JP2007138001A - Mat thermoplastic resin film, mat thermoplastic resin laminate film or sheet, and method for producing mat thermoplastic resin laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film having a good mat appearance and a good printability, and being reduced in the return of fish eyes or gloss in a process of insert molding or in-mold molding. <P>SOLUTION: The mat thermoplastic resin film having a 60 degree surface glossiness on one surface of not more than 100% is produced by niping a film-like transparent thermoplastic resin, that has been molded previously into a film form and cooled below its heat deformation temperature, at a temperature higher than the heat deformation temperature, using a mirror roll or mirror belt for one surface of the film-like resin and using a rubber roll, embossed roll, rubber belt, or embossed belt for the other surface of the resin. The laminated thermoplastic resin film or the sheet is produced by using the mat film, and the transparent thermoplastic resin laminate product is produced by laminating the film or the sheet on a base material. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a matte thermoplastic resin film, a matte thermoplastic resin film laminate film or sheet, and a method for producing a matte thermoplastic resin laminate.

  Examples of a method for imparting design properties to a molded product at a low cost include 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 unnecessary film or sheet portions are removed. Thereafter, the molded product is transferred into an injection mold, and then a resin as a base material is injection-molded to obtain an integrated molded product. On the other hand, the in-mold molding method is a method in which a sheet or film made 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 in the same mold In this way, an integrated molded product is obtained by injection molding a resin as a base material.

  In particular, according to this 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. The member having an acrylic resin film on the surface layer thus obtained is used as a component for vehicle use.

  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 an acrylic resin film subjected to high-luminance printing such as a metallic tone being matt. Such a request can be realized by printing on a matte acrylic resin film.

  In general, when printing is performed on an acrylic resin film, if many printing defects occur, not only the design and appearance are impaired, but also the yield is reduced. In particular, in the case of a matte acrylic resin film, the surface has large irregularities, and it is difficult for printing ink to enter the concave portions, so that there is a problem that the printed pattern becomes unclear or printing failure occurs at the convex portions.

  Therefore, in order to solve such a problem, an acrylic resin film having good printability such as few printing omissions when printing is performed and a method for producing the same are disclosed (for example, Patent Documents 1 to 5).

  In Patent Documents 1 to 3, an acrylic resin composition having excellent printability with a smooth surface on one side and a matte surface with low gloss on one side is formed by sandwiching the acrylic resin composition into a film. A method for producing a resin film is disclosed. Since all of these acrylic resin compositions have been given a matte property by blending a matte material, there is a considerable decrease in physical properties and there is room for improvement.

  In addition, in the acrylic resin film obtained by the manufacturing method described in Patent Documents 1 to 3, although it can be apparently improved by surface clamping defects such as fish eyes once sandwiched by a roll, in-mold molding When secondary processing such as the above is performed, a phenomenon in which convex defects on the film surface appear again due to heat (hereinafter referred to as “recovery”) may be observed. This defect was very conspicuous especially when high-brightness printing such as silver metallic tone was performed on the smooth surface side of the acrylic resin film, and a good decorative film and laminated molded product could not be obtained.

  Furthermore, in the production methods of Patent Documents 1 to 3, since the acrylic resin composition is sandwiched between rolls when it is formed into a film, it is not in a state where surface convex defects such as fish eyes are expressed. There was virtually no means to inspect surface defects such as fish eyes in the process. For this reason, the fish eye defect due to loosening was found for the first time in the process of obtaining the laminated molded product, and the industrial utility value was low from the viewpoint of manufacturing cost, and there was room for improvement.

  In addition, when performing secondary processing such as in-mold molding, a phenomenon that the gloss value on the matte surface side increases (hereinafter referred to as “matte return”) may be observed depending on the film heating conditions.

Patent Documents 4 and 5 disclose a method in which both sides of a resin composition are brought into contact with a roll surface or a metal belt surface to form a film from the viewpoint of preventing printing loss. However, these patent documents do not describe a method for obtaining a matte film. Even in the methods described in these patent documents, it is expected that a matte film can be obtained if a roll type to be brought into contact with the resin composition is selected. At the same time, it is not a method for providing a means for inspecting defects such as fish eyes.
JP 2002-361712 A JP 2002-254495 A JP 2001-81266 A JP-A-10-279766 Japanese Patent Laid-Open No. 10-306192

  An object of the present invention is to provide a matte thermoplastic resin film having a good matte appearance and good printability, and having little flaking and matting when subjected to insert molding or in-mold molding, and this film And providing a method capable of confirming whether or not the matte acrylic resin film has returned in a later step.

  The present invention relates to a transparent thermoplastic resin film-like material that has been previously formed into a film shape and cooled to a temperature equal to or lower than the heat distortion temperature, at a set temperature equal to or higher than the heat deformation temperature of the transparent thermoplastic resin film-like material A matte thermoplastic resin having a 60 ° surface glossiness of 100% or less on one side is sandwiched between a mirror roll or mirror belt on one side of the object, and the other side is sandwiched between a rubber roll, a wrinkled roll, a rubber belt or a wrinkled belt. It is in the manufacturing method of a film.

  Moreover, this invention exists in the manufacturing method of the matte thermoplastic resin laminated | multilayer film or sheet which laminate | stacks the matte thermoplastic resin film obtained by the said method on a thermoplastic resin film or sheet.

  Furthermore, this invention exists in the manufacturing method of the matte thermoplastic resin laminated body which laminates | stacks the matte thermoplastic resin film obtained by the said method, or said matte thermoplastic resin laminated film or sheet | seat on a base material.

  According to the present invention, a matte thermoplastic resin film having a good matte appearance and good printability, and having little backlash and matte return when subjected to insert molding or in-mold molding, and this film And a method capable of confirming whether or not the matte thermoplastic resin film has returned in a later step can be provided.

In the present invention, the transparent thermoplastic resin film-like material is used that has been previously formed into a film shape and cooled to a heat distortion temperature (hereinafter referred to as “T _T ”) or lower.

In the present invention, _{T T} is based on ASTM D648, indicating the value obtained by measuring under a load of 0.45 MPa. The measurement of the T _T after molding the raw material pellets of transparent thermoplastic resin film material by injection molding is performed using the measurement test piece annealed for 4 hours at 60 ° C..

  The transparent thermoplastic resin is not particularly limited as long as it has a heat distortion temperature, and includes known thermoplastic resins such as acrylic resin, polyester resin, and polycarbonate resin. In these, an acrylic resin is preferable at points, such as a weather resistance.

Transparent thermoplastic resin film material used in the present invention, it is preferred that T _T is 80 ° C. or higher. For T _T is 80 ° C. or more thermoplastic resin film, the melt viscosity of the resin composition when formed into a film shape by a melt extrusion method raw material of the resin composition becomes moderately high, releasability from the mirror roll And the problem of winding around a mirror surface roll can be prevented. Further, for example, in a vehicle application, a film using an acrylic resin as the thermoplastic resin of the matte thermoplastic resin film obtained in the present invention, a decorative film, and a laminated molded product including these are a front control panel, etc. It can also be used in parts that receive direct sunlight in the car. From the viewpoint of applications further expansion, it is preferred T _T is 90 ° C. or higher. Although not particularly limited, from the viewpoint of film forming property and the like of the film, T _T of the transparent thermoplastic resin film material in the present invention is preferably 130 ° C. or less.

  As the transparent acrylic resin film-like material, for example, those having scratch resistance, pencil hardness, heat resistance, chemical resistance and the like that can be used for vehicles are disclosed in JP-A-8-323934 and JP-A-11-147237. Those disclosed in Japanese Patent Laid-Open No. 2002-80678, Japanese Patent Laid-Open No. 2002-80679, and Japanese Patent Laid-Open No. 2005-97351 are preferable. Further, from the viewpoint of resistance to molding whitening when insert molding or in-mold molding is performed, those disclosed in JP-A-2005-163003 and JP-A-2005-139416 are preferable.

  For example, as a specific example of a transparent acrylic resin film material excellent in scratch resistance, pencil hardness, heat resistance, chemical resistance and the like that can be used for vehicles, the following rubber-containing polymer (I) alone or rubber-containing A preferable example is an acrylic resin composition comprising the polymer (I) and a low-viscosity thermoplastic polymer.

  Specific examples of the rubber-containing polymer (I) include the following rubber-containing polymer (I-1) and rubber-containing polymer (I-2).

  Specific examples of the rubber-containing polymer (I-1) include an alkyl methacrylate as a main component in the presence of an elastic polymer obtained by polymerizing the monomer (i) containing an alkyl acrylate. And a polymer composed of an elastic polymer and a hard polymer obtained by graft polymerization of the monomer (ii) to form a hard polymer. Here, as a method for polymerizing the elastic polymer and the hard polymer, when the monomers (i) and (ii) are polymerized, they can be polymerized at once, or polymerized in two or more stages. You can also

  Examples of the alkyl acrylate ester that is a constituent of the monomer (i) include various conventionally known alkyl acrylate esters, and the alkyl group may be either linear or branched. Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. These can be used alone or in admixture of two or more. Of these, n-butyl acrylate, 2-ethylhexyl acrylate, and the like are preferable.

  The amount of the acrylic acid alkyl ester used is preferably 35 to 99.9% by mass, more preferably 50 to 99.9% by mass, in 100% by mass of the monomer (i). The moldability of a film becomes favorable that the usage-amount of acrylic acid alkylester is 35 mass% or more.

  When obtaining an elastic polymer, the monomer (i) can be polymerized in one step or in two or more stages depending on the purpose, and the polymerization can be performed in two or more stages. In such a case, the amount of alkyl acrylate used may be 35% by mass or more in monomer (i). For example, in the case of an elastic polymer polymerized in two or more stages, if the total amount of alkyl acrylate ester used in each polymerization stage is 35% by mass or more, the amount of alkyl acrylate ester used in the first stage is It can also be set arbitrarily.

