JP2006327173A - Matt acrylic resin film, manufacturing method thereof and laminated body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a matt acrylic resin film which exhibits a superior mar resistance, and is free from the occurrence of a crack in a matt layer even when the insert molding or the inmold molding is applied and it is formed into a deep-drawn shape and further has a surface hardness, a chemical resistance, a heat resistance and a matt property needed to members for a vehicle. <P>SOLUTION: The problem described above can be solved by forming the matt layer containing a matting material, a scratch preventing agent and a binder resin on the base of the acrylic resin film. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a matte acrylic resin film, a method for producing the same, and a laminate in which a matte acrylic resin film is laminated on a substrate.

  As a method for imparting design properties to a molded product at a low cost, there are an insert molding method and an in-mold molding method. In the insert molding method, a decorative film or sheet of polyester resin, polycarbonate resin, acrylic resin or the like that has been decorated by printing or the like is previously molded into a three-dimensional shape by vacuum molding or the like, and unnecessary portions are removed. This is a method for obtaining a molded product in which a decorative film or sheet and a base material are integrated by transferring the resin into an injection mold and injection molding a resin to be the base material. On the other hand, the in-mold molding method involves placing a decorative film or sheet in an injection mold, performing vacuum molding in the mold, and then injecting a resin as a base material in the same mold. Is a method for obtaining a molded product in which a decorative film or sheet and a substrate are integrated.

  As an acrylic resin film excellent in surface hardness and heat resistance that can be used for insert molding or in-mold molding, an acrylic resin comprising a resin composition in which a rubber-containing polymer having a specific composition and a thermoplastic polymer having a specific composition are mixed. A film is disclosed (for example, see Patent Documents 1 to 4). Such an acrylic resin film not only imparts decorativeness to a molded product, but also has a function as an alternative material for clear coating.

  Acrylic resin containing a rubber-containing polymer having a specific composition and a thermoplastic polymer having a specific composition in a specific ratio as a matte acrylic resin film used for producing a molded article having a matte appearance. A film (see, for example, Patent Document 5) is an acrylic resin film having a matte surface and no printing omission, a rubber-containing polymer having a specific composition, a thermoplastic polymer having a specific composition, and a matting agent An acrylic resin film containing a specific ratio (for example, see Patent Document 6) is known. Such an acrylic resin film not only imparts decorativeness to a molded product, but also has a function as an alternative material for matte coating.

  As a thermoplastic resin composition that gives an acrylic resin film having excellent matting properties, a thermoplastic resin composition comprising an acrylic resin and a linear polymer having a hydroxyl group having a specific composition has been disclosed. A specific rubber-containing multilayer polymer is preferred (for example, see Patent Document 7).

  Further, a matte acrylic resin film obtained by forming a film by sandwiching a thermoplastic resin composition containing a cross-linked acrylic polymer for matting and an acrylic resin with a roll set at a predetermined roll temperature is disclosed. (See, for example, Patent Document 8).

  There is also disclosed a matted acrylic resin film comprising a matte layer made of a heat or photocurable resin and inorganic fine particles and an acrylic resin film substrate and capable of maintaining good matting performance even after molding ( For example, see Patent Document 9).

  Further, a matte acrylic resin insert film in which a matte layer is formed on one surface of a transparent acrylic resin film and at least a pattern layer is formed on the other surface is disclosed (for example, see Patent Document 10).

  And the sheet | seat for suede tone shaping | molding which provided the coating film of the specific matte paint on the base film with a good moldability is disclosed (for example, refer patent document 11).

  In recent years, a molded product having a matte acrylic resin film layer on the surface layer, which is molded by an insert molding method or an in-mold molding method, has been used as a vehicle member.

  The acrylic resin film described in Patent Document 5 is excellent in matte property, surface hardness, heat resistance, moldability, etc. by containing a specific amount of a matte material and a rubber-containing polymer having a specific average particle diameter. It is said that. In addition, the acrylic resin film described in Patent Document 6 has a specific film surface glossiness, and thus has good printability and is excellent in matteness, surface hardness, heat resistance, moldability, and the like. .

  However, since these acrylic resin films contain a matting material in the acrylic resin film substrate, there are restrictions on the matting material that can be used. Specifically, when organic fine particles or inorganic fine particles having a cross-linking structure mainly containing components other than acrylic resin are used, the haze value of the matte acrylic resin film is increased although it is in a matte state. Therefore, when a pattern layer is formed on one side of a matte acrylic resin film and laminated so that the pattern layer is in contact with the base material, the pattern of the molded product appears cloudy. Is low.

  In addition, when organic fine particles or inorganic fine particles having a crosslinked structure are used, the matte acrylic resin film becomes brittle. Depending on the amount added, it may be difficult to handle the film in the film forming process, or in-mold molding. Alternatively, when the insert molding is used under severe conditions such as deep drawing, the film may be broken or torn.

  In addition, when used for vehicle interior applications, scratch resistance is required, so although these acrylic resin films have reached a certain level, the surface wears over time, so they can be used for a long time. In such a case, the appearance may have a glossy appearance.

  The acrylic resin film described in Patent Document 7 is said to be excellent in weather resistance, solvent resistance, stress whitening resistance, water whitening resistance and matteness. However, since this acrylic resin film contains a matting material in the acrylic resin film substrate, there are restrictions on the matting material that can be used. Further, Patent Document 7 has no description regarding the use of an acrylic resin film for insert molding or in-mold molding, and further has no description regarding surface hardness and heat resistance. Moreover, neither the surface hardness nor the heat resistance of the acrylic resin film having the composition described in the examples has reached the level required for a vehicle member.

  The matte acrylic resin film described in Patent Document 8 is excellent in bending whitening resistance and does not cause printing omission. However, since the core-shell type acrylic cross-linked polymer used as a matting material has a soft core portion, the surface hardness of the matte acrylic resin film is lowered. Moreover, neither the surface hardness nor the heat resistance of the matte acrylic resin film described in the Examples has reached the level required for a vehicle member.

  The acrylic resin film described in Patent Document 9 is said to be able to maintain good matte properties after molding. However, since the matte layer is made of a heat or photocurable resin, the matte layer may be broken when the acrylic resin film substrate is stretched during vacuum molding during in-mold molding or insert molding. In particular, in the matte acrylic resin film described in the examples, the matting layer is easy to break, and thus there are restrictions on molding conditions. In addition, when the matte layer is formed by a printing method or a coating method, the physical properties of the acrylic resin film serving as the substrate are lowered by the solvent attack.

  In addition, when used for vehicle interior applications, scratch resistance is required, so although these acrylic resin films have reached a certain level, the surface wears over time, so they can be used for a long time. In such a case, the appearance may have a glossy appearance. In order to improve the scratch resistance, a wax is often used, but there is no description about an optimal wax.

  The matte layer of the matte acrylic insert film described in Patent Document 10 is a layer made of a matte material of fluororesin-based true spherical fine particles and a binder resin. However, Patent Document 10 does not describe the optimum type and particle size of the matte material. There is no specific description of the wax. It is considered that the fluororesin-based spherical fine particles also play a role of wax, but there is a possibility that there is a problem in the long run property. Furthermore, the curable resin used as the binder resin is not specifically described. Moreover, there is no specific description regarding a transparent acrylic resin film base | substrate. For example, when the acrylic resin films described in Patent Documents 1 to 4 are used as the acrylic resin film substrate, there is a concern about the molding whitening resistance at the time of in-mold molding or insert molding.

  Specifically, in the acrylic resin films described in Patent Literatures 1 to 4, (1) To remove unnecessary portions of the acrylic resin film after insert molding, after vacuum molding, or from in-mold molding, from the base resin When punching is performed to remove the protruding acrylic resin film, whitening occurs at the end of the molded product, and the design of the molded product is impaired. (2) When removing a molded product with an undercut design from the mold (3) When using a mold with dents or protrusions to obtain a molded product with a concavo-convex design such as letters, the acrylic resin film remains on the dents or protrusions even after vacuum or pressure forming. Since the base resin must be injection molded without following the mold and the acrylic resin film temperature is below Tg, the film is stretched by the resin pressure. Whitening occurs, it cracked in some cases with.

  Thus, when the acrylic resin films described in Patent Documents 1 to 4 are used, due to the problem of resistance to molding whitening, it is necessary to remove the film that protrudes manually instead of punching, and there are design restrictions. In some cases, the industrial utility value is low, for example, an operation step of removing the whiteness by reheating the whitened portion is necessary.

  Insert molding may be performed using a laminated sheet made of an acrylic resin film and a base sheet. At this time, if the heat shrinkage rate of the acrylic resin film is large, the acrylic resin film is peeled off from the base sheet during insert molding. However, Patent Documents 9 and 10 specifically describe the heat shrinkage rate of the acrylic resin film. There is no.

  Since the sheet for suede tone molding described in Patent Document 11 uses an ionizing radiation curable resin as a binder resin for a coating film, the ionizing radiation curable resin and the base film have different moldability. Therefore, when it is formed into a deep-drawn shape during in-mold molding or insert molding, the industrial application value is low because molding defects such as cracking and tearing of the coating film occur due to insufficient stretching of the coating film. . Patent Document 11 does not describe means for solving this problem, and does not describe an acrylic resin film suitable for the base film.

In addition, the addition of wax is described to improve the scratch resistance, but when it is molded into a deep drawing shape during in-mold molding or insert molding, mold contamination may occur depending on the type of wax. The utility value is low. Patent Document 11 does not specifically describe means for solving this problem.
JP-A-8-323934 Japanese Patent Laid-Open No. 11-147237 JP 2002-080678 A JP 2002-080679 A Japanese Patent Laid-Open No. 10-237261 JP 2002-361712 A JP 07-238202 A JP 2002-254495 A JP 2003-111598 A Japanese Patent Laid-Open No. 10-034703 Japanese Patent Publication No. 07-110531

  That is, the present invention expresses excellent scratch resistance that is difficult to realize when a matte layer made of a matting material and a binder resin is simply formed on an acrylic resin film substrate, and performs insert molding or in-mold molding. Provides a matte acrylic resin film that does not crack in the matte layer even when molded into a deep-drawn shape, and has the surface hardness, chemical resistance, heat resistance, and matte properties required for automotive components The purpose is to do.

  Another object of the present invention is to provide an optimum production method for obtaining the matte acrylic resin film.

  Furthermore, an object of the present invention is to provide a laminate in which the matte acrylic resin film is laminated on a base material.

  The present invention is a matte acrylic resin film having a matte layer containing an acrylic resin film substrate and a matting material, an anti-scratch agent and a binder resin provided on the substrate.

  Moreover, this invention is the said matt acrylic resin film which has a pattern layer on the surface opposite to the surface in which the matt layer of the acrylic resin film base | substrate was provided.

  The present invention also provides a glossy layer for forming a matte layer by applying a paint having a matte material, an anti-scratch agent and a binder resin as essential components on the surface of an acrylic resin film substrate by a printing method or a coating method. It is a manufacturing method of an erase acrylic resin film.

  The present invention also provides the above-mentioned method for producing a matte acrylic resin film, wherein the scratch preventing agent is a polyolefin wax.

  Furthermore, this invention is the laminated body which laminated | stacked the said matt acrylic resin film on the base material.

  The matte acrylic resin film of the present invention expresses excellent scratch resistance, which is difficult to realize when a matte layer comprising a matting material and a binder resin is simply formed on an acrylic resin film substrate, and insert molding or Even if it is molded in-mold and formed into a deep-drawn shape, the matte layer does not crack and has the surface hardness, chemical resistance, heat resistance, and matte properties required for vehicle components It is.

  Moreover, according to the manufacturing method of the mat | matte acrylic resin film of this invention, such a mat | matte acrylic resin film can be manufactured stably.

  Furthermore, the laminate of the present invention is excellent in design, has scratch resistance, surface hardness, chemical resistance, heat resistance, and matte properties, and the surface matte layer has no defects such as cracks.

<Matte acrylic resin film>
The matte acrylic resin film of the present invention comprises at least an acrylic resin film substrate and a matte layer containing a matting material, a scratch inhibitor and a binder resin on one surface of the substrate.

(Hardness of matte layer surface)
The matte acrylic resin film of the present invention preferably has a matte layer surface hardness (pencil hardness based on JIS K5600-5-4: 1999) of 2B or more. When the matte layer surface hardness is 2B or more, the matte acrylic resin film surface is hardly damaged during the insert molding or in-mold molding process, and the scratch resistance of the laminate is also improved.

  Considering the case where it is used in a laminate such as a vehicle member, the hardness of the matte layer surface of the matte acrylic resin film of the present invention is more preferably HB or more. Laminates using a matte acrylic resin film with a matte layer surface hardness of HB or higher are suitable for use in various vehicle components such as door waist garnish, front control panel, power window switch panel, and air bag cover. can do. It is very useful industrially from the viewpoint of expanding applications.

  Further, if the hardness of the matte layer surface is F or more, scratches are not noticeable even when scratched with a coarse cloth such as gauze, and it is equivalent to a laminate using a conventional acrylic resin film having a surface hardness of 2H. Since practical scratch resistance can be imparted, the industrial utility value is very high.

  When a known thermosetting resin or photocurable resin is used as the binder resin for the matte layer, the hardness of the acrylic resin film serving as the substrate can be maintained or increased. Impairs moldability and insert moldability. In other words, due to the high crosslink density, when the matte acrylic resin film is stretched during vacuum forming, the matte layer cannot follow the elongation of the acrylic resin film substrate, resulting in poor adhesion, cracking, and tearing. May occur. On the other hand, in order to improve the in-mold moldability and insert moldability, it is necessary to reduce the cross-linked structure density, and the surface hardness tends to deteriorate. When using a thermosetting resin or a photocurable resin, it is important to optimize the crosslink density structure and balance the surface hardness and moldability.

<Acrylic resin film substrate>
(Heat shrinkage of acrylic resin film substrate)
The acrylic resin film base is preferably one that does not shrink as much as possible during heating. In a matte acrylic resin film consisting of two layers, a matte layer and an acrylic resin film substrate, if the shrinkage rate during heating of the acrylic resin film substrate is large, the matte layer will not be formed when heated and molded during vacuum forming. It becomes impossible to follow the shrinkage of the acrylic resin film substrate, and the adhesiveness is lowered.

  As the acrylic resin film substrate, an acrylic resin film substrate having a MD direction heat shrinkage of 50% or less and a TD direction heat shrinkage of −10 to 10% by heat treatment at 130 ° C. for 60 minutes is preferable. Such an acrylic resin film substrate is subjected to insert molding or in-mold molding, resulting in good adhesion between the matte layer and the acrylic resin film substrate when formed into a laminate, and has high industrial utility value. Specifically, in a laminate for use in vehicles, a laminate that does not peel at the interface between the matte layer and the acrylic resin film substrate when the adhesion between the matte acrylic resin film and the laminate substrate is evaluated. Is obtained. In addition, when a laminated sheet obtained by laminating a matte acrylic resin film on a base sheet is used as a decorative film or sheet, the base sheet and the acrylic resin film base are heated during insert molding or in-mold molding. From the viewpoint of suppressing peeling at the interface, it is preferable that the acrylic resin film substrate has a small shrinkage ratio upon heating. The MD direction heat shrinkage of the acrylic resin film substrate is preferably 30% or less, and more preferably 15% or less. Moreover, 0% or more is preferable. The TD-direction heat shrinkage of the acrylic resin film substrate is preferably 0 to 5%.

The measurement of the heat shrinkage rate is performed as follows. First, three parallel straight lines are drawn at intervals of 5 cm in the MD direction (flow direction during film formation) and the TD direction (direction perpendicular to the MD direction) on the surface of the acrylic resin film substrate cut out to A4 size. Measure the interval accurately with calipers. The interval is measured at two locations, and the measured locations are marked. Thereafter, the sample is left in an atmosphere at 130 ° C. for 60 minutes and taken out, and then the interval between the same positions as previously measured is measured again. The heat shrinkage rate is calculated from the following formula using the average value of the distance between the two locations.
Heat shrinkage rate (%) = ((interval before heating−interval after heating) / interval before heating) × 100

  In the acrylic resin film in which the MD direction and the TD direction are unknown, in order to specify the MD direction and the TD direction, first, a circle is drawn on the film, and the circle on the film obtained by heat treatment under the above conditions From the shape (or an ellipse if there is anisotropy), the direction in which the shrinkage rate is maximized is determined, the direction is the MD direction, and the direction perpendicular to the direction is the TD direction.

(Hardness of acrylic resin film substrate)
The hardness of the acrylic resin film substrate (pencil hardness based on JIS K5600-5-4: 1999) is desirably 2B or more, and is preferably HB or more in order to increase the surface hardness of the matte acrylic resin film of the present invention. Is preferably F or more, more preferably 2H or more.

(Rubber-containing polymer (I '))
The acrylic resin film substrate is preferably made of an acrylic resin composition (III) containing the following rubber-containing polymer (I ′) in order to make its hardness 2B or more.

  The rubber-containing polymer (I ′) is a monomer having a methacrylic acid alkyl ester as a main component in the presence of an elastic polymer obtained by polymerizing a monomer (i) having an acrylic acid alkyl ester as a main component. 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, when polymerizing each monomer (i) and (ii), the elastic polymer and the hard polymer can be polymerized at once or can be polymerized in two or more stages. .

  As the alkyl acrylate ester that is the main component of the monomer (i), various conventionally known alkyl acrylate esters can be used. In particular, butyl acrylate, 2-ethylhexyl acrylate, and the like are preferable.

  35-99.9 mass% is preferable in the total monomer (i) (100 mass%), and, as for the usage-amount of acrylic acid alkylester, 50-99.9 mass% is more preferable. The moldability of a film becomes favorable as the usage-amount of acrylic acid alkylester is 35 mass% or more.

  Even when the monomer (i) is polymerized in two or more stages when the elastic polymer is obtained, the amount of alkyl acrylate ester used is 35% by mass or more in the monomer (i). Good. 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), other vinyl monomers copolymerizable therewith can be used together with the alkyl acrylate ester. When other vinyl monomers are used, the amount used is preferably 64.9% by mass or less in the total monomer (i) (100% by mass). 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). Examples of the crosslinkable monomer include ethylene glycol dimethacrylate, butanediol dimethacrylate, allyl acrylate, allyl methacrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, diallyl maleate , Trimethylolpropane triacrylate, and allyl cinnamate. These can be used individually by 1 type or in combination of 2 or more types. As for the usage-amount of a crosslinkable monomer, 0.1-10 mass% is preferable in all the monomers (i) (100 mass%).

  Examples of the alkyl methacrylate that is the main component of the monomer (ii) used for the graft polymerization include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, and the like. As for the usage-amount of the methacrylic acid alkylester, 50 mass% or more is preferable in all the monomers (ii) (100 mass%).

  As the monomer (ii), other vinyl monomers copolymerizable therewith can be used together with the methacrylic acid alkyl ester. When other vinyl monomers are used, the amount used is preferably 50% by mass or less in the total monomer (ii) (100% by mass). As other vinyl monomers, for example, acrylic acid alkyl esters such as methyl acrylate, butyl acrylate, cyclohexyl acrylate, styrene, acrylonitrile and the like are preferable. These can be used individually by 1 type or in combination of 2 or more types.

  In the case of polymerizing the rubber-containing polymer (I ′), the amount of the monomer (ii) mainly composed of methacrylic acid alkyl ester is 100 parts by mass of the monomer (i) mainly composed of acrylic acid alkyl ester. The amount is preferably 10 to 400 parts by mass, more preferably 20 to 200 parts by mass.

  The average particle size of the rubber-containing polymer (I ′) is preferably from 0.01 to 0.5 μm, more preferably from 0.08 to 0.3 μm. In particular, the average particle diameter of the rubber-containing polymer (I ′) is preferably 0.08 μm or more from the viewpoint of film forming properties and handleability of the resulting matte acrylic resin film.

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

  A known polymerization initiator can be appropriately selected and used as the polymerization initiator. Further, the polymerization initiator may be added to either one of the aqueous phase or the monomer phase or to both.

  Examples of the emulsifier used in the emulsion polymerization include anionic, cationic and nonionic surfactants, and anionic surfactants are particularly preferable. Anionic surfactants include, for example, carboxylate surfactants such as potassium oleate, sodium stearate, sodium myristate, sodium N-lauroyl sarcosinate, dipotassium alkenyl succinate; sulfate esters such as sodium lauryl sulfate Salt surfactants; sulfonate surfactants such as sodium dioctylsulfosuccinate, sodium dodecylbenzenesulfonate, sodium alkyldiphenyl ether disulfonate; phosphate ester surfactants such as sodium polyoxyethylene alkylphenyl ether phosphate Agents and the like.

  The polymer latex obtained by emulsion polymerization is, for example, filtered through a filter having an opening of 100 μm or less, and then recovered by a known method such as an acid precipitation coagulation method, a salting out coagulation method, a freeze drying method, or a spray drying method. The In the acid precipitation solidification method, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and organic acids such as acetic acid can be used. In the salting out coagulation method, inorganic salts such as sodium sulfate, magnesium sulfate, aluminum sulfate and calcium chloride, and organic salts such as calcium acetate and magnesium acetate can be used. The coagulated polymer is further washed, dehydrated, dried and the like to obtain a rubber-containing polymer (I ′).

(Rubber-containing multistage polymer (I))
The rubber-containing polymer (I ′) is more preferably a rubber-containing multistage polymer (I) shown below from the viewpoint of molding whitening resistance during in-mold molding or insert molding.

  The rubber-containing multistage polymer (I) is obtained by polymerizing the monomer components shown in Table 1. (1) Elastic polymer (IA), (2) Glass transition temperature is 25 to 100 ° C., elasticity The intermediate polymer (IB) having a composition different from that of the polymer (IA), and (3) the hard polymer (IC) are polymerized in this order. In the rubber-containing multistage polymer (I), the elastic polymer (IA) corresponds to the elastic polymer in the rubber-containing polymer (I ′), and the intermediate polymer (IB) and the hard polymer (I -C) corresponds to the hard polymer in the rubber-containing polymer (I '). Here, “different composition” means that the kind and / or amount of at least one component of the monomer component which is a raw material of each polymer is different.

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

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

  Other monomers (I-A3) having a copolymerizable double bond include acrylic monomers such as lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, methacrylic acid, styrene, alkyl-substituted styrene, acrylonitrile And methacrylonitrile. These can be used alone or in admixture of two or more.

  The polyfunctional monomer (I-A4) is defined as a monomer having two or more copolymerizable double bonds in one molecule. As the polyfunctional monomer (I-A4), alkylene glycol dimethacrylates such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and propylene glycol dimethacrylate are preferable. In addition, polyvinylbenzene such as divinylbenzene and trivinylbenzene can be used. In addition, triallyl cyanurate, triallyl isocyanurate and the like are also useful. These can be used alone or in admixture of two or more. Of these, 1,3-butylene glycol dimethacrylate is preferred. Even when no polyfunctional monomer (I-A4) is used, a fairly stable rubber-containing multistage polymer (I) is obtained as long as the grafting agent (I-A5) is present. The polyfunctional monomer (I-A4) is arbitrarily used depending on the purpose, for example, when the hot strength or the like is strictly required.

  The graft crossing agent (I-A5) is defined as a monomer having two or more different copolymerizable double bonds in one molecule. Specific examples thereof include esters of copolymerizable α, β-unsaturated carboxylic acid or dicarboxylic acid such as allyl, methallyl, crotyl and the like. Particularly preferred are allyl esters of acrylic acid, methacrylic acid, maleic acid, or fumaric acid. Of these, allyl methacrylate is preferable because it has excellent effects. These can be used alone or in admixture of two or more. In the graft crossing agent (I-A5), the conjugated unsaturated bond of the ester reacts much faster than the allyl group, methallyl group, and crotyl group, and chemically bonds.

  The raw material monomer component of the elastic polymer (IA) may be polymerized in the presence of a chain transfer agent.

  The content of the acrylic acid alkyl ester (I-A1) is preferably 50 to 99.9% by mass in the raw material monomer component (100% by mass) of the elastic polymer (IA). In light of molding whitening resistance of the matte acrylic resin film obtained, 55% by mass or more is more preferable, and 60% by mass or more is particularly preferable. In addition, from the viewpoint of surface hardness and heat resistance of the matte acrylic resin film to be obtained, 79.9% by mass or less is more preferable, and 69.9% by mass or less is particularly preferable.

  The content of the methacrylic acid alkyl ester (I-A2) is preferably 0 to 49.9% by mass in the raw material monomer component (100% by mass) of the elastic polymer (IA). 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 other monomer (I-A3) having a copolymerizable double bond is preferably 0 to 20% by mass in the raw material monomer component (100% by mass) of the elastic polymer (IA). More preferably, it is 15 mass% or less.

  As for content of a polyfunctional monomer (IA-4), 0-10 mass% is preferable in the raw material monomer component (100 mass%) of an elastic polymer (IA). From the viewpoint of molding whitening resistance of the resulting matte acrylic resin film, it is more preferably 0.1% by mass or more, and particularly preferably 3% by mass or more. From the viewpoint of imparting sufficient flexibility and toughness to the resulting matte acrylic resin film, it is preferably 6% by mass or less, and particularly preferably 5% by mass or less.

  The content of the graft crossing agent (IA-5) is preferably 0.1 to 10% by mass in the raw material monomer component (100% by mass) of the elastic polymer (IA). By setting the content of the graft crossing agent (I-A5) to 0.1% by mass or more, the matte acrylic resin film obtained has good whitening resistance and does not deteriorate optical properties such as transparency. Can be molded. More preferably, it is 0.5 mass% or more. Moreover, sufficient softness | flexibility and toughness can be provided to the matt acrylic resin film obtained by making content of a graft crossing agent (I-A5) into 10 mass% or less. More preferably, it is 5 mass% or less, Most preferably, it is 2 mass% or less.

  The Tg (glass transition temperature) of the elastic polymer (IA) 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. The Tg in the present invention is a Tg calculated from the FOX equation using values described in Polymer Handbook (Polymer HandBook, J. Brandrup, Interscience, 1989).

  The amount of the raw material monomer component of the elastic polymer (IA) includes the raw material monomer component of the elastic polymer (IA), the raw material monomer component of the intermediate polymer (IB), and the hard 15-50 mass% is preferable in the total amount (100 mass%) of the raw material monomer component of a polymer (IC). By setting the amount of the raw material monomer component of the elastic polymer (IA) to 15% by mass or more, it is possible to impart molding whitening resistance to the matte acrylic resin film to be obtained. Both toughness required for molding and in-mold molding can be achieved. Moreover, the film which has surface hardness and heat resistance required for the laminated body of a vehicle member is obtained by making the amount of raw material monomer components of an elastic polymer (IA) into 50 mass% or less. More preferably, it is 35 mass% or less.

  When the elastic polymer (IA) is obtained, the raw material monomer component of the elastic polymer (IA) can be polymerized in a lump or in two or more stages. Polymerization is preferably carried out in stages. When the polymerization is performed in two or more stages, it is preferable that the constitutional ratio of the monomer units in each polymerization stage is different.

  When the elastic polymer (IA) is polymerized in two or more stages, from the viewpoint of molding whitening resistance, impact resistance, heat resistance and surface hardness of the matte acrylic resin film to be obtained, The polymerized elastic polymer (IA-1) preferably has a lower Tg than the polymerized elastic polymer (IA-2) in the second stage. Specifically, the first stage From the viewpoint of molding whitening resistance and impact resistance, the elastic polymer (IA-1) polymerized in the following manner preferably has a Tg of less than −30 ° C., and the elastic polymer polymerized in the second stage ( IA-2) preferably has a Tg of −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 monomer component amount used to obtain the first stage elastic polymer (IA-1) is the raw material single amount of the elastic polymer (IA). 1 to 20% by mass is preferable in the body component (100% by mass), and the amount of the monomer component used to obtain the second-stage elastic polymer (IA-2) is the elastic polymer (I− 80-99 mass% is preferable in the raw material monomer component (100 mass%) of A).

  The acrylic acid alkyl ester (I-B1) may have a linear or branched alkyl group. Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. These can be used alone or in admixture of two or more. Of these, methyl acrylate and n-butyl acrylate are preferred.

  The alkyl methacrylate (I-B2) may have a linear or branched alkyl group. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate. These can be used individually or in mixture of 2 or more types. Of these, methyl methacrylate is preferred.

  Examples of other monomers having a copolymerizable double bond (I-B3) include acrylic monomers such as lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, and methacrylic acid, styrene, alkyl-substituted styrene, Examples include acrylonitrile and methacrylonitrile. These can be used individually or in mixture of 2 or more types.

  As the polyfunctional monomer (I-B4), alkylene glycol dimethacrylates such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and propylene glycol dimethacrylate are preferable. In addition, polyvinylbenzene such as divinylbenzene and trivinylbenzene can be used. In addition, triallyl cyanurate, triallyl isocyanurate and the like are also useful. Of these, 1,3-butylene glycol dimethacrylate is preferred. These can be used individually or in mixture of 2 or more types. Even when no polyfunctional monomer (I-B4) is used, a fairly stable rubber-containing multistage polymer (I) is obtained as long as the grafting agent (I-B5) is present. The polyfunctional monomer (I-B4) can be arbitrarily used depending on the purpose, for example, when the hot strength or the like is strictly required.

  Examples of the graft crossing agent (I-B5) include esters of copolymerizable α, β-unsaturated carboxylic acid or dicarboxylic acid such as allyl, methallyl, crotyl and the like. 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. These can be used individually or in mixture of 2 or more types. In the graft crossing agent (I-B5), the conjugated unsaturated bond of the ester reacts much faster than the allyl group, methallyl group, and crotyl group, and chemically bonds.

  The raw material monomer component of the intermediate polymer (IB) may be polymerized in the presence of a chain transfer agent.

  The content of the acrylic acid alkyl ester (IB1) is preferably 9.9 to 90% by mass in the raw material monomer component (100% by mass) of the intermediate polymer (IB). From the viewpoint of molding whitening resistance, surface hardness, and heat resistance of the resulting 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 (IB2) is preferably 9.9 to 90% by mass in the raw material monomer component (100% by mass) of the intermediate polymer (IB). From the viewpoint of molding whitening resistance, surface hardness, and heat resistance of the resulting 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.

  Content of the other monomer (IB3) having a copolymerizable double bond is 0 to 20% by mass in the raw material monomer component (100% by mass) of the intermediate polymer (IB). Is preferred. More preferably, it is 15 mass% or less.

  The content of the polyfunctional monomer (IB4) is preferably 0 to 10% by mass in the raw material monomer component (100% by mass) of the intermediate polymer (IB). From the viewpoint of imparting sufficient flexibility and toughness to the matte acrylic resin film to be obtained, it is preferably 6% by mass or less, particularly preferably 3% by mass or less.

  The content of the graft crossing agent (IB5) is preferably 0.1 to 10% by mass in the raw material monomer component (100% by mass) of the intermediate polymer (IB). By making the content of the graft crossing agent (I-B5) 0.1% by mass or more, the resulting matte acrylic resin film has good molding whitening resistance and does not deteriorate optical properties such as transparency. Can be molded. More preferably, it is 0.5 mass% or more. Moreover, sufficient softness | flexibility and toughness can be provided to the matt acrylic resin film obtained by making content of a graft crossing agent (I-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 (IB) alone is preferably 25 to 100 ° C. When Tg is 25 ° C. or higher, the surface hardness and heat resistance of the resulting matte acrylic resin film are at the levels required for the 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, the matt acrylic resin 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.

  In this way, a matte acrylic having both molding whitening resistance, surface hardness and heat resistance, which has been difficult to achieve by providing the intermediate polymer (IB) having a specific composition and Tg. A resin film can be obtained.

  When the intermediate polymer (IB) is polymerized, the amount of raw material monomer component of the intermediate polymer is as follows: the raw material monomer component of the elastic polymer, the raw material monomer component of the intermediate polymer, and the raw material of the hard polymer 5-35 mass% is preferable in the total amount (100 mass%) of a monomer component. Within this range, the function of the intermediate polymer (IB) important for achieving both the above-described molding whitening resistance, surface hardness, and heat resistance can be exhibited, and the matte obtained can be obtained. Other physical properties of the acrylic resin film, for example, film-forming property and toughness required for insert molding and in-mold molding can be imparted. More preferably, it is 20 mass% or less.

  When obtaining the intermediate polymer (IB), the raw material monomer components of the intermediate polymer (IB) can be polymerized in a lump, or can be polymerized in two or more stages.

  The alkyl methacrylate (I-C1) may have a linear or branched alkyl group. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate. These can be used individually or in mixture of 2 or more types. Of these, methyl methacrylate is preferred.

  The alkyl acrylate (I-C2) may have a linear or branched alkyl group. Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. These can be used alone or in admixture of two or more. Of these, methyl acrylate and n-butyl acrylate are preferred.

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

  The content of the methacrylic acid alkyl ester (I-C1) is preferably 80 to 100% by mass in the raw material monomer component (100% by mass) of the hard polymer (IC). From the viewpoint of the surface hardness and heat resistance of the resulting 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 (I-C2) is preferably 0 to 20% by mass in the raw material monomer component (100% by mass) of the hard polymer (IC). 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 (IC3) having a copolymerizable double bond is 0 to 20% by mass in the raw material monomer component (100% by mass) of the hard polymer (IC). Is preferred. More preferably, it is 15 mass% or less.

  A chain transfer agent can be used during the polymerization of the raw material monomer component of the hard polymer (IC) to adjust the molecular weight of the hard polymer (IC). The chain transfer agent can be selected from those used in normal radical polymerization. Specific examples include alkyl mercaptans having 2 to 20 carbon atoms, mercapto acids, thiophenol, carbon tetrachloride and the like. These can be used individually or in mixture of 2 or more types. As for content of a chain transfer agent, 0.01-5 mass parts is preferable with respect to 100 mass parts of raw material monomer components of a hard polymer (IC). 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 (IC) alone is preferably 60 ° C. or higher. When Tg is 60 ° C. or higher, a matte acrylic resin 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 (IC), the amount of the raw material monomer component of the hard polymer (IC) is the same as the amount of the raw material monomer component of the elastic polymer (IA), the intermediate polymer (I). 15-80 mass% is preferable in the total amount (100 mass%) of the raw material monomer component of -B) and the raw material monomer component of hard polymer (IC). If the quantity of the raw material monomer component of hard polymer (IC) is 15 mass% or more, the surface hardness and heat resistance of the matte acrylic resin film obtained will become favorable. More preferably, it is 45 mass% or more. If the amount of the raw material monomer component of the hard polymer (IC) is 80% by mass or less, the resulting matte acrylic resin film is imparted with molding whitening resistance, toughness necessary for insert molding and in-mold molding can do.

  When obtaining the hard polymer (IC), the monomer component that is the raw material of the hard polymer (IC) can be polymerized in a lump or in two or more stages. .

The gel content of the rubber-containing multistage polymer (I) is preferably 50% by mass or more, and more preferably 60% by mass or more from the viewpoint of obtaining more excellent molding whitening resistance. From the viewpoint of molding whitening resistance, the larger the gel content, the more advantageous, but from the viewpoint of easy moldability, the presence of a certain amount or more of free polymer is necessary, so the gel content is 80% by mass or less. Is preferred. The gel content means that a predetermined amount (mass before extraction) of the rubber-containing multistage polymer (I) is extracted under reflux in an acetone solvent, the treated solution is separated by centrifugation, dried, and then insoluble in acetone. The mass is measured (mass after extraction), and is a value calculated by the following formula.
Gel content (mass%) = (mass after extraction (g) / mass before extraction (g)) × 100

  The mass average particle diameter of the rubber-containing multistage polymer (I) is preferably 0.03 to 0.3 μm. From the viewpoint of the mechanical properties of the matte acrylic resin film obtained, it is more preferably 0.07 μm or more, particularly preferably 0.09 μm or more. In addition, from the viewpoint of molding whitening resistance and transparency of the matte acrylic resin film to be obtained, it is more preferably 0.15 μm or less, and particularly preferably 0.13 μm or less. The mass average particle diameter is measured by a dynamic light scattering method using a light scattering photometer DLS-700 (trade name) manufactured by Otsuka Electronics Co., Ltd.

  As the method for producing the rubber-containing multistage polymer (I), the sequential multistage polymerization method by the 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 polymer (IC) is converted into a suspension polymerization system.

  When the rubber-containing multistage polymer (I) is produced by emulsion polymerization, the raw material monomer component of the elastic polymer (IA) in the rubber-containing multistage polymer (I) is previously mixed with water and a surfactant. The emulsion prepared in this manner is supplied to the reactor for polymerization, and then the raw material monomer component of the intermediate polymer (IB) and the raw material monomer component of the hard polymer (IC) are sequentially added. A method of supplying to the reactor and polymerizing is preferable.

  When an emulsion prepared by mixing the raw material monomer component of the elastic polymer (IA) with water and a surfactant in advance is supplied to the reactor and polymerized to be dispersed in acetone. The rubber-containing multistage polymer (I) 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 multistage polymer (I) can be easily obtained. The matte acrylic resin film using the rubber-containing multi-stage polymer (I) thus obtained as a raw material has a characteristic that the number of fish eyes in the film is small, and printing failure is particularly likely to occur, and the printing pressure is low. Even when light-colored gravure printing or solid gravure printing such as metallic tone or jet black tone is applied, it is preferable because there is little printing loss and high level printability.

  As the surfactant used in preparing the emulsion, anionic, cationic and nonionic surfactants can be used, and anionic surfactants are particularly preferable. Examples of anionic surfactants include rosin soap, potassium oleate, sodium stearate, sodium myristate, sodium N-lauroylsarcosate, dipotassium alkenyl succinate; sulfate esters such as sodium lauryl sulfate; dioctyl Sulfonates such as sodium sulfosuccinate, sodium dodecylbenzenesulfonate, sodium alkyldiphenyl ether disulfonate; phosphate esters such as sodium polyoxyethylene alkylphenyl ether phosphate; phosphate esters such as sodium polyoxyethylene alkyl ether phosphate Examples include salts. Among these, phosphate ester salts such as sodium polyoxyethylene alkyl ether phosphate are preferable. Preferred specific examples of the surfactant include NC-718 manufactured by Sanyo Chemical Industries, Ltd., Phosphanol LS-529, Phosphanol RS-610NA, and Phosphanol RS-620NA manufactured by Toho Chemical Industry Co., Ltd. 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.

  As a method for preparing an emulsion, a method in which a monomer component is charged into water and then a surfactant is added; a method in which a surfactant is charged in water and then a monomer component is charged; a monomer component Examples thereof include a method in which water is added after a surfactant is charged therein. Of these methods, a method in which a monomer component is charged in water and then a surfactant is charged, and a method in which a monomer component is charged after a surfactant is charged in water are preferable.

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

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

  As the polymerization initiator used for forming the elastic polymer (IA), the intermediate polymer (IB), and the hard polymer (IC), known ones can be used. Examples of the polymerization initiator include peroxides, azo initiators, or redox initiators in which an oxidizing agent / reducing agent is combined. Among these, redox initiators are preferable, and in particular, ferrous sulfate / ethylenediamine. A sulfoxylate-based initiator in which tetrasodium disodium salt / longalite / hydroperoxide is combined is preferable. What is necessary is just to determine the addition amount of a polymerization initiator suitably according to superposition | polymerization conditions.

  The polymerization initiator can be added to the aqueous phase or the monomer phase (oil phase) or both.

  As a method for obtaining the rubber-containing multistage polymer (I), in particular, after raising the aqueous solution containing ferrous sulfate, ethylenediaminetetraacetic acid disodium salt and Rongalite charged in the reactor to the polymerization temperature, the elastic polymer An emulsion prepared by mixing a raw material monomer component of (IA) and a polymerization initiator such as peroxide with water and a surfactant is supplied to a reactor for polymerization, and then an intermediate polymer ( The raw material monomer component of IB) is supplied to the reactor together with a polymerization initiator such as peroxide to polymerize, and finally, the raw material monomer component of the hard polymer (IC) is converted to the peroxide. A method in which the polymerization is carried out by supplying it to a reactor together with a polymerization initiator and the like.

  The polymerization temperature varies depending on the type and amount of the polymerization initiator used, but 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.

  It is preferable to treat the polymer latex containing the rubber-containing multistage polymer (I) obtained by the above method, using a filtration device provided with a filter medium as necessary. This filtration treatment is a treatment for removing scales generated during the polymerization from the latex, and removing impurities mixed in from the polymerization raw material or from the outside during the polymerization.

  As a filtering device with a filter medium, a GAF filter system (trade name) of ISP Filters PTE Ltd. using a bag-shaped mesh filter; a cylindrical filter medium is arranged on the inner surface of a cylindrical filter chamber; A centrifugal type filtration device in which a stirring blade is disposed in the filter medium; or a vibration type filter device in which the filter medium performs horizontal circular motion and vertical amplitude motion with respect to the filter medium surface is preferable.

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

  When the rubber-containing multistage polymer (I) is recovered by salting out coagulation using a metal salt, the residual metal content in the finally obtained rubber-containing multistage polymer (I) is preferably 800 ppm or less. . 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 rubber-containing multistage polymer (I When a matte acrylic resin film made from) is immersed in boiling water, whitening occurs, which is a serious problem in practice. In addition, although 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, the amount of residual metal is It is desirable to make it 800 ppm or less, and it is so good that it is a trace amount.

(Thermoplastic polymer (II))
As the raw material for the acrylic resin film substrate, the rubber-containing polymer (I ′) (preferably the rubber-containing multistage polymer (I)) may be used alone, but the rubber-containing polymer (I ′) (preferably containing the rubber) It is preferable to use an acrylic resin composition (III) containing a multistage polymer (I)) and a thermoplastic polymer (II) shown below.

  As thermoplastic polymer (II), what has a methacrylic acid alkylester (II-A) unit as a main component is preferable. Specifically, it has a C1-C4 methacrylic acid alkyl ester (II-A) 50-100 mass%, an acrylic acid alkyl ester (II-B) 0-50 mass%, and a copolymerizable double bond. The other monomer (II-C) is obtained by polymerizing a raw material monomer component composed of 0 to 50% by mass, and reduced viscosity (0.1 g of a polymer is dissolved in 100 mL of chloroform). , Measured at 25 ° C.) is preferably 0.15 L / g or less. By using such a thermoplastic polymer (II) in combination, the surface hardness and heat resistance of the matte acrylic resin film obtained can be increased. Accordingly, the Tg of the thermoplastic polymer (II) is preferably 80 ° C. or higher, more preferably 90 ° C. or higher.

  Examples of the alkyl methacrylate (II-A) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate. Of these, methyl methacrylate is preferred. These can be used alone or in admixture of two or more.

  Examples of the acrylic acid alkyl ester (II-B) include methyl acrylate, ethyl acrylate, propyl acrylate, and n-butyl acrylate. Of these, methyl acrylate is preferred. These can be used alone or in admixture of two or more.

  As another monomer (II-C) having a copolymerizable double bond, a known monomer can be used as necessary. For example, aromatic vinyl compounds such as styrene, vinyl cyanide monomers such as acrylonitrile, unsaturated dicarboxylic anhydrides such as maleic anhydride and itaconic anhydride, N-phenylmaleimide, N-cyclohexylmaleimide and the like can be mentioned. . These can be used alone or in admixture of two or more.

  The content of the methacrylic acid alkyl ester (II-A) is selected from the viewpoint of the surface hardness and heat resistance of the matte acrylic resin film obtained, in the raw material monomer component (100% by mass) of the thermoplastic polymer (II). 50 to 100% by 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 (II-B) is that of the thermoplastic polymer (II) from the viewpoint of imparting the toughness required for the matte acrylic resin film to be obtained and insert molding or in-mold molding. 0-50 mass% is preferable in a raw material monomer component (100 mass%). More preferably, it is 0.1 mass% or more and 20 mass% or less.

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

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

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

(Acrylic resin composition (III))
The acrylic resin film substrate may be a rubber-containing polymer (I ′) or a rubber-containing multistage polymer (I) alone as described above, but preferably an acrylic resin composition containing a thermoplastic polymer (II). It is preferable that it is a thing (III).

  When the rubber-containing polymer (I ′) is used together with the thermoplastic polymer (II), the content of the rubber-containing polymer (I ′) is an acrylic resin composition from the viewpoint of film formability, hardness, and moldability. 5-30 mass% is preferable in thing (III) (100 mass%). 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 film hardness.

  In the case of the acrylic resin composition (III) in which the rubber-containing multistage polymer (I) and the thermoplastic polymer (II) are used in combination, the rubber-containing multistage polymer (100 mass%) in the acrylic resin composition (III) (100% by mass) I) 1 to 99% by mass and thermoplastic polymer (II) 1 to 99% by mass are preferred. From the viewpoint of molding whitening resistance of the matte acrylic resin film obtained, the content of the rubber-containing multistage polymer (I) is more preferably 50% by mass or more, particularly preferably 70% by mass or more. The content of the thermoplastic polymer (II) is more preferably 50% by mass or less, particularly preferably 30% by mass or less.

It is preferable that the gel content rate of acrylic resin composition (III) 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. The gel content means that a predetermined amount (mass before extraction) of the acrylic resin composition (III) is extracted under reflux in an acetone solvent, this treated solution is separated by centrifugation, dried, and then mass of insoluble acetone. (Mass after extraction) is a value calculated by the following formula.
Gel content (mass%) = (mass after extraction (g) / mass before extraction (g)) × 100

(Thermoplastic polymer (IV))
As a raw material for the acrylic resin film substrate, apart from the thermoplastic polymer (II), a thermoplastic weight having a reduced viscosity (0.1 g of polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) exceeding 0.15 L / g. Combined (IV) may be used.

  The thermoplastic polymer (IV) is specifically 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 monomer components. Other monomers having a copolymerizable double bond can be used alone or in admixture of two or more.

  The thermoplastic polymer (IV) is a component that makes the film-forming property better. The thermoplastic polymer (IV) exceeds 0 parts by mass with respect to 100 parts by mass in total of the rubber-containing polymer (I ′) (rubber-containing multistage polymer (I)) and the thermoplastic polymer (II). It is preferable to use in the range of 20 parts by mass or less. More preferably, it is the range of 1-10 mass parts from a film film forming viewpoint.

(Combination agent)
Acrylic resin film base is a general compounding agent, for example, a stabilizer, a lubricant, a processing aid, a plasticizer, a foaming agent, a filler, an antibacterial agent, an antifungal agent, a release agent, and an antistatic agent, if necessary. , A colorant, an ultraviolet absorber, a light stabilizer and the like may be contained.

  In order to impart weather resistance to the acrylic resin film substrate, 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 performing vacuum molding or pressure molding in an injection mold can be prevented. In general, the higher the molecular weight of the ultraviolet absorber, the longer the bleed out after processing into a film will occur in the long term, and the ultraviolet absorption performance will be sustained for a longer period than the one having a low molecular weight. Furthermore, when the molecular weight of the ultraviolet absorber is 300 or more, the amount of the ultraviolet absorber that volatilizes before the acrylic resin film substrate is extruded from the T die and cooled by the cooling roll is small. Accordingly, the amount of the remaining ultraviolet absorber becomes sufficient, and good performance is exhibited. Also, the volatilized UV absorber recrystallizes on the chain or exhaust hood that suspends the T die at the top of the T die and grows over time, eventually falling on the film and causing defects 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 ultraviolet absorber is a total of rubber-containing polymer (I ′) (rubber-containing multistage polymer (I)), thermoplastic polymer (II) and thermoplastic polymer (IV) (hereinafter referred to as “acrylic resin raw material” and It is preferably used in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass. 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, and 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, the amount is more preferably 0.1 parts by mass, particularly preferably 0.2 parts by mass or more. 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 an acrylic resin raw material together with an acrylic resin raw material to an extruder for forming an acrylic resin film substrate; It is done. Examples of the kneader used in the latter method include ordinary single screw extruders, twin screw extruders, Banbury mixers, roll kneaders, and the like.

(Method for producing acrylic resin film substrate)
Examples of the method for producing the acrylic resin film substrate include known 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. Of these, the T-die method is preferred from the viewpoint of economy.

  When the acrylic resin film substrate is formed by the T-die method, it is preferable to use a method in which a film is formed by being sandwiched between a plurality of rolls or belts selected from metal rolls, non-metal rolls, and metal belts. According to this method, the surface smoothness of the resulting matte acrylic resin film is improved, the coating missing when forming the matte layer on the acrylic resin film substrate, and the printing missing when printing on the matte acrylic resin film. Can be suppressed. As a metal roll, a metallic mirror touch roll; used in a sleeve touch system comprising a metal sleeve (metal thin-film pipe) and a molding roll described in Japanese Patent No. 2808251 or International Publication No. 97/28950. Rolls and the like. Examples of the non-metallic roll include a touch roll made of silicon rubber. Examples of the metal belt include a metal endless belt. A plurality of these metal rolls, non-metal rolls and metal belts may be used in combination.

  In the method of forming a film by sandwiching a plurality of rolls or belts selected from metal rolls, non-metal rolls and metal belts, the raw material after melt extrusion is sandwiched in a state where there is substantially no bank (resin pool). However, it is preferable to form a film by transferring the surface without substantially rolling. When the film is formed without forming a bank (resin pool), the raw material in the cooling process is surface-transferred without being rolled, so the heat shrinkage rate of the acrylic resin film substrate formed by this method is reduced. be able to.

  Moreover, when performing melt extrusion by the T-die method or the like, it is also preferable to extrude while filtering the acrylic resin raw material in a molten state with a screen mesh of 200 mesh or more.

  The thickness of the acrylic resin film substrate is preferably 10 to 500 μm. By setting the thickness of the acrylic resin film substrate to 500 μm or less, rigidity suitable for insert molding and in-mold molding can be obtained, and the film can be manufactured more stably. Moreover, by making the thickness of the acrylic resin film substrate 10 μm or more, the sense of depth can be more sufficiently imparted to the resulting laminate together with the protection of the substrate. The thickness of the acrylic resin film substrate is more preferably 30 μm or more, and particularly preferably 50 μm or more. The thickness of the acrylic resin film substrate is more preferably 300 μm or less, and particularly preferably 200 μm or less.

<Matte layer>
The thickness of the matte layer provided on one side of the acrylic resin film substrate is preferably 0.1 to 5 μm. If the thickness of the matte layer is 0.1 μm or more, surface properties such as scratch resistance when it becomes a laminate can be exhibited. More preferably, it is 0.5 μm or more, and most preferably 0.8 μm or more. If the thickness of the matte layer is 5 μm or less, the amount of paint per unit area used in coating is reduced, so that the physical property deterioration of the acrylic resin film substrate due to the solvent can be reduced. Further, when the thickness of the matte layer is 5 μm or less, good matting properties can be expressed. By reducing the thickness of the matte layer, the matte property is exhibited well, so that the amount of the matte material per unit volume can be reduced, and the physical property deterioration of the matte layer can be reduced. In addition, by reducing the thickness of the matte layer, the effect of adding an anti-scratch agent is enhanced, so that good scratch resistance is exhibited. The thickness of the matte layer is preferably 3 μm or less, more preferably less than 2 μm.

  In addition, when a thermosetting resin or a photo-curable resin is used as the binder resin, insert molding or in-mold molding is performed by forming the mat layer to a thickness of 5 μm or less to form a deep drawing shape. Even in this case, the occurrence of cracks in the matte layer can be reduced. The thickness of the matte layer is preferably 3 μm or less, more preferably less than 2 μm.

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

(Matte material)
As the matting material, it is preferable to use organic or inorganic particles having a mass average particle diameter of 0.5 to 50 μm. From the viewpoint of matteness and appearance, the mass average particle diameter is more preferably 2 μm or more. By making the mass average particle diameter 2 μm or more, not only the matteness will be good, but also the reflection of fluorescent lamps will be reduced. For example, when combined with a metallic pattern, the appearance of scraping aluminum The appearance is rich in luxury. The mass average particle diameter is more preferably 30 μm or less, and particularly preferably 10 μm or less, from the viewpoints of moldability when forming the matte layer, appearance, and removal of the matting material from the binder resin. By making it 10 μm or less, not only the moldability of the matte layer will be improved, but also the reflection of the fluorescent lamp will be slightly visible, so when it is combined with a metallic pattern, for example, it looks close to the appearance of scraping aluminum It has a high-class appearance and high industrial utility value. For example, when a matte acrylic resin film is obtained by gravure coating or gravure reverse coating, the mass average particle diameter is more preferably 30 μm or less, and particularly preferably 10 μm or less, from the viewpoint of reducing doctor lines.

  Known materials can be used as the organic particles. Examples include silicone resins, styrene resins, styrene / acrylic resins, acrylic resins, fluororesins, benzoguanamine / formaldehyde condensates, benzoguanamine / melamine / formaldehyde condensates, and melamine / formaldehyde condensates.

  As a material for the organic particles, it is preferable to select a material having a refractive index as close as possible to that of the binder resin in order to make the pattern clear from the viewpoint of the design feeling when the pattern layer is formed. For example, when an acrylic resin is used as the binder resin, it is preferable to select beads made of cross-linked polymethyl methacrylate (cross-linked PMMA) as the matting material. On the contrary, the matte material can be selected according to the type of the pattern, such as a matte layer having a white feeling by using a matte material having a slightly different refractive index.

  Known materials can be used for the inorganic particles. For example, mica, talc, silica, calcium carbonate, titanium oxide, iron oxide and the like can be mentioned. In addition, inorganic particles surface-treated with an acrylic resin, a polyurethane resin, a surfactant, or the like can also be used. Of these, silica is particularly preferred from the viewpoints of the appearance and physical properties of the resulting matte acrylic resin film. As the silica, known ones that are commercially available can be used, for example, Mizusukasil (trade name) manufactured by Mizusawa Chemical Co., Ltd., Cicilia (trade name) manufactured by Fuji Silysia Chemical Ltd., and the like.

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

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

(Abrasion prevention agent)
As an anti-scratch agent, known natural waxes such as carnauba wax, wood wax, montan wax, paraffin wax, known synthetic waxes such as fatty acid amide, polyethylene, polypropylene, polytetrafluoroethylene, alkyl-modified silicone oil, Known silicone waxes such as polyether-modified silicone oil can be used. In addition, a block copolymer containing a silicone-based or fluorine-based component can be used.

  From the standpoint of mold contamination during in-mold molding and insert molding, the higher the melting point, the more difficult the wax is to bleed due to the heat during molding. Therefore, a wax having a melting point of 100 ° C. or higher is preferable, and 120 ° C. or higher is more preferable. 180 ° C. or higher is most preferable. In addition, regarding the block copolymer containing a silicone type and a fluorine-type component, it is possible to express the outstanding bleeding resistance even if melting | fusing point is 100 degrees C or less by selecting another copolymer component.

  Examples of the wax having such a melting point include polyethylene, polypropylene, a composite of polyethylene and polypropylene, and polytetrafluoroethylene. From the viewpoint of the melting point, a composite of polyethylene and polypropylene is more preferable, and polytetrafluoroethylene is particularly preferable. From the viewpoint of the effect of preventing scratches, polytetrafluoroethylene is more preferable, and polyethylene, polypropylene, and a composite of polyethylene and polypropylene are particularly preferable. Further, by using these in combination, it is possible to express more excellent scratch resistance, and a combination of polyethylene and polytetrafluoroethylene is particularly preferable.

  Since the scratch-preventing agent settles during coating, it is desirable that the specific gravity is small from the viewpoint of no sedimentation. For example, a material having a specific gravity of more than 2 such as polytetrafluoroethylene tends to settle, although it depends on the viscosity of the paint at the time of coating. If the wax settles down during coating, the amount of wax contained in the matte layer is reduced, resulting in a decrease in scratch resistance. In addition, white streaks generated by winding up the precipitated wax by the plate roll are matte acrylic resin film Transferred as a defect on top.

  Therefore, polyolefin-based waxes such as polyethylene, polypropylene, and a composite of polyethylene and polypropylene are preferable as the scratch-preventing agent.

  In many cases, a wax such as polyethylene, polypropylene, and polytetrafluoroethylene is used in the form of ultrafine powder obtained by dry pulverization. In the present invention, the wax has a mass average particle diameter larger than the thickness of the matte layer. Is preferably used. From the viewpoint of scratch resistance, it is more preferable to use a wax having a mass average particle diameter larger than a value obtained by doubling the thickness of the matte layer.

  The addition amount of the scratch preventing agent is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin. The addition amount of the scratch preventing agent is more preferably 3 parts by mass or more, particularly preferably 5 parts by mass or more, from the viewpoint of scratch resistance. The addition amount of the scratch preventing agent is preferably 20 parts by mass or less from the viewpoint of the scratch preventing effect.

(Binder resin)
As the binder resin, it is preferable to use a known acrylic thermoplastic resin from the viewpoints of in-mold moldability and insert moldability. Since the acrylic thermoplastic resin is very close to the moldability with the acrylic resin film substrate, it is not cracked or torn even if it is molded into a shape such as deep drawing. As the acrylic thermoplastic resin, for example, it is possible to use the thermoplastic polymer (II) mainly composed of the above-mentioned methacrylic acid alkyl ester unit, chemical resistance, weather resistance, heat resistance, pencil hardness, moldability, Particularly preferred from the viewpoint of transparency. The thermoplastic polymer (II) can be used for an acrylic resin film substrate, but its constituent components, amount used, characteristics, and production method may be appropriately selected independently.

  Moreover, it is preferable from a viewpoint of abrasion resistance to use well-known thermosetting resin and photocurable resin as binder resin. For example, acrylic resins, urethane acrylate resins, silicone acrylate resins, epoxy resins, and ester resins can be used. Of these, urethane acrylate resins are preferred from the viewpoint of physical properties.

  As the urethane acrylate resin, known resins can be used, and in particular, a hydroxyl group having a methacrylic acid alkyl ester unit as a main component, a hydroxyl value of 20 to 120 mgKOH / g, and a glass transition temperature of 50 to 110 ° C. A urethane acrylate-based thermosetting resin containing a containing acrylic resin and a known diisocyanate or / and polyisocyanate is preferred.

  The hydroxyl value of the hydroxyl group-containing acrylic resin is preferably 20 mgKOH / g or more, and more preferably 50 mgKOH / g or more, from the viewpoints of pencil hardness and scratch resistance on the surface of the matte layer. The hydroxyl value of the hydroxyl group-containing acrylic resin is preferably 120 mgKOH / g or less, more preferably 100 mgKOH / g or less, from the viewpoint of chemical resistance, adhesion, and cracking of the matte layer during molding.

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

  As the diisocyanate (curing agent), known ones can be used. In particular, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate and the like that cause little yellowing are preferable. . In addition, a known polyisocyanate can also be used from the viewpoint of volatility. For example, burettes, trimethylolpropane adducts, isocyanurate trimers, etc. containing the diisocyanates listed above as constituents are preferred.

  The diisocyanate and / or polyisocyanate may be used so as to have an addition amount corresponding to a range of 0.5 to 1.5 times as the molar amount of the isocyanate group with respect to the molar amount of the hydroxyl group in the hydroxyl group-containing acrylic resin. preferable. By setting it to 0.5 times or more, the amount of isocyanate groups is sufficient with respect to the hydroxyl group, so that the curing is sufficiently advanced and the pencil hardness and scratch resistance on the surface of the matte layer are improved. When the addition amount is 1.5 times or less, sufficient pencil hardness and scratch resistance on the surface of the matte layer will be exhibited, and the matte layer will not easily crack during molding, and the film of excess diisocyanate and / or polyisocyanate Problems such as blocking are less likely to occur.

  In order to further reduce cracking or tearing during in-mold molding or insert molding, or to improve the adhesion between the matte layer and the acrylic resin film substrate, it is preferable to add a known rubber-like material to the binder resin. .

  As the rubber-like material, the above-mentioned rubber-containing polymer (I ′) is preferable. By adding the rubber-containing polymer (I ′), cracking or tearing during in-mold molding or insert molding can be further reduced. Further, the adhesion between the matte layer and the acrylic resin film substrate is improved, and the matte layer is difficult to peel off during use of the laminate. Among the rubber-containing polymers (I ′), the rubber-containing multistage polymer (I) is preferable from the viewpoint of resistance to molding whitening. The rubber-containing polymer (I ′) and the rubber-containing multistage polymer (I) can be used for an acrylic resin film substrate, but their constituent components, amount used, characteristics, and production methods are independent of each other. Can be selected as appropriate.

  The amount of the rubber-containing polymer (I ′) added is determined by the amount of the elastic copolymer contained in the rubber-containing polymer (I ′) from the viewpoint of pencil hardness on the matte layer surface of the matte acrylic resin film. An amount of 50% by mass or less is preferable with respect to 100% by mass, an amount of 30% by mass or less is more preferable, and an amount of 20% by mass or less is particularly preferable.

  In addition, other known rubber-like materials may be added to the binder resin in order to improve moldability.

(Method of forming matte layer)
The matte layer can be formed by a known method. For example, after obtaining a film to become a matte layer by a known molding method such as a melt extrusion method such as a melt casting method, a T-die method, an inflation method, or a calendar method, an acrylic resin film substrate, a dry laminate, a wet Laminating methods such as laminating, laminating by hot melt laminating and the like can be mentioