of the rubber roll. As the textured roll, various conventionally known rolls can be used.

  Moreover, when performing melt extrusion, it is also preferable to extrude while filtering the acrylic resin in a molten state with a screen mesh of 200 mesh or more.

  It is particularly useful to use the acrylic resin film of the present invention after printing a pattern by an appropriate printing method. For example, by stacking a printed acrylic resin film on a desired base material (molded product, etc.) as a paint substitute film, etc., it is possible to easily obtain a laminate (laminated molded product) with design properties. it can.

  When printing on an acrylic resin film, it is preferable to perform printing on one side of the film, and in particular, printing on the surface having a higher 60 ° surface glossiness from the viewpoint of reducing printing omissions. preferable. When laminating an acrylic resin film on a substrate, it is preferable from the viewpoint of protecting the printed surface and imparting a high-class feeling that the printed surface is in contact with the substrate. As a printing method, various conventionally known printing methods such as a gravure printing method, a flexographic printing method, and a silk screen printing method can be used. Moreover, a coloring process can also be given as needed.

  The thickness of the acrylic resin film is 300 μm or less. When used as a paint substitute film, the thickness is preferably 50 μm to 300 μm. When this thickness is 50 μm or more, a sufficient depth can be obtained in the appearance of the molded product. In particular, when molding into a complicated shape, a sufficient thickness can be obtained by stretching. On the other hand, when the thickness is 300 μm or less, since it has appropriate rigidity, laminating property, secondary workability and the like are improved. In addition, it is economically advantageous in terms of mass per unit area. Furthermore, the film forming property is stable and the production of the film becomes easy.

  In order to form a coating film having a sufficient thickness on the surface of a molded article by ordinary coating, ten or more times of overcoating are required, which is costly and extremely deteriorates in productivity. On the other hand, if the acrylic resin film of the present invention is used, it becomes a coating film itself, so that a very thick coating film can be easily formed, which is industrially very advantageous.

  When laminating an acrylic resin film on a substrate, the surface of the film having the higher 60 ° surface glossiness (the surface on which printing has been applied if desired) may be laminated so that the surface is printed. It is preferable from the viewpoint of protection of the film and imparting a high-class feeling.

  As a base material, a resin molded product is mentioned, for example. The resin constituting the molded article may be any resin that can be melt-bonded to the acrylic resin film. For example, ABS resin, AS resin, polystyrene resin, polycarbonate resin, vinyl chloride resin, acrylic resin, polyester resin, or Resins containing these as main components can be mentioned. Among these, ABS resin, AS resin, polycarbonate resin, vinyl chloride resin, or a resin containing these as a main component is preferable from the viewpoint of adhesiveness. In particular, an ABS resin, polycarbonate resin, or a resin containing these as a main component is more preferable. preferable. However, even if the base resin is not heat-sealed, such as polyolefin resin, it is possible to laminate the acrylic resin film and the base material by interposing an adhesive layer.

  When the acrylic resin film of the present invention is laminated on a two-dimensional base material, a known method such as thermal lamination can be used for the base material that can be heat-sealed. Moreover, it is also possible to stick together through the adhesive agent with respect to the base material which is not heat-seal | fused. In the case of performing lamination molding on a three-dimensional base material, a known molding method such as an insert molding method or an in-mold molding method can be used. Among these, the in-mold molding method is particularly preferable from the viewpoint of productivity.

  In the in-mold molding method, after the acrylic resin film is heated, vacuum molding is performed in a mold having a vacuuming function. According to this in-mold molding method, film molding and injection molding can be performed in one step, which is preferable in terms of workability and economy. The heating temperature is preferably equal to or higher than the temperature at which the acrylic resin film is softened. Although it depends on the thermal properties of the film or the shape of the molded product, the heating temperature is usually 70 ° C. or higher. However, if the temperature is too high, matting will occur and the matting properties will be impaired. Although the temperature at which gloss return or the like occurs depends on the thermal properties of the film or the shape of the molded product, the heating temperature is usually preferably 170 ° C. or lower.

  In general, when a three-dimensional shape is imparted to a film by vacuum forming, it is important that the mold corners do not whiten and followability to the corners. In that respect, the vacuum forming method is an acrylic resin film. It is a processing method that can make the most of the characteristics of. That is, the acrylic resin film has a high degree of elongation at high temperatures and is very advantageous in the vacuum forming method.

  Moreover, it is preferable that the metal mold | die which an acrylic resin film touches at the time of vacuum forming is embossed. This embossing process reduces gloss return during in-mold molding.

  According to the in-mold molding method, after giving a three-dimensional shape by vacuum molding in this way, the acrylic resin film and the base resin are melted and integrated by injection molding, so that an acrylic resin having an acrylic resin laminated film layer on the surface layer is obtained. A laminated molded product can be obtained.

  The use of this acrylic laminated molded product is not particularly limited, for example, automobile interior parts such as console boxes and shift lever boxes, vehicle exterior parts such as two-wheeled cowlings, home appliances, furniture, and building materials. It can be used for various members that have been matte.

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

MMA: methyl methacrylate MA: methyl acrylate BA: butyl acrylate St: styrene HEMA: hydroxyethyl methacrylate AMA: allyl methacrylate 1,3BD: 1,3-butylene glycol dimethacrylate tBH: t-butyl hydroperoxide tHH: t-hexyl hydro Peroxide LPO: Lauryl peroxide nOM: n-octyl mercaptan nDM: n-dodecyl mercaptan

The various physical properties in the examples were measured according to the following methods.
1) Reduced viscosity, intrinsic viscosity:
The reduced viscosity of the thermoplastic polymers (A-2) and (F) and the intrinsic viscosity of the polymers (C) and (D) having a hydroxyl group were measured using an AVL-2C automatic viscometer manufactured by San Electronics Industry, Chloroform was used as a solvent, and measurement was performed at 25 ° C. In the measurement of the reduced viscosity, a solution prepared by dissolving 0.1 g of a sample in 100 ml of chloroform was used.

2) Particle size:
About the mass average particle diameter of the rubber-containing polymer (A-1), the final particle diameter of the polymer latex of those polymers obtained by emulsion polymerization was used using a light scattering photometer DLS-700 manufactured by Otsuka Electronics Co., Ltd. , Measured by a dynamic light scattering method.
The mass average particle diameter of the thermoplastic polymer (A-2), the polymers (C) and (D) having a hydroxyl group, and the crosslinked polymer (E) is a laser diffraction scattering particle size distribution manufactured by Horiba, Ltd. Measurement was performed using a measuring apparatus LA910.

3) 60 ° surface glossiness The 60 ° surface glossiness was measured using a gloss meter (manufactured by Murakami Color Research Laboratory, model GM-26D). The surface that was not in contact with the mirror roll was measured.

<Production Example 1: Production of acrylic resin composition (A)>
In a nitrogen atmosphere, put 244 parts of deionized water in a reaction vessel equipped with a reflux condenser, raise the temperature to 80 ° C., add the following component (a), and stir the following raw materials (b) [heavy] 1/15 of a part of the raw material for coalescence (a-1)] was charged and held for 15 minutes. Subsequently, the remaining raw materials (b) were continuously added at an increase rate of the monomer mixture with respect to water at 8% / hour. Thereafter, the polymerization was carried out for 1 hour to obtain a polymer latex. Subsequently, 0.6 parts of sodium formaldehyde sulfoxylate was added to the latex, and then kept for 15 minutes. While stirring at 80 ° C. in a nitrogen atmosphere, the following raw materials (c) [polymer (a-1 ) A part of the raw material] was continuously added at an increase rate of the monomer mixture with respect to water at 4% / hour. Thereafter, the polymerization was carried out for 2 hours to obtain a latex of an elastic copolymer (a-1).

  Subsequently, 0.4 part of sodium formaldehyde sulfoxylate was added to the latex of the elastic copolymer (a-1), and then held for 15 minutes, followed by stirring at 80 ° C. in a nitrogen atmosphere. Raw material (d) [raw material for hard polymer (a-2)] was continuously added at an increase rate of 10% / hour of the monomer mixture with respect to water. Thereafter, the polymerization was carried out for 1 hour to obtain a latex of the rubber-containing polymer (A-1). The particle size of the rubber-containing polymer (A-1) was 0.28 μm.

  This rubber-containing polymer (A-1) latex is filtered through a filter having an opening of 50 μm, and then coagulated, agglomerated and solidified using calcium acetate, filtered, washed with water, dried and contains rubber. A polymer (A-1) was obtained.

(I)
Sodium formaldehyde sulfoxylate 0.6 parts Ferrous sulfate 0.00012 parts Disodium ethylenediaminetetraacetate 0.0003 parts

(B)
MMA 18.0 parts BA 20.0 parts St 2.0 parts AMA 0.4 parts 1,3BD 0.14 parts tBH 0.18 parts Emulsifier (trade name “Phosphanol RS610NA” manufactured by Toho Chemical Co., Ltd.)
0.75 parts

(C)
BA 50.0 parts St 10.0 parts AMA 0.4 parts 1,3BD 0.14 parts tHH 0.2 parts Emulsifier (trade name “Phosphanol RS610NA” manufactured by Toho Chemical Industry Co., Ltd.)
0.6 parts

(D)
MMA 57.0 parts MA 3.0 parts nOM 0.3 parts tBH 0.06 parts

  23 parts of the rubber-containing polymer (A-1) obtained as described above and a MMA / MA copolymer (MMA / MA = 99/99) obtained by suspension polymerization as a thermoplastic polymer (A-2). 1, 77 parts of a reduced viscosity of 0.06 L / g, a spherical shape having a mass average particle diameter of 320 μm, and no coarse particles exceeding 2 mm) were mixed to obtain an acrylic resin composition (A).

<Production Example 2: Production of acrylic resin composition (B) -1>
The following mixture was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, and the like.
MA 1 part MMA 79 parts HEMA 20 parts n-DM 0.23 parts LPO 0.53 parts Methyl methacrylate / methacrylate /
Copolymer of ethyl methacrylate sulfonate 0.05 part Sodium sulfate 0.5 part Ion exchange water 300 parts

  The inside of the container was sufficiently replaced with nitrogen gas, and then heated to 78 ° C. with stirring, and polymerization was advanced in a nitrogen gas stream. After 3 hours, the temperature was raised to 90 ° C. and held for another 1 hour to complete the polymerization. The obtained polymer beads were dehydrated and dried to obtain a polymer (C) having a hydroxyl group. The polymer (C) had a mass average particle diameter of 115 μm, an intrinsic viscosity of 0.062 L / g, and a glass transition temperature of 93 ° C. An acrylic resin composition (B) -1 was obtained by mixing 10 parts of the polymer (C) having a hydroxyl group with 100 parts of the acrylic resin composition (A) obtained in Production Example 1 as a matting agent. .

<Production Example 3: Production of acrylic resin composition (B) -2>
The following mixture was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, and the like.
ST 20 parts MMA 60 parts HEMA 20 parts n-OM 0.1 part LPO 0.5 part Methyl methacrylate / methacrylate /
Copolymer of ethyl methacrylate sulfonate 0.05 part Sodium sulfate 0.5 part Ion exchange water 250 parts

  The interior of the container was sufficiently replaced with nitrogen gas, and then heated to 75 ° C. with stirring, and polymerization was advanced in a nitrogen gas stream. After 2 hours, the temperature was raised to 90 ° C. and maintained for an additional 45 minutes to complete the polymerization. The obtained polymer beads were dehydrated and dried to obtain a polymer (D) having a hydroxyl group. The polymer (D) had a mass average particle diameter of 160 μm, an intrinsic viscosity of 0.11 L / g, and a glass transition temperature of 93 ° C.

<Production Example 4: Production of acrylic resin composition (B) -3>
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 were classified with an air classifier (manufactured by Nissin Engineering Co., Ltd .; trade name “TC-15N”) to obtain a crosslinked polymer (E) having a mass average particle diameter of 4 μm.

  An acrylic resin composition (B) -3 was obtained by mixing 10 parts of this crosslinked polymer (E) with 100 parts of the acrylic resin composition (A) obtained in Production Example 1 as a matting agent.

<Production Example 5: Production of thermoplastic polymer (F)>
The reaction vessel was charged with 200 parts of ion-exchanged water substituted with nitrogen, and 1 part of emulsifier potassium oleate and 0.3 part of potassium persulfate were charged. Subsequently, 40 parts of MMA, 10 parts of BA, and 0.005 part of nOM were charged and stirred at 65 ° C. for 3 hours in a nitrogen atmosphere to complete the polymerization. Subsequently, a monomer mixture consisting of 48 parts of MMA and 2 parts of BA was added dropwise over 2 hours, and maintained for 2 hours after the completion of the addition to complete the polymerization. The obtained latex was added to a 0.25% aqueous sulfuric acid solution, the polymer was acid coagulated, then dehydrated, washed with water and dried to recover the polymer in powder form. The reduced viscosity ηsp / c of the obtained copolymer [thermoplastic polymer (F)] was 0.38 L / g.

<Example 1>
100 parts of the acrylic resin composition (B) -1 of Production Example 2, 6 parts of the thermoplastic polymer (F) of Production Example 5, “Tinuvin 234” (trade name, manufactured by Ciba Specialty Chemicals) 1 as an ultraviolet absorber .4 parts, "LA67" (trade name, manufactured by Asahi Denka Co., Ltd.) 0.3 parts as light stabilizer, "AO60" (trade name, manufactured by Asahi Denka Co.) 0.1 parts as an antioxidant, phosphite 0.3 part of “JP333E” (trade name, manufactured by Johoku Chemical Co., Ltd.), a system antioxidant, was mixed with a Henschel mixer. Next, about 20 kg is put into a hopper of a 35 mmφ screw type twin screw extruder (L / D = 26), melt kneaded and pelletized under conditions of a cylinder temperature of 200 ° C. to 260 ° C. and a die temperature of 250 ° C. The pellet of the composition for films was obtained. The pellets were sampled as 5 kg (I) extruded at the beginning of extrusion, then 5 kg (II), and finally 5 kg (III) as the later stage of extrusion, 3 kg each for a total of 3 points.

  Each of these three pellets was dried at 80 ° C. all day and night, and a cylinder temperature of 200 mm was used using a 40 mmφ non-vent screw type extruder (L / D = 26) equipped with a 300 mm T die and provided with a 400 mesh screen mesh. Melt extrusion was performed through a T die under the conditions of ℃ to 240 ° C. and a T die temperature of 250 ° C. The extruded resin was formed into an acrylic resin film having a thickness of 125 μm while being cooled by a cooling mirror roll (temperature of 0.2S having a surface roughness of 0.2S that was chrome-plated) adjusted to 75 ° C.

  On the cooling roll contact surface side of the obtained acrylic resin film, scaly aluminum pigment is added to 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%. Using an ink containing 2 parts, silver metallic printing was performed by gravure printing. The printed layer had a thickness of 3 μm.

  Next, using a heat-resistant ABS resin bulk sum TM25B (trade name; manufactured by UMGABS) as a base resin and a printed acrylic resin film, it has a vacuum drawing function, and a mold (molded product shape: 150 mm length) × Box shape with width 120mm × thickness 2mm, depth 10mm, gate position: 1 location at the center of the molded product, and 1 location at 40mm above and below the center gate (vertical direction of the molded product), gate shape: Using a pinpoint gate with a diameter of 1 mm, an in-mold molding apparatus (trade name; manufactured by Nippon Steel Co., Ltd.) and a hot pack system (manufactured by Nissha Printing Co., Ltd.) is used to perform 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 250 ° C, injection speed 30%, injection pressure 43%, mold temperature 60 ° C, vacuum-molded so that the non-decorated surface is in contact with the mold, and the base resin was injected from the decorated surface side) A molded product was obtained.

<Example 2>
It implemented similarly to Example 1 except having used 100 parts of acrylic resin compositions (B) -2 of manufacture example 3 instead of 100 parts of acrylic resin compositions (B) -1.

<Example 3>
Implemented except that 100 parts of the acrylic resin composition (B) -3 of Production Example 4 was used instead of 100 parts of the acrylic resin composition (B) -1, and the screen mesh during film formation was changed to 100 mesh. Performed as in Example 1.

<Comparative Examples 1-3>
In Production Example 1, an MMA / MA copolymer (MMA / MA = 99/1, reduced viscosity 0.06 L / g, spherical shape having a mass average particle diameter of 320 μm) obtained by suspension polymerization was previously prepared in a screw type 2 having a diameter of 35 mmφ. The same procedure as in Examples 1 to 3 was performed except that the pellet was formed using a shaft extruder (L / D = 26) and this pellet was used. In addition, it cut | disconnected with the strand cutter so that the magnitude | size of a pellet might be about 3.5 mm (The long side length of the cross section was about 2.5 mm, and the short side length was about 1.5 mm).

<Comparative example 4>
In Production Example 1, instead of the MMA / MA copolymer obtained by suspension polymerization (MMA / MA = 99/1, reduced viscosity 0.06 L / g, spherical with mass average particle diameter of 320 μm), This was carried out in the same manner as in Example 1 except that the MMA / MA copolymer having a mass average particle size of 8 μm was used by changing the number of stirring revolutions and increasing the amount of the dispersing agent at the time of polymerization. As a result, pellets of the film composition could not be obtained.

  According to the present invention, when a matting material is added to a conventionally known acrylic resin composition, an acrylic resin film-like material excellent in surface hardness and heat resistance that exhibits a stable matting property that is difficult to realize, And the laminated body which laminated | stacked these on the base material can be provided.

  Laminated molded products with the acrylic resin film of the 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, bumpers Automobiles such as guards, side mudguards, body panels, spoilers, front grills, strut mounts, wheel caps, center pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, windows, headlamp covers, tail lamp covers, windshield parts, etc. Exterior applications, front panels for AV equipment and furniture products, buttons, emblems, surface cosmetics, housings for mobile phones, display windows, buttons, etc. Applications, further exterior materials for furniture, interior materials for buildings such as walls, ceilings and floors, exterior walls for siding, etc., exterior materials for buildings such as fences, roofs, gates, windbreak boards, window frames, doors, handrails Surface decoration materials for furniture such as sills and duck, various optical components such as displays, lenses, mirrors, goggles and window glass, interior and exterior applications for various vehicles other than automobiles such as trains, airplanes and ships, bottles It can be suitably used for various packaging containers and materials such as cosmetic containers and accessory cases, and other various uses such as miscellaneous goods such as prizes and accessories.

Claims (4)

Acrylic for extruding pellets containing acrylic resin composition (B) as a constituent component by adding 0.1 to 40 parts by mass of matting agent to 100 parts by mass of acrylic resin composition (A) shown below It is a manufacturing method of a resin film, Comprising: The manufacturing method characterized by using the thermoplastic polymer of the granule whose mass mean particle diameter is 10 micrometers-2 mm as a following thermoplastic polymer (A-2).
Acrylic resin composition (A)
5.5 to 80 parts by mass of the following rubber-containing polymer (A-1) and 20 to 94.5 parts by mass of a thermoplastic polymer (A-2) obtained by using an alkyl methacrylate as a main component [component Acrylic resin composition comprising (A-1) and 100 parts by mass of component (A-2)] Rubber-containing polymer (A-1)
In the presence of an elastic copolymer (a-1) as an inner layer having a structure of one layer or two or more layers obtained with alkyl acrylate as a main component, a monomer having alkyl methacrylate as a main component in the presence of A rubber-containing polymer having a multilayer structure of two or more layers formed by graft polymerization to form a hard polymer (a-2) as an outer layer having a structure of one layer or two or more layers The method for producing an acrylic resin film according to claim 1, wherein the matting agent is a polymer (C) or (D) containing a hydroxyl group having a mass average particle diameter of 1 to 500 µm shown below.
Polymer containing hydroxyl group (C)
1 to 80 parts by mass of an acrylic acid hydroxyalkyl ester or methacrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms, 10 to 99 parts by mass of an alkyl methacrylate having an alkyl group having 1 to 13 carbon atoms, and carbon The polymer containing the hydroxyl group obtained by superposing | polymerizing the monomer composition which consists of 100 mass parts in total of 0-79 mass parts of acrylic acid alkylesters which have a C1-C8 alkyl group.
Polymer (D) containing hydroxyl group
5 to 80 parts by mass of an acrylic acid hydroxyalkyl ester or methacrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms, 10 to 94 parts by mass of an alkyl methacrylate having an alkyl group having 1 to 13 carbon atoms, and aromatic vinyl The polymer containing the hydroxyl group obtained by superposing | polymerizing the monomer composition which consists of a total of 100 mass parts of 1-80 mass parts of monomers.   The method for producing an acrylic resin film according to claim 1, wherein the matting agent is a cross-linked polymer (E) having a mass average particle diameter of 0.5 to 50 µm and comprising an alkyl methacrylate as a main component.   The laminated body formed by laminating | stacking the acrylic resin film obtained by the manufacturing method of any one of Claims 1-3 on a base material.