  As the monomer (i), together with an alkyl acrylate, other vinyl monomers copolymerizable therewith can also be used. The amount of the other vinyl monomer used is preferably 64.9% by mass or less in 100% by mass of the monomer (i).

  As other vinyl monomers, for example, methacrylic acid alkyl esters such as methyl methacrylate, butyl methacrylate and 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.

  It is preferable to use a crosslinkable monomer as a part of the monomer (i). As the crosslinkable monomer, a monomer having two or more copolymerizable double bonds in one molecule is used. As the crosslinkable 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 preferable. In addition, polyvinylbenzene such as divinylbenzene and trivinylbenzene can be used. In addition, triallyl cyanurate, triallyl isocyanurate and the like are also effective. These can be used alone or in admixture of two or more. Of these, 1,3-butylene glycol dimethacrylate is preferred.

  As for the usage-amount of a crosslinkable monomer, 0.1-10 mass% is preferable in 100 mass% of monomers (i).

  The methacrylic acid alkyl ester that is the main component of the monomer (ii) used in the graft polymerization 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 alone or in admixture of two or more. Of these, methyl methacrylate is preferred.

  The amount of methacrylic acid alkyl ester used is preferably 50% by mass or more in 100% by mass of monomer (ii).

  As the monomer (ii), other vinyl monomers copolymerizable therewith can be used together with alkyl methacrylate. The amount of such other vinyl monomers used is preferably 50% by mass or less in 100% by mass of the monomer (ii). As such 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.

  When the rubber-containing polymer (I-1) is polymerized, the amount of the monomer (ii) is preferably 10 to 400 parts by mass, more preferably 20 to 200, relative to 100 parts by mass of the monomer (i). Part by mass.

  The mass average particle diameter of the rubber-containing polymer (I-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-forming properties and handleability of the finally obtained matte acrylic resin film, the mass average particle diameter of the rubber-containing polymer (I-1) is preferably 0.08 μm or more.

  In the present invention, the mass average particle diameter is measured by a dynamic light scattering method using a light scattering photometer DLS-700 (trade name) manufactured by Otsuka Electronics Co., Ltd.

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

  Known polymerization initiators can be used. Examples of the polymerization initiator include a peroxide, an azo initiator, or a redox initiator in which an oxidizing agent and a reducing agent are combined, and among these, a redox initiator is preferable. A sulfoxylate-based initiator in which ethylenediaminetetraacetic acid disodium salt, longalite, and hydroperoxide are combined is preferable. What is necessary is just to determine the addition amount of a polymerization initiator suitably according to superposition | polymerization conditions.

  Examples of the method for adding a polymerization initiator include a method of adding to one or both of an aqueous phase and a monomer phase (oil phase).

  As the emulsifier, anionic, cationic and nonionic surfactants can be used, and anionic surfactants are particularly preferable. Examples of the anionic surfactant include rosin soap, potassium oleate, sodium stearate, sodium myristate, sodium N-lauroylsarcosate, dipotassium alkenyl succinate; sulfate salts such as sodium lauryl sulfate; Sulfonates such as sodium dioctylsulfosuccinate, sodium dodecylbenzenesulfonate, sodium alkyldiphenyl ether disulfonate; phosphate salts such as sodium polyoxyethylene alkylphenyl ether phosphate; phosphoric acid such as sodium polyoxyethylene alkyl ether phosphate Examples include ester salts. Among these, phosphate ester salts such as sodium polyoxyethylene alkyl ether phosphate are preferable. Preferable specific examples of the surfactant include NC-718 manufactured by Sanyo Kasei Kogyo Co., Ltd., Phosphanol LS-529, Phosphanol RS-610NA, Phosphanol RS- manufactured by Toho Chemical Industry Co., Ltd. 620NA, Phosphanol RS-630NA, Phosphanol RS-640NA, Phosphanol RS-650NA, Phosphanol RS-660NA, Latemul P-0404, Latemul P-0405, Latemul P-0406 manufactured by Kao Corporation Latemul P-0407 (above, trade name) and the like.

  The polymer latex containing the rubber-containing polymer (I-1) obtained by the above method is filtered using a filter medium, for example, a filter having a filter with an opening of 100 μm or less, as necessary. Is preferred. This filtration treatment is a treatment for removing scales generated during the polymerization from the latex and removing foreign substances mixed in the polymerization raw material or during the polymerization.

  As a filtration device with filter media, a GAF filter system of ISP Filters PTA Ltd. using a bag-like mesh filter; a cylindrical filter media is arranged on the inner surface of a cylindrical filter chamber, and the filter media is stirred. A centrifugal type filtration device provided with blades; or a vibration type filtration device in which the filter medium performs a horizontal circular motion and a vertical amplitude motion with respect to the filter medium surface is preferable.

  The rubber-containing polymer (I-1) can be produced by recovering the rubber-containing polymer (I-1) from the polymer latex produced by the above method. Examples of the method for recovering the rubber-containing polymer (I-1) from the polymer latex include known methods such as salting out or acid precipitation coagulation, spray drying, freeze drying and the like. Next, the coagulated polymer is further washed, dehydrated, dried, etc., and finally recovered in powder form.

  When recovering the rubber-containing polymer (I-1) by salting out coagulation using a metal salt, the residual metal content in the finally obtained rubber-containing polymer (I-1) should be 800 ppm or less. Is preferred. In particular, when a metal salt having a strong affinity for water, such as magnesium salt or sodium salt, is used as a salting-out agent, the final rubber-containing polymer (I- When a matte acrylic resin film made from 1) is immersed in boiling water, whitening tends to occur. In addition, when salting out coagulation using calcium salt or aciding out coagulation using sulfuric acid shows a relatively good tendency, in order to give excellent water whitening resistance in any case, It is preferable to make it 800 ppm or less, and it is so good that it is a trace amount.

  As the rubber-containing polymer (I), the following rubber-containing polymer (I-2) is preferable from the viewpoint of resistance to molding whitening during in-mold molding or insert molding.

The rubber-containing polymer (I-2) is obtained by sequentially polymerizing the monomer components (1) to (3) in Table 1 below. Here, (2) the monomer composition of the intermediate polymer (I-2-B) is different from (1) the monomer composition of the elastic polymer (I-2-A) in the kind or amount of at least one component. Is.

  In Table 1, acrylic acid alkyl esters (A1, B1, C2), methacrylic acid alkyl esters (A2, B2, C1) and cross-linkable monomers (A4, B4) are those of rubber-containing polymer (I-1). It is the same as that used in the polymerization.

  In Table 1, as other monomers (A3, B3, C3) having a copolymerizable double bond, acrylic monomers such as lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, methacrylic acid, Examples include styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile, unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride, N-phenylmaleimide, N-cyclohexylmaleimide and the like. These can be used alone or in admixture of two or more.

  The crosslinkable monomers (A4, B4) can be arbitrarily added depending on the purpose, for example, when the hot strength or the like is strictly required.

  In Table 1, graft crossing agents (A5, B5) refer to monomers having two or more different copolymerizable double bonds in one molecule. Specific examples thereof include allyl, methallyl, or crotyl ester of copolymerizable α, β-unsaturated carboxylic acid or dicarboxylic acid. Particularly preferred are allyl esters of acrylic acid, methacrylic acid, maleic acid, or fumaric acid. Of these, allyl methacrylate is preferable because of its excellent effect. In addition, triallyl cyanurate, triallyl isocyanurate and the like are also effective. These can be used alone or in admixture of two or more.

  The content of the acrylic acid alkyl ester (A1) is preferably 50 to 99.9% by mass in 100% by mass of the monomer that is a raw material of the elastic polymer (I-2-A). From the viewpoint of molding whitening resistance of the finally obtained matte acrylic resin film, 55% by mass or more is more preferable, and 60% by mass or more is particularly preferable. Further, from the viewpoint of surface hardness and heat resistance of the finally obtained matte acrylic resin film, it is more preferably 79.9% by mass or less, and particularly preferably 69.9% by mass or less.

  The content of the methacrylic acid alkyl ester (A2) is preferably 0 to 49.9% by mass in 100% by mass of the monomer that is a raw material of the elastic polymer (I-2-A). More preferably, it is 20 mass% or more, Most preferably, it is 30 mass% or more. Further, it is more preferably 44.9% by mass or less, particularly preferably 39.9% by mass or less.

  The content of the other monomer (A3) having a copolymerizable double bond is 0 to 20% by mass in 100% by mass of the monomer which is a raw material of the elastic polymer (I-2-A). preferable. More preferably, it is 15 mass% or less.

  As for content of a crosslinkable monomer (A4), 0-10 mass% is preferable in 100 mass% of monomers which are the raw materials of an elastic polymer (I-2-A). From the viewpoint of molding whitening resistance of the finally obtained matte acrylic resin film, 0.1% by mass or more is more preferable, and 3% by mass or more is particularly preferable. From the viewpoint of imparting sufficient flexibility and toughness to the finally obtained matte acrylic resin film, it is preferably 6% by mass or less, particularly preferably 5% by mass or less.

  The content of the graft crossing agent (A5) is preferably 0.1 to 10% by mass in 100% by mass of the monomer that is a raw material of the elastic polymer (I-2-A). By setting the content of the graft crossing agent (A5) to 0.1% by mass or more, the molding whitening resistance of the finally obtained matte acrylic resin film is improved, and optical properties such as transparency are lowered. It can be molded without. More preferably, it is 0.5 mass% or more. Moreover, sufficient softness | flexibility and toughness can be provided to the matte acrylic resin film finally obtained by making content of a graft crossing agent (A5) into 10 mass% or less. More preferably, it is 5 mass% or less, Most preferably, it is 2 mass% or less.

  The glass transition temperature (hereinafter referred to as “Tg”) of the elastic polymer (I-2-A) alone is preferably 10 ° C. or less, and more preferably 0 ° C. or less. When Tg is 10 ° C. or less, the resulting rubber-containing multistage polymer (I) exhibits favorable impact resistance.

  Tg in the present invention is a polymer handbook [Polymer HandBook, J. et al. Calculated from the FOX equation using the homopolymer values described in Brandrup, Interscience, 1989].

  When the elastic polymer (I-2-A) is polymerized, the amount of the monomer that is a raw material of the elastic polymer (I-2-A) is the same as that of the rubber-containing polymer (I-2). 15-50 mass% is preferable in the total amount of a mass body of 100 mass%. By setting the amount of the monomer as the raw material of the elastic polymer (I-2-A) to 15% by mass or more, it is possible to impart molding whitening resistance to the finally obtained matte acrylic resin film. The film forming property and the toughness required for insert molding or in-mold molding can be made compatible. Moreover, the film which has surface hardness and heat resistance required for the laminated body of a vehicle member by making content of the monomer which is a raw material of an elastic polymer (I-2-A) into 50 mass% or less Is obtained. More preferably, it is 35 mass% or less.

  When obtaining the elastic polymer (I-2-A), the monomer that is the raw material of the elastic polymer (I-2-A) can be polymerized in one batch, or polymerized in two or more stages. You can also It is preferable to polymerize in two or more stages. When polymerizing in two or more stages, it is preferable that the monomer composition ratios in the respective polymerization stages are different from each other.

  For example, when the elastic polymer (I-2-A) is polymerized in two stages, from the viewpoint of molding whitening resistance, impact resistance, heat resistance and surface hardness of the finally obtained matte acrylic resin film The Tg of the elastic polymer (I-2-A-1) polymerized in the first stage is preferably lower than the Tg of the elastic polymer (I-2-A-2) polymerized in the second stage. . Specifically, Tg of the elastic polymer (I-2-A-1) polymerized in the first stage is preferably less than −30 ° C. from the viewpoint of molding whitening resistance and impact resistance. The Tg of the elastic polymer (I-2-A-2) polymerized in the eye is preferably −15 ° C. to 10 ° C. from the viewpoints of surface hardness and heat resistance.

  Further, from the viewpoint of surface hardness and heat resistance, the amount of monomer polymerized to obtain the elastic polymer (I-2-A-1) polymerized in the first stage is determined by the elastic polymer (I-2- Monomer polymerized in order to obtain elastic polymer (I-2-A-2) polymerized in the second stage in 100% by mass of monomer A) which is preferably 1 to 20% by mass The amount is preferably 80 to 99% by mass in 100% by mass of the monomer that is the raw material of the elastic polymer (I-2-A).

  The monomer that is a raw material of the elastic polymer (I-2-A) may be polymerized in the presence of a chain transfer agent. As for content of a chain transfer agent, 0-5 mass parts is preferable with respect to 100 mass parts of monomers which are the raw materials of an elastic polymer (I-2-A).

  The content of the acrylic acid alkyl ester (B1) is preferably 9.9 to 90% by mass in 100% by mass of the monomer that is a raw material for the intermediate polymer (I-2-B). From the viewpoint of molding whitening resistance, surface hardness, and heat resistance of the finally obtained matte acrylic resin film, 19.9% by mass or more is more preferable, and 29.9% by mass or more is particularly preferable. Further, it is more preferably 60% by mass or less, particularly preferably 50% by mass or less.

  The content of the methacrylic acid alkyl ester (B2) is preferably 9.9 to 90% by mass in 100% by mass of the monomer that is a raw material for the intermediate polymer (I-2-B). From the viewpoint of molding whitening resistance, surface hardness, and heat resistance of the finally obtained matte acrylic resin film, 39.9% by mass or more is more preferable, and 49.9% by mass or more is particularly preferable. Further, it is more preferably 80% by mass or less, particularly preferably 70% by mass or less.

  The content of the other monomer (B3) having a copolymerizable double bond is 0 to 20% by mass in 100% by mass of the monomer that is a raw material of the intermediate polymer (I-2-B). preferable. More preferably, it is 15 mass% or less.

  The content of the polyfunctional monomer (B4) is preferably 0 to 10% by mass in 100% by mass of the monomer that is a raw material for the intermediate polymer (I-2-B). From the viewpoint of imparting sufficient flexibility and toughness to the finally obtained matte acrylic resin film, it is preferably 6% by mass or less, particularly preferably 3% by mass or less.

  The content of the graft crossing agent (B5) is preferably 0.1 to 10% by mass in 100% by mass of the monomer which is a raw material for the intermediate polymer (I-2-B). By setting the content of the graft crossing agent (B5) to 0.1% by mass or more, the molded whiteness resistance of the finally obtained matte acrylic resin film is improved, and optical properties such as transparency are lowered. It can be molded without. More preferably, it is 0.5 mass% or more. Moreover, sufficient softness | flexibility and toughness can be provided to the matte acrylic resin film finally obtained by making content of a graft crossing agent (B5) into 10 mass% or less. More preferably, it is 5 mass% or less, Most preferably, it is 2 mass% or less.

  The Tg of the intermediate polymer (I-2-B) alone is preferably 25 to 100 ° C. When Tg is 25 ° C. or higher, the surface hardness and heat resistance of the finally obtained matte acrylic resin film are at levels necessary for a vehicle member. More preferably, it is 40 degreeC or more, Most preferably, it is 50 degreeC or more. Moreover, if Tg is 100 degrees C or less, a film with favorable shaping | molding whitening-proof property and film forming property will be obtained. More preferably, it is 80 degrees C or less, Most preferably, it is 70 degrees C or less.

  As described above, by providing the intermediate polymer (I-2-B) having a specific composition and Tg, it has been difficult to realize until now, which is an acrylic having both molding whitening resistance, surface hardness and heat resistance. A resin film can be obtained.

When the intermediate polymer (I-2-B) is polymerized, the amount of the monomer that is the raw material of the intermediate polymer (I-2-B) is the same as that of the rubber-containing polymer (I-2). 5 to 35 mass% is preferable in 100 mass% of the total amount of the monomer. Within this range, the function of the intermediate polymer (I-2-B) important for achieving both the above-described molding whitening resistance, surface hardness and heat resistance can be expressed, and finally It is possible to impart other physical properties of the matte acrylic resin film obtained, for example, film forming property, toughness required for insert molding or in-mold molding. More preferably, it is 20 mass% or less.

  The monomer that is a raw material of the intermediate polymer (I-2-B) may be polymerized in the presence of a chain transfer agent. The content of the chain transfer agent is preferably 0 to 5 parts by mass with respect to 100 parts by mass of the monomer that is a raw material for the intermediate polymer (I-2-B).

  When obtaining the intermediate polymer (I-2-B), the monomer as the raw material of the intermediate polymer (I-2-B) can be polymerized in one batch, or polymerized in two or more stages. You can also.

  The content of the methacrylic acid alkyl ester (C1) is preferably 80 to 100% by mass in 100% by mass of the monomer that is a raw material of the hard polymer (I-2-C). From the viewpoint of surface hardness and heat resistance of the finally obtained matte acrylic resin film, 90% by mass or more is more preferable, and 93% by mass or more is particularly preferable. Moreover, it is 99 mass% or less more preferably.

  The content of the acrylic acid alkyl ester (C2) is preferably 0 to 20% by mass in 100% by mass of the monomer that is a raw material of the hard polymer (I-2-C). More preferably, it is 1 mass% or more. Further, it is more preferably 10% by mass or less, particularly preferably 7% by mass or less.

  The content of the other monomer (C3) having a copolymerizable double bond is 0 to 20% by mass in 100% by mass of the monomer which is a raw material of the hard polymer (I-2-C). preferable. More preferably, it is 15 mass% or less.

  A chain transfer agent can be used at the time of the polymerization of the monomer which is a raw material of the hard polymer (I-2-C), and the molecular weight of the hard polymer (I-2-C) can be adjusted.

  In the present invention, the chain transfer agent can be selected from those used in ordinary radical polymerization. Specific examples include alkyl mercaptans having 2 to 20 carbon atoms, mercapto acids, thiophenol, carbon tetrachloride and the like. These can be used alone or in admixture of two or more. As for content of a chain transfer agent, 0.01-5 mass parts is preferable with respect to 100 mass parts of monomers which are the raw materials of a hard polymer (I-2-C). More preferably, it is 0.2 mass part or more, Most preferably, it is 0.4 mass part or more.

  The Tg of the hard polymer (I-2-C) alone is preferably 60 ° C. or higher. When Tg is 60 ° C. or higher, a film having surface hardness and heat resistance suitable for a vehicle member can be obtained. More preferably, it is 80 degreeC or more, Most preferably, it is 90 degreeC or more.

  When polymerizing the hard polymer (I-2-C), the amount of the monomer that is the raw material of the hard polymer (I-2-C) is the same as that of the rubber-containing polymer (I-2). 15-80 mass% is preferable in the total amount of a mass body of 100 mass%. If the amount of the monomer that is the raw material of the hard polymer (I-2-C) is 15% by mass or more, the surface hardness and heat resistance of the finally obtained matte acrylic resin film will be good. More preferably, it is 45 mass% or more. If the amount of the monomer that is the raw material of the hard polymer (I-2-C) is 80% by mass or less, the matte acrylic resin film finally obtained has a molding whitening resistance, insert molding and The toughness required for molding can be imparted.

  When obtaining the hard polymer (I-2-C), the monomer that is the raw material of the hard polymer (I-2-C) can be polymerized in one batch, or polymerized in two or more stages. You can also

  The gel content of the rubber-containing polymer (I-2) is preferably 50% or more, and more preferably 60% or more, from the viewpoint of obtaining better molding whitening resistance. From the viewpoint of molding whitening resistance, the larger the gel content, the more advantageous. However, from the viewpoint of easy moldability, the presence of a certain amount or more of free polymer is necessary, so the gel content should be 80% or less. preferable. The gel content means that a predetermined amount (mass before extraction) of the rubber-containing polymer (I-2) is extracted under reflux in an acetone solvent, the treated solution is separated by centrifugation, dried, and then insoluble in acetone. This is a value calculated by the following formula.

Gel content (%) = mass after extraction (g) / mass before extraction (g) × 100
The rubber-containing polymer (I-2) preferably has a mass average particle diameter of 0.03 to 0.3 μm. From the viewpoint of mechanical properties of the obtained thermoplastic resin film, the thickness is more preferably 0.07 μm or more, and particularly preferably 0.09 μm or more. Moreover, from a viewpoint of the shaping | molding whitening-proof property and transparency of the matt thermoplastic resin film finally obtained, More preferably, it is 0.15 micrometer or less, Most preferably, it is 0.13 micrometer or less.

  As a method for producing the rubber-containing polymer (I-2), a sequential multi-stage polymerization method by an emulsion polymerization method is the most suitable polymerization method, but is not particularly limited thereto. It can also be carried out by an emulsion suspension polymerization method in which the polymerization of the monomer as the raw material of the polymer (I-2-C) is converted into a suspension polymerization system.

  When the rubber-containing polymer (I-2) is produced by emulsion polymerization, the monomer that is a raw material of the elastic polymer (I-2-A) in the rubber-containing polymer (I-2) is previously added with water and After the emulsion prepared by mixing with the emulsifier is supplied to the reactor and polymerized, the monomer as the raw material of the intermediate polymer (I-2-B), and the hard polymer (I-2-C) A method in which the monomers as raw materials are sequentially fed to the reactor and polymerized is preferable.

  When the monomer, which is a raw material of the elastic polymer (I-2-A), is mixed with water and an emulsifier in advance and supplied to the reactor and polymerized to be dispersed in acetone. Furthermore, the rubber-containing polymer (I-2) in which the number of particles having a diameter of 55 μm or more present in the dispersion is 0 to 50 per 100 g of the rubber-containing polymer (I-2) can be easily obtained. . A film using the rubber-containing polymer (I-2) thus obtained as a raw material has a characteristic that the number of fish eyes in the film is small, and particularly a light color with a low printing pressure that is liable to cause printing omission. Even when a gravure printing of a wood grain pattern or a solid gravure printing such as a metallic tone or a jet black tone is performed, it is preferable because there is little printing omission and a high level of printability.

  As the emulsifier used when preparing the emulsion, the same emulsifier as used when the rubber-containing polymer (I-1) is produced by emulsion polymerization is used.

    As a method for preparing an emulsified liquid, a method in which a monomer is charged in water and then an emulsifier is added; a method in which a surfactant is charged in water and then a monomer is charged; and an emulsifier is added in the monomer. A method of adding water after charging is mentioned. Among these, the method of charging the monomer into water and then adding the emulsifier, and the method of charging the monomer and then adding the emulsifier to water are preferable.

  Examples of the mixing device for preparing the emulsion include various forced emulsification devices such as a stirrer equipped with a stirring blade, a homogenizer, and a homomixer, a membrane emulsification device, and the like.

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

  As a polymerization initiator used when forming an elastic polymer (I-2-A), an intermediate polymer (I-2-B), and a hard polymer (I-2-C), a rubber-containing polymer The thing similar to what is used when manufacturing (I-1) is used.

  As a method for producing the rubber-containing polymer (I-2), an aqueous solution containing ferrous sulfate, disodium ethylenediaminetetraacetic acid and Rongalite charged in a reactor is heated to a polymerization temperature, and then an elastic polymer ( An emulsion prepared by mixing a monomer as a raw material of I-2-A) and a polymerization initiator such as peroxide with water and an emulsifier is supplied to the reactor for polymerization, and then an intermediate polymer ( A monomer that is a raw material of I-2-B) is supplied to a reactor together with a polymerization initiator such as a peroxide and polymerized, and then a monomer that is a raw material of a hard polymer (I-2-C) A method is preferred in which the polymer is supplied to a reactor together with a polymerization initiator such as a peroxide and polymerized.

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

  The polymer latex containing the rubber-containing polymer (I-2) obtained by the above method is used, as in the case of the rubber-containing polymer (I-1), using a filtration device in which a filter medium is arranged as necessary. And filtering. As the filtration device provided with the filter medium, the same one as in the case of the rubber-containing polymer (I-1) is used.

  The rubber-containing polymer (I-2) can be recovered from the polymer latex produced by the above method by the same method as that for the rubber-containing polymer (I-1).

  As the raw material for the transparent acrylic resin film, the rubber-containing polymer (I) described above may be used alone, but an acrylic resin comprising the rubber-containing polymer (I) and the following low-viscosity thermoplastic polymer. It is preferable to use a composition.

  As the low-viscosity thermoplastic polymer, those having a methacrylic acid alkyl ester unit as a main component are preferable. Specifically, C1-C4 methacrylic acid alkyl ester 50-100 mass%, acrylic acid alkyl ester 0-50 mass%, and other monomer 0-50 mass% which has a copolymerizable double bond A polymer having a reduced viscosity of 0.15 L / g or less is preferable.

  In the present invention, the reduced viscosity refers to a value obtained when 0.1 g of a polymer is dissolved in 100 mL of chloroform and measured at 25 ° C.

  By using such a low viscosity thermoplastic polymer in combination, the surface hardness and heat resistance of the finally obtained matte acrylic resin film can be increased. In this case, the Tg of the low viscosity thermoplastic polymer is preferably 80 ° C. or higher, more preferably 90 ° C. or higher.

  As the methacrylic acid alkyl ester and acrylic acid alkyl ester, those similar to those used in the production of the rubber-containing polymer (I) are used.

  Examples of the other monomer having a double bond capable of copolymerization include various monomers used in the production of the rubber-containing polymer (I). These monomers may be used alone or in combination of two or more. Can be used in combination.

  From the viewpoint of the surface hardness and heat resistance of the finally obtained matte acrylic resin film, the content of the alkyl methacrylate is 50 to 50% in 100% by mass of the monomer component that is a raw material for the low-viscosity thermoplastic polymer. 100 mass% is preferable. More preferably, it is 80 mass% or more, and is 99.9 mass% or less.

  The content of the acrylic acid alkyl ester is a raw material for the low-viscosity thermoplastic polymer from the viewpoint of imparting the toughness necessary for the matte acrylic resin film finally obtained and insert molding or in-mold molding. 0-100 mass% is preferable in 100 mass% of monomer components. More preferably, it is 0.1 mass% or more and 20 mass% or less.

  The content of the other monomer having a copolymerizable double bond is preferably 0 to 50 mass in 100 mass% of the monomer component which is a raw material for the low viscosity thermoplastic polymer.

  The reduced viscosity of the low-viscosity thermoplastic polymer is more preferably 0.1 L / g or less from the viewpoint of insert moldability, in-mold moldability, and film formability of the finally obtained matte acrylic resin film. Moreover, 0.01 L / g or more is preferable from a viewpoint of film forming property, and 0.03 L / g or more is more preferable.

  It does not specifically limit as a manufacturing method of a low-viscosity thermoplastic polymer, Methods, such as normal suspension polymerization, emulsion polymerization, and block polymerization, are mentioned.

  When the rubber-containing polymer (I-1) is used, the content of the rubber-containing polymer (I-1) is 100 parts by mass of the acrylic resin composition from the viewpoint of film forming property, pencil hardness, and moldability. 5-30 mass% is preferable. 10 mass% or more is more preferable from a viewpoint of film forming property and moldability, and 25 mass% or less is more preferable from a viewpoint of pencil hardness.

  Moreover, when rubber-containing polymer (I-2) is used, the content of rubber-containing polymer (I-2) is preferably 1 to 99 mass% in 100 mass% of the acrylic resin composition. From the viewpoint of molding whitening resistance of the finally obtained matte acrylic resin film, the content of the rubber-containing polymer (I-2) is more preferably 50% by mass or more, particularly preferably 70% by mass or more. . The content of the low-viscosity thermoplastic polymer is more preferably 50% by mass or less, and particularly preferably 30% by mass or less.

  It is preferable that the gel content rate of an acrylic resin composition is 10-80 mass% from a viewpoint of shaping | molding whitening-proof property and film forming property. More preferably, it is 20 mass% or more, Most preferably, it is 40 mass% or more. Further, it is more preferably 75% by mass or less, particularly preferably 70% by mass or less.

  In the present invention, if necessary, a high-viscosity thermoplastic polymer having a reduced viscosity exceeding 0.15 L / g may be used as a raw material for the transparent acrylic resin film.

  Specifically, the high-viscosity thermoplastic polymer is a monomer composed of 50 to 100% by mass of methyl methacrylate and 0 to 50% by mass of another monomer having a double bond copolymerizable therewith. It is obtained by polymerizing a monomer. Examples of the other monomer include various monomers used in the production of the rubber-containing polymer (I). These monomers can be used alone or in admixture of two or more.

  By adding a high-viscosity thermoplastic polymer, the film-forming property of the transparent acrylic resin film can be improved. The high viscosity thermoplastic polymer is preferably used in an amount of 20 parts by mass or less with respect to 100 parts by mass of the acrylic resin composition. More preferably, it is in the range of 1 to 10 parts by mass from the viewpoint of film formability.

  In the present invention, the transparent thermoplastic resin film is a general compounding agent such as a stabilizer, a lubricant, a processing aid, a plasticizer, a foaming agent, a filler, an antibacterial agent, an antifungal agent, if necessary. A release agent, an antistatic agent, a colorant, an ultraviolet absorber, a light stabilizer and the like may be contained.

  In order to impart weather resistance to the transparent thermoplastic resin film, it is preferable to add an ultraviolet absorber. As an ultraviolet absorber, a well-known thing can be used and a copolymer type thing may be used. The molecular weight of the ultraviolet absorber is preferably 300 or more, and more preferably 400 or more. If the molecular weight of the ultraviolet absorber is 300 or more, mold contamination due to volatilization of the ultraviolet absorber when vacuum molding or pressure molding is performed in an injection mold can be prevented. In general, the higher the molecular weight of the ultraviolet absorber, the less likely it is to bleed out after being processed into a film, and the ultraviolet absorption performance is sustained for a longer period than the one with a lower molecular weight. Furthermore, when the molecular weight of the ultraviolet absorber is 300 or more, the ultraviolet absorber tends not to volatilize until the transparent thermoplastic resin film is extruded from the T-die and cooled by a cooling roll. In addition, the volatilized UV absorber recrystallizes on the chain that suspends the T die on the top of the T die or the exhaust hood and grows over time. This eventually falls on the film and becomes a defect in appearance. This also reduces the problem.

  As the ultraviolet absorber, a benzotriazole-based ultraviolet absorber having a molecular weight of 400 or more or a triazine-based ultraviolet absorber having a molecular weight of 400 or more is particularly preferable. Specific examples of the benzotriazole ultraviolet absorber include Tinuvin 234 (trade name) manufactured by Ciba Specialty Chemicals, and Adeka Stub LA-31 (trade name) manufactured by Asahi Denka Kogyo Co., Ltd. Specific examples of the triazine ultraviolet absorber include Tinuvin 1577 (trade name) manufactured by Ciba Specialty Chemicals.

  The addition amount of the ultraviolet absorber is not particularly limited, but the rubber-containing polymer (I-1) or the rubber-containing polymer (I-2), the low-viscosity thermoplastic polymer, and the high-viscosity thermoplastic polymer are not limited. It is preferably used in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the total (hereinafter referred to as “acrylic resin raw material”). From the viewpoint of improving weather resistance, it is more preferably 0.5 parts by mass or more, and particularly preferably 1 part by mass or more. From the viewpoint of roll stain during film formation, chemical resistance and transparency, it is more preferably 5 parts by mass or less, particularly preferably 3 parts by mass or less.

  As the light stabilizer, known ones can be used, and among them, a hindered amine light stabilizer is preferable.

  The hindered amine light stabilizer is preferably used in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the acrylic resin raw material. From the viewpoint of improving light resistance, it is more preferably at least 0.1 part by mass, particularly preferably at least 0.2 part by mass. From the viewpoint of roll contamination during film formation, it is more preferably 2 parts by mass or less, and particularly preferably 1 part by mass or less.

  As a method for adding a compounding agent, a method of supplying a transparent thermoplastic resin film material to an extruder together with a resin raw material, a method of kneading and mixing a mixture obtained by adding a compounding agent in advance to a resin raw material in various kneaders Etc.

  Examples of the kneader used in the latter method include ordinary single screw extruders, twin screw extruders, Banbury mixers, roll kneaders, and the like.

  The manufacturing method of a transparent thermoplastic resin film-like thing is not specifically limited, A well-known method is used. Specific examples include various methods such as a melt casting method such as a melt casting method, a T die method, and an inflation method, and a calendar method, but the T die method is preferable from the viewpoint of economy.

  As a method of cooling and solidifying a transparent thermoplastic resin composition in a molten state when the resin composition which is a raw material of the transparent thermoplastic resin film is formed into a film shape by a melt extrusion method such as a T-die method, two mirror surfaces are used. Either a method of sandwiching with a metal roll and / or two mirror-surface metal belts or a method of not sandwiching can be selected. The transparent thermoplastic resin film obtained by this method can easily detect surface convex defects such as fish eyes with a known film surface defect system.

  It does not specifically limit as a surface defect system for films, A generally well-known apparatus can be used. Specific examples include LSC-3000 series (manufactured by Mitsubishi Rayon Engineering Co., Ltd., line CCD camera; 7450 pixels / 20 MHz drive, illumination device; optical fiber illumination / transmission system, image processing device; LSC-300).

  In addition, when manufacturing a film-form thing by a melt extrusion method, it is preferable to extrude, filtering the resin composition in a molten state with the screen mesh of 200 mesh or more.

  The thickness of the transparent thermoplastic resin film is preferably 10 to 500 μm. By setting the thickness to 500 μm or less, the finally obtained matte thermoplastic resin film can obtain rigidity suitable for insert molding and in-mold molding, and more stably produce a matte thermoplastic resin film. can do.

  Moreover, by setting it as thickness 10 micrometers or more, while improving the protection property of the thermoplastic resin layer which is a base material, a feeling of depth can be more fully provided to the laminated body obtained. The thickness is more preferably 30 μm or more, and particularly preferably 50 μm or more. Further, the thickness is more preferably 300 μm or less, and particularly preferably 200 μm or less.

In the present invention, the transparent thermoplastic resin film produced by the above method is set again to a temperature _{equal to} or higher than the thermal deformation temperature T _T , and one side of the transparent thermoplastic resin film is mirror mirror roll or mirror belt, A matte thermoplastic resin film having a 60 ° surface glossiness of 100% or less on one side can be obtained by subjecting the surface to a heat treatment by sandwiching the surface with a rubber roll, a textured roll, a rubber belt or a textured belt. .

By setting the set temperature of heat treatment (hereinafter referred to as “T _N ”) to be equal to or higher than the thermal deformation temperature T _{T of} the transparent thermoplastic resin film-like material, the surface of the transparent thermoplastic resin film material (hereinafter referred to as the mirror-like roll or mirror belt). The smooth surface transfer property of the “smooth surface” is improved, the smoothness of the smooth surface is increased, and printing omission is reduced. Furthermore, the followability of the surface of a transparent thermoplastic resin film (hereinafter referred to as “matte surface”) to the rubber roll, wrinkled roll, rubber belt or wrinkled belt is also improved, and the matte surface has good matting properties. To do. More preferable T _N is T _T + 40 ° C. or more, and most preferable T _T + 80 ° C. or more.

  The 60 ° surface glossiness of one surface of the matte thermoplastic resin film, that is, the matte surface, is 100% or less. The 60 degree surface glossiness is a gloss value obtained by measuring the matte surface side of the film at an angle of 60 degrees using a gloss meter (Murakami Color Research Laboratory, GM-26D type). The 60 degree surface glossiness is preferably 50% or less, and more preferably 30% or less.

  Further, the surface pressure when the transparent thermoplastic resin film is sandwiched between the rolls or the belt is not particularly limited, but is preferably sandwiched with a surface pressure of 0.2 MPa or more. More preferably, it is 0.5 MPa or more, and most preferably 1 MPa or more.

  As the mirror roll or mirror belt in the present invention, various known ones can be used. In particular, the surface roughness after chrome plating is preferably 0.5S (also referred to as the maximum height Ry = 0.5 μm) or less.

  As the rubber roll and rubber belt in the present invention, various known ones can be used. From the viewpoint of heat resistance, the material is preferably silicone rubber. In order to obtain good matting properties, silicone rubber containing alumina is preferable. Since the preferable matte appearance of the thermoplastic resin film varies depending on the use, the particle size and amount of alumina added to the silicone rubber may be changed according to the use. Specific examples of the silicone rubber containing alumina include silicone rubber to which 50% by mass of alumina having an average particle size of 40 μm is added.

  As the textured roll and the textured belt used in the present invention, various known materials can be used, and the material is not particularly limited, such as metal and rubber.

  The hardness of the matte thermoplastic resin film obtained by the present invention is not particularly limited, but the pencil hardness on the matte surface side (measurement based on JIS K5400) is preferably 2B or more. Further, it is preferably HB or more, and most preferably F or more. When a matte thermoplastic resin film with a pencil hardness of 2B or more is used, the matte thermoplastic resin film and various decorative thermoplastics such as patterns, printing, and vapor deposition described later in the process of insert molding or in-mold molding The resin film is not easily scratched, and the laminate molded product obtained by laminating these has good scratch resistance.

  For example, when used for a vehicle, the pencil hardness of the thermoplastic resin film of the present invention is preferably HB or higher. Acrylic resin as a thermoplastic resin, pencil hardness of HB or higher acrylic resin film, decorative acrylic resin film, and laminated molded products laminated with these are door waist garnish, front control panel, power window switch panel, air Since it can be suitably used for various vehicle members such as bag covers, it is very useful industrially from the viewpoint of expanding applications. Further, when the pencil hardness is F or more, the scratches are not noticeable even when scratched with a cloth having a rough surface such as gauze, and the practical scratch resistance performance equivalent to a molded product using a thermoplastic resin film having a pencil hardness of 2H. Therefore, industrial utility value becomes very high.

  The matte thermoplastic resin film produced according to the present invention may be formed with a pattern layer in order to be laminated on various base materials and impart design properties. In this case, it is preferable to form a picture layer on the smooth surface of the matte thermoplastic resin film. In addition, when a matte thermoplastic resin film is laminated on a thermoplastic resin layer as a base material to produce a laminate, it is necessary to laminate the pattern layer so that it adheres to the base material. And it is preferable from the viewpoint of imparting a sense of quality.

  The pattern layer can be formed by a known method. As a picture layer, the printing layer formed by the printing method and / or the vapor deposition layer formed by the vapor deposition method are preferable.

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

  As binders for the printing layer, polyvinyl resins such as vinyl chloride / vinyl acetate copolymers, polyamide resins, polyester resins, acrylic resins, polyurethane resins, polyvinyl acetal resins, polyester urethane resins, cellulose esters Resin such as olefin resin, alkyd resin, and chlorinated polyolefin resin. As an acrylic resin, you may use the acrylic resin composition containing the above-mentioned rubber-containing polymer (I-2), for example.

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

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

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

  Examples of the method for forming the printing layer include known printing methods such as offset printing, gravure rotary printing, and screen printing; known coating methods such as roll coating and spray coating; and flexographic printing.

  What is necessary is just to determine the thickness of a printing layer suitably as needed. For example, what is necessary is just to select the thickness suitably according to the expansion | extension degree at the time of insert molding or in-mold molding so that a desired surface appearance may be obtained in the laminated body obtained by insert molding or in-mold molding. Usually, it is 0.5-30 micrometers.

The number of missing prints in the print layer is preferably 10 pieces / m ² or less from the viewpoints of design properties and decorating properties. By setting the number of printing omissions to 10 pieces / m ² or less, the appearance of the laminate using the matte acrylic resin film becomes better. The number of missing prints in the print layer is more preferably 5 pieces / m ² or less, and particularly preferably 1 piece / m ² or less.

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

  The thickness of the vapor-deposited layer is not particularly limited. For example, depending on the degree of extension during insert molding or in-mold molding, a desired surface appearance can be obtained in a laminate obtained by insert molding or in-mold molding. The thickness may be selected as appropriate.

  The matte thermoplastic resin film produced according to the present invention may be provided with an adhesive layer as necessary. The adhesive layer is preferably formed on the surface of the matte thermoplastic resin film on the smooth surface side. As the adhesive for forming the adhesive layer, a known adhesive can be used depending on the purpose.

  Moreover, you may provide a cover film further in the matte thermoplastic resin film manufactured by this invention. This cover film is effective for dust-proofing the surface of the matte thermoplastic resin film. The cover film can be provided on either the matte surface side or the smooth surface side of the matte thermoplastic resin film. It is preferable to provide at least on the matte surface side.

  When the cover film is provided on the matte surface side, the cover film adheres to the matte surface side before in-mold molding or insert molding, and immediately peels off when in-mold or insert molding. It is preferable to have moderate adhesion to the side and good releasability. As the cover film, any film can be selected and used as long as it satisfies such conditions. Examples of such a film include a polyethylene film, a polypropylene film, and a polyester film.

  The matte thermoplastic resin film produced according to the present invention may be further laminated on a thermoplastic resin film or sheet to form a laminated film or sheet. When the matte thermoplastic resin film is laminated on the thermoplastic resin film or sheet, the matte thermoplastic resin film is preferably laminated so that the smooth surface side of the matte thermoplastic resin film is in contact with the thermoplastic resin film or sheet.

  The thermoplastic resin film or sheet is preferably made of a material having compatibility with the matte thermoplastic resin film for the purpose of improving the adhesion with the matte thermoplastic resin film. Moreover, what consists of a material compatible with base-material resin is preferable from the objective of improving adhesiveness with base-material resin mentioned later. More preferably, the thermoplastic resin film or sheet is made of the same material as the base resin.

  As the resin constituting the thermoplastic resin film or sheet, a known thermoplastic resin can be used, for example, acrylic resin; ABS resin (acrylonitrile-butadiene-styrene copolymer); AS resin (acrylonitrile-styrene copolymer). Polyvinyl chloride resin; Polyolefin resin such as polyethylene, polypropylene, polybutene, polymethylpentene; Polyolefin copolymer such as ethylene-vinyl acetate copolymer or saponified product thereof, ethylene- (meth) acrylic acid ester copolymer Polymer: Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, etc .; Polyamide trees such as 6-nylon, 6,6-nylon, 6,10-nylon, 12-nylon Polystyrene resin; cellulose derivatives such as cellulose acetate and nitrocellulose; fluororesins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, and ethylene-tetrafluoroethylene copolymer; or 2 selected from these Examples include three or more kinds of copolymers or mixtures, composites, and laminates.

  Among these, pattern layer formability (when forming on a thermoplastic resin film or sheet instead of forming a pattern layer on a matte thermoplastic resin film), secondary moldability of matte thermoplastic resin laminated film or sheet In view of the above, acrylic resin, ABS resin, vinyl chloride resin, polyolefin or polycarbonate is preferable.

  For the thermoplastic resin film or sheet, if necessary, a general compounding agent such as a stabilizer, an antioxidant, a lubricant, a processing aid, a plasticizer, an impact resistance agent, a foaming agent, a filler, an antibacterial agent, You may mix | blend an antifungal agent, a mold release agent, an antistatic agent, a coloring agent, a ultraviolet absorber, a light stabilizer, a heat stabilizer, a flame retardant, etc.

  The thickness of the thermoplastic resin film or sheet may be appropriately determined as necessary, and is usually preferably about 20 to 500 μm.

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

  When the matte thermoplastic resin film produced according to the present invention is used, it is possible to suppress the back and gloss return due to heat when forming a laminated film or sheet, and the design can be retained before and after forming the laminated film or sheet. It becomes possible. Moreover, since the temperature condition range of lamination | stacking film or sheet formation can be set widely, industrial utility value is high.

  By using the matte thermoplastic resin film produced according to the present invention as a laminated film or sheet, sufficient strength for handling against external forces such as impact and deformation is exhibited. For example, the thermoplasticity of the present invention can be applied to impact, deformation, etc., when the film is vacuum-molded by insert molding and then removed from the mold or when the vacuum-molded product is mounted on an injection mold. By using the resin laminated film or sheet, cracks and the like are hardly generated, and the handleability is improved. Further, when producing a matte thermoplastic resin laminate described later, for example, the surface defects of the injection-molded base material for constituting the laminate are minimized to be propagated to the matte thermoplastic resin film. Or the advantage that the pattern layer hardly disappears when the substrate is injection-molded.

  In the present invention, if necessary, on one surface of the matte thermoplastic resin film or the surface of the thermoplastic resin film or sheet side in the laminated film or sheet, for example, corona treatment, ozone treatment, plasma treatment, ionizing radiation treatment, Surface treatments such as dichromic acid treatment, anchor treatment, and primer treatment may be applied. By carrying out these treatments, the matte thermoplastic resin film and the picture layer, the thermoplastic resin film or sheet and the picture layer, the matte thermoplastic resin film and the thermoplastic resin film or sheet, It is possible to improve the adhesion such as a gap.

  The matte thermoplastic resin film or matte thermoplastic resin laminated film or sheet produced according to the present invention can be laminated on a substrate. At this time, the matte thermoplastic resin film or matte so that the surface of the thermoplastic resin film or sheet of the matte thermoplastic resin film or the matte thermoplastic resin laminated film or sheet is in contact with the substrate. A thermoplastic resin laminated film or sheet is laminated on a substrate to form a laminate.

  Examples of the material of the substrate include resin; wood veneer such as wood veneer, wood plywood, particle board, medium density fiber board (MDF); wood board such as wood fiber board; metal such as iron and aluminum.

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

  Of these, the material for the substrate is preferably a matte thermoplastic resin film, or a material that can be melt bonded to a thermoplastic resin film or sheet. For example, an ABS resin, an AS resin, a polystyrene resin, a polycarbonate resin, a vinyl chloride resin, an acrylic resin, a polyester resin, or a resin containing these as a main component 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.

  Even with a resin that is not heat-sealed, such as a polyolefin-based resin, it is possible to adhere the matte thermoplastic resin film or laminated film or sheet thereof to the substrate at the time of molding by providing the above-mentioned adhesive layer. .

  As a manufacturing method of a laminated body, in the case of a two-dimensionally shaped laminated body and a base material that can be heat-sealed, a known method such as thermal lamination can be used. For example, for wood substrates such as wood veneer, wood plywood, particle board, medium density fiber board (MDF), water quality boards such as wood fiber board, metals such as iron and aluminum, etc. It is possible to bond them through an adhesive layer.

  In the case of a three-dimensional laminated body, a laminated molded body can be obtained using a known method such as an insert molding method or an in-mold molding method.

  In-mold molding method involves heating a matte thermoplastic resin film, or its laminated film or sheet, then vacuum forming in a mold having a vacuuming function, and then a resin that becomes a base material in the same mold Is a method for obtaining a matte thermoplastic resin film, or a laminate in which a laminated film or sheet thereof and a substrate are integrated. The in-mold molding method is preferable from the viewpoints of workability and economy because the film molding and the injection molding can be performed in one step.

  When in-mold molding is performed using a known acrylic resin film having a pattern layer, the pattern layer near the gate may disappear depending on the shape of the mold and injection molding conditions. The gate is roughly classified into a non-restricted gate in which the resin flow path is not narrowed in the gate portion and a restricted gate in which the flow path is narrowed. Representative examples of the latter include pinpoint gates, side gates, submarine gates, and the like. In the case of a restricted gate, although the residual stress near the gate is reduced, 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. Is easy to disappear. On the other hand, when the matte acrylic resin film containing the rubber-containing polymer (I) of the present invention is used, the disappearance of the pattern layer is reduced as compared with the case where a conventionally known acrylic resin film is used. Can do.

  The matte thermoplastic resin laminated film or sheet is preferable in that the disappearance of the pattern layer can be further reduced because of the presence of the thermoplastic resin film or sheet layer.

  The heating temperature at the time of in-mold molding is preferably equal to or higher than the temperature at which the matte thermoplastic resin film or the laminated film or sheet thereof is softened. Specifically, it may be set as appropriate depending on the thermal properties and shape of the matte thermoplastic film, laminated film or sheet, and 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. Usually, it is 170 degrees C or less. 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 formed even when 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.

  In addition, when the matte thermoplastic resin film manufactured according to the present invention is used, it is possible to suppress the back and gloss return due to heat during preheating during vacuum forming, and the design can be maintained before and after heating. It becomes. Moreover, since the condition range of preheating temperature can be set widely, industrial utility value is high.

  When a three-dimensional shape is imparted to a film by vacuum forming, the matte thermoplastic resin film produced according to the present invention, or a laminated film or sheet thereof, has a high degree of elongation at high temperatures, which is very advantageous.

  As the resin to be injection-molded, any resin that can be injection-molded can be used regardless of the type. It is possible to approximate the shrinkage rate of the resin after injection molding to the shrinkage rate of the matte thermoplastic resin film, or its laminated film or sheet, warpage of the laminate obtained by in-mold molding, insert molding, film, This is preferable because problems such as sheet peeling can be solved.

  The laminate comprising the matte thermoplastic resin film produced according to the present invention is particularly suitable for vehicle members and building materials. Specific examples include automotive interior components such as instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, dashboards, weather strips, bumpers, bumper guards, side mud guards, body panels. , Spoilers, front grills, strut mounts, wheel caps, center pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, windows, headlamp covers, tail lamp covers, windshield parts, etc .; AV equipment, furniture Front panels of products, buttons, emblems, surface cosmetics, etc .; mobile phone housings, display windows, buttons, etc .; furniture exterior materials; walls, ceilings, floors, etc. Interior materials for buildings: Exterior walls for buildings such as sidings, fences, roofs, gates, windbreak boards, etc. Surface decoration materials for furniture such as window frames, doors, handrails, sills, duck, various displays, lenses, mirrors, Optical members such as goggles and window glass; Interior and exterior members of various vehicles other than automobiles such as trains, airplanes, and ships; Various packaging containers such as bottles, cosmetic containers, and accessories; Packaging materials; Miscellaneous goods such as prizes and accessories It can be suitably used for various other purposes.

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

MMA Methyl methacrylate MA Methyl acrylate n-BA n-Butyl acrylate St Styrene 1,3-BD 1,3-butylene glycol dimethacrylate AMA Allyl methacrylate CHP Cumene hydroperoxide t-BH t-butyl hydroperoxide n-OM n- Octyl mercaptan EDTA Disodium ethylenediaminetetraacetate The physical properties of rubber-containing polymer (I), low-viscosity thermoplastic polymer and high-viscosity thermoplastic polymer, transparent heat produced in Examples 1-9 and Comparative Examples 1-4 The physical properties of the plastic resin film-like material, the matte thermoplastic resin film, the matte thermoplastic resin laminate film or sheet and the matte thermoplastic resin laminate were measured and evaluated by the following test methods.

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

(2) Heat distortion temperature (T _T ) of transparent thermoplastic resin film
The raw material pellets of the transparent thermoplastic resin film were formed into a heat distortion temperature measurement test piece 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).

(3) Surface gloss of matte thermoplastic resin film Using a gloss meter (Murakami Color Research Laboratory, GM-26D type), the matte surface side of the film was measured at an angle of 60 degrees.

(4) Number of missing prints After a gravure printing of the pattern on the smooth surface side of the matte thermoplastic resin film, a visual inspection of 5 m ² was performed, and the number of missing prints was measured and displayed as a number per 1 m ² .

(5) Unevenness of matte thermoplastic resin film In the final matte thermoplastic resin film, when producing a transparent thermoplastic resin film, a surface defect system for film LSC-3000 (Mitsubishi Rayon) A 100 mm square film was cut out centering on the part detected as fish eye by Engineering Co., Ltd., and fixed to an aluminum frame as a sample, and the film appearance after holding for 1 minute in a 140 ° C. oven was as follows: It was evaluated as follows.

○: No return (no return in all samples of 10 samples)
△: Almost no return (less than 2 samples out of 10 samples)
×: There is a loose return (3 or more samples return within 10 samples)
(6) Surface gloss of laminated molded body The gloss value on the matte surface side of the laminated molded body was measured according to the measurement method of (3).

[Production Example 1] (Production of rubber-containing polymer (I-2))
After charging 10.8 parts of deionized water into a vessel equipped with a stirrer, it consists of MMA 0.3 part, n-BA 4.5 part, 1,3-BD 0.2 part, AMA 0.05 part and CHP 0.025 part. 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 deionized water was charged into the polymerization vessel at once. Subsequently, the above 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 first stage polymerization of the elastic polymer (I-2-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 was dropped into the polymerization vessel over 90 minutes together with 0.016 part of CHP. Thereafter, the reaction was continued for 60 minutes to complete the polymerization of the second stage polymer of the elastic polymer (I-2-A-2) to obtain an elastic polymer (I-2-A). The Tg of the polymer (I-2-A-1) alone was −48 ° C., and the Tg of the polymer (I-2-A-2) alone was −10 ° C.

  Subsequently, a monomer mixture composed 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 polymer (I- 2-B) was formed. The Tg of the intermediate polymer (I-2-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 to obtain a hard polymer ( I-2-C) was formed to obtain a polymer latex of the rubber-containing polymer (I-2). The Tg of the hard polymer (I-2-C) alone was 99 ° C. Moreover, the mass average particle diameter of the rubber-containing polymer (I-2) measured after polymerization was 0.11 μm.

  The polymer latex of the obtained rubber-containing polymer (I-2) was filtered using a vibration type filtration apparatus equipped with a SUS mesh (average opening: 62 μm) as a filter medium, and then calcium acetate 3.5 It was salted out in an aqueous solution containing parts, washed with water and collected, and then dried to obtain a powdery rubber-containing polymer (I-2). The gel content of the rubber-containing polymer (I-2) was 70%.

  Further, 214.3 g of the obtained rubber-containing polymer (I-2) was filtered through a nylon mesh having an opening of 25 μm, and then charged into 1500 ml of acetone, followed by stirring for 3 hours to obtain a rubber-containing polymer (I-2). Acetone dispersion was prepared. This dispersion was filtered through a nylon mesh having a mesh size of 32 μm, and then ultrasonically washed in chloroform with the nylon mesh for 15 minutes. The captured substance after ultrasonic cleaning was put into 150 ml of acetone together with the nylon mesh, and this liquid was subjected to ultrasonic treatment for 15 minutes, after which the nylon mesh was removed to prepare 150 ml of an acetone dispersion of the captured substance on the mesh. About 70 ml of this dispersion, it 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 to be 10. It was.

[Production Example 2] (Production of rubber-containing polymer (I-1))
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, (i) shown in Table 2 was added, and while stirring, 1/15 of the raw material (b) (monomer (i) -1) for the first stage polymerization of the elastic polymer was charged for 15 minutes. Retained. Next, the remainder of the raw material (b) is continuously added at a rate such that the rate of increase of the monomer of the raw material (b) with respect to water is 8% / hr, and then held for 60 minutes. A stage polymer latex was obtained. The polymer obtained had a Tg of 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) (monomer (i) -2) for the second stage polymerization of the elastic polymer is replaced with the monomer of the raw material (c) with respect to water. After continuously adding at a rate of 4% / hr increase rate, it was held for 120 minutes to form a second stage polymer of an elastic polymer, and an elastic polymer latex was obtained. The Tg of the second stage polymer 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 rate of increase of the monomer of the raw material (d) (monomer (ii)) with respect to water is 10% / hr. After adding continuously at such a rate, it was held for 60 minutes to form a hard polymer, and a polymer latex of a rubber-containing polymer (I-1) was obtained. The Tg of the hard polymer alone was 99 ° C. Moreover, the mass average particle diameter of the rubber-containing polymer (I-1) measured after the polymerization was 0.28 μm.

Calcium acetate is added to the polymer latex of the obtained rubber-containing polymer (I-1), and coagulation, aggregation, and solidification reaction are performed, followed by filtration, washing with water, and drying to obtain a powdery rubber-containing polymer. (I-1) was obtained. The gel content of the rubber-containing polymer (I-1) was 90%.

[Production Example 3] (Production of high viscosity thermoplastic polymer)
The reaction vessel was charged with 200 parts of deionized water substituted with nitrogen, and as an emulsifier, 1 part of a trade name “Latemul ASK” and 0.15 part of potassium persulfate were added.

  Next, 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 dropped over 2 hours, and then kept for 2 hours to complete the polymerization.

  The obtained polymer latex was added to a 0.25% aqueous sulfuric acid solution to acidify the polymer, and then dehydrated, washed with water, and dried to recover a powdery thermoplastic polymer. The reduced viscosity of the obtained high viscosity thermoplastic polymer was 0.38 L / g.

Example 1
16 parts of the rubber-containing polymer (I-1) obtained in Production Example 2 and a low-viscosity thermoplastic polymer (1) (reduced viscosity 0.06 L / g, separately produced by suspension polymerization) (MMA / MA copolymer) Combined, manufactured by Mitsubishi Rayon Co., Ltd .; 84 parts of Acripet MD # 001 (trade name)), 1 part of the high viscosity thermoplastic polymer obtained in Production Example 3 as a compounding agent, manufactured by Ciba Specialty Chemicals Co., Ltd .; After adding 1.4 parts of “Tinubin 234”, manufactured by Asahi Denka Kogyo; 0.1 part of the trade name “Adeka Stub AO-50”, and 0.3 parts of trade name “LA-67” manufactured by Asahi Denka Kogyo Co., Ltd. And mixing with a Henschel mixer. The obtained acrylic resin composition was supplied to a degassing extruder (manufactured by Ikekai Tekko Co., Ltd .; trade name “PCM-30”) heated to 230 ° C., kneaded, and foreign matter with a 300 mesh screen mesh. It was extruded while removing to obtain pellets.

  The pellets produced by the above method were dried at 80 ° C. all day and night, and a cylinder temperature of 180 to 240 ° C. was used using a 40 mmφ non-vent screw extruder (L / D = 26) equipped with a 300 mm wide T-die. For extruding while removing foreign matter with a 500 mesh screen mesh, extruding under conditions of T die temperature of 240 ° C and T die slit width of 0.3mm, one side of the molten acrylic resin film was cooled to 75 ° C. A transparent acrylic resin film having a thickness of 125 μm was formed by bringing it into contact with a roll (roll having a chromium-plated surface roughness of 0.2S) and winding it on a paper roll with a winder. At this time, when using a film surface defect system LSC-3100V (manufactured by Mitsubishi Rayon Engineering Co., Ltd., line CCD camera; 7450 pixels, 20 MHz drive, illumination device; optical fiber illumination / transmission method, image processing device; LSC-300), Fisheye defects could be easily detected.

Incidentally, T _T of the transparent acrylic resin film material was 90 ° C..

The obtained transparent acrylic resin film-like material is a combination of a mirror surface belt having a surface roughness of 0.5 S and a belt with a textured surface, _TN 180 ° C. (T _N = T _T + 90 ° C.), and 1 MPa for 2 minutes. A matte acrylic resin film which was sandwiched and mirrored on one side and matted on one side was obtained. The surface glossiness on the matte surface side was 7%.

On the smooth surface side of the resulting matte acrylic resin film, 10 parts of a solution (Mitsubishi Rayon Co., Ltd .; Dianar LR469 (trade name)) prepared by dissolving an acrylic resin in a mixed solution of MEK and toluene, Using an ink added with 2 parts of scaly aluminum pigment, silver metallic printing was performed by gravure printing. The printed layer had a thickness of 5 μm. The number of missing prints was as good as 0.2 per 1 m ² .

  Next, a heat-resisting ABS resin bulk sum TM25B (trade name; manufactured by UMGABS) and a matte acrylic resin film subjected to the above-described gravure printing are used as a base material resin, and a mold ( Molded product shape: 150 mm long × 120 mm wide × 2 mm thick, 10 mm deep box shape, gate position: one at the center of the molded product and one each at a position 40 mm above and below the central gate (vertical direction of the molded product) An in-mold molding device that combines a J85 ELII type injection molding machine (trade name; manufactured by Nippon Steel Co., Ltd.) and a hot pack system (manufactured by Nissha Printing Co., Ltd.) In-mold molding (film vacuum molding conditions: heater temperature 350 ° C., heating time 12 seconds, distance between heater and film 15 mm, film surface Surface temperature of about 140 ° C, injection molding conditions: cylinder to nozzle temperature of 250 ° C, injection speed of 30%, injection pressure of 43%, mold temperature of 60 ° C, vacuum-molded so that the non-decorated surface is in contact with the mold, and decorated A base resin was injected from the surface side) to obtain a laminated molded body.

(Example 2)
In Example 1, instead of the low-viscosity thermoplastic polymer (1), the low-viscosity thermoplastic polymer (2) (MMA / MA copolymer, manufactured by Mitsubishi Rayon Co., Ltd.) having a reduced viscosity of 0.06 L / g. A laminated molded product was obtained in the same manner as in Example 1 except that ACRYPET VH # 001 (trade name) was used. Table 3 shows various evaluation results for the evaluation of the possibility of detecting fish eye defects in the transparent acrylic resin film-like material, the matte acrylic resin film and the laminated molded body.

The heat deformation temperature _{T T} of the transparent acrylic resin film material is 100 ° _C., was _{T N = T T + 80 ℃} .

(Example 3)
In Example 2, instead of the rubber-containing polymer (I-1), 75 parts of the rubber-containing polymer (I-2) produced in Production Example 1 and 25 parts of the low-viscosity thermoplastic polymer (2) are used. Except for the above, a laminated molded body was obtained in the same manner as in Example 2, various evaluations were performed, and the results are shown in Table 3.

The heat deformation temperature _{T T} of the transparent acrylic resin film material is 88 ° _C., was _{T N = T T + 92 ℃} .

Example 4
In Example 1, a laminated molded body was obtained in the same manner as in Example 1 except that _TN was set to 140 ° C. (T _N = T _T + 50 ° C.), various evaluations were performed, and the results are shown in Table 3. It was.

(Example 5)
In Example 2, except that _TN was set to 140 ° C. (T _N = T _T + 40 ° C.), a laminated molded body was obtained in the same manner as in Example 2, and various evaluations were performed. The results are shown in Table 3. It was.

(Example 6)
In Example 3, except that _TN was set to 140 ° C. (T _N = T _T + 52 ° C.), a laminated molded body was obtained in the same manner as in Example 3, and various evaluations were performed. The results are shown in Table 3. It was.

(Example 7)
In Example 1, when _{TN is set} to 100 ° C. (T _N = T _T + 10 ° C.), printing is performed on the smooth surface side of the obtained matte acrylic resin film, and then in-mold molding is performed. A laminated molded body was obtained in the same manner as in Example 1 except that the heating time under the conditions was 9 seconds (film surface temperature of about 100 ° C.), various evaluations were performed, and the results are shown in Table 3.

(Example 8)
In Example 2, _TN was set to 100 ° C. (T _N = T _T ), and after printing on the smooth surface side of the obtained matte acrylic resin film, when performing in-mold molding, film vacuum molding conditions A laminated molded body was obtained in the same manner as in Example 2 except that the heating time was 9 seconds (film surface temperature of about 100 ° C.). Various evaluations were performed, and the results are shown in Table 3.

Example 9
In Example 3, when _TN was set to 100 ° C. (T _N = T _T + 12 ° C.), printing was performed on the smooth surface side of the obtained matte acrylic resin film, and then in-mold molding was performed. A laminated molded body was obtained in the same manner as in Example 3 except that the heating time under the conditions was 9 seconds (film surface temperature of about 100 ° C.). Various evaluations were performed, and the results are shown in Table 3.

(Comparative Example 1)
The molten acrylic resin film obtained by extrusion in the same manner as in Example 1 was passed between two metal cooling rolls, and the resin was sandwiched without any bank (resin pool), and the surface was not rolled. After the transfer, this was wound into a paper roll with a winder to form a transparent acrylic resin film having a thickness of 125 μm. At this time, when the film surface defect system LSC-3100V was used, it was possible to easily detect fish eye defects.

Further, except that the _{T N 70 ℃ (T N =} T T -20 ℃) is to obtain a molded laminate in the same manner as in Example 1, carried out various evaluations, the results are shown in Table 3.

(Comparative Example 2)
In Comparative Example 1, a laminated molded body was obtained in the same manner as in Comparative Example 1 except that the low-viscosity thermoplastic polymer (2) was used instead of the low-viscosity thermoplastic polymer (1), and various evaluations were performed. The results are shown in Table 3.

(Comparative Example 3)
In Comparative Example 1, 75 parts of rubber-containing polymer (I-2) was used instead of 16 parts of rubber-containing polymer (I-1), and low-viscosity thermoplastic resin was used instead of 84 parts of low-viscosity thermoplastic resin (1). (2) A laminated molded body was obtained in the same manner as in Comparative Example 1 except that the amount was 25 parts, and various evaluations were performed. The results are shown in Table 3.

(Comparative Example 4)
A molten acrylic resin film obtained by extrusion in the same manner as in Example 1 was cooled to 75 ° C. (a chrome-plated roll having a surface roughness of 0.2S) and an average particle size of 40 μm. It was manufactured by passing between silicone rubber rolls containing 50 parts of alumina, holding the resin in a state without a bank (resin pool), transferring the surface without rolling, and then winding it on a paper roll with a winder A laminated molded body was obtained in the same manner as in Example 1 except that a matte acrylic resin film having a thickness of 125 μm was used. Various evaluations were performed, and the results are shown in Table 3.

When producing this matte acrylic resin film, it was impossible to detect fish eye defects using the film surface defect system LSC-3100V.

As is clear from Table 3, a transparent acrylic resin film that has been previously formed into a film and cooled to a temperature equal to or lower than the thermal deformation temperature T _T is again sandwiched between the mirror belt and the wrinkled belt at a set temperature T _N equal to or higher than T _T. In Examples 1-9 manufactured by doing, the film which has favorable matteness on one side was obtained. This film was excellent in printability in the step of printing on the smooth surface side, and also had excellent resistance to the gulp return phenomenon due to heating. Furthermore, in the process which performs in-mold shaping | molding using the decorative acrylic resin film which performed printing, it had the outstanding tolerance with respect to the gloss return phenomenon by heating. Furthermore, in the construction methods of Examples 1 to 9 and Comparative Examples 1 to 3, in-line detection of surface defects such as fish eyes was possible.

On the other hand, the films of Comparative Examples 1 to 3 in which the set temperature T _{N of} the mirror belt and the wrinkled belt is not within the appropriate range with respect to the heat deformation temperature T _T of the transparent acrylic resin film-like material are the phenomenon of the back-fluctuation and gloss return due to heating. It was not resistant to the phenomenon.

  Further, in the case of Comparative Example 4 in which a matte acrylic resin film having a thickness of 125 μm was produced by sandwiching a pellet of an acrylic resin composition into a film shape and sandwiched between a mirror roll for cooling and a silicone rubber roll containing alumina, the printability was Although it was excellent, there was a case where lumps and gloss return occurred. In addition, this method cannot detect in-line surface defects such as fish eyes.

Claims (3)

A transparent thermoplastic resin film that has been previously formed into a film and cooled to a temperature equal to or lower than the heat distortion temperature is set to a temperature equal to or higher than the heat distortion temperature of the transparent thermoplastic resin film, and one side of the transparent thermoplastic resin film is A process for producing a matte thermoplastic resin film having a 60 ° surface glossiness of 100% or less on one side, wherein a mirror roll or a mirror belt, and the other side is sandwiched between a rubber roll, a roll containing a grain, a rubber belt or a belt containing a grain . A method for producing a matte thermoplastic resin laminated film or sheet in which the matte thermoplastic resin film obtained in claim 1 is laminated on a thermoplastic resin film or sheet. A method for producing a matte thermoplastic resin laminate in which the matte thermoplastic resin film obtained in claim 1 or the matte thermoplastic resin laminate film or sheet obtained in claim 2 is laminated on a substrate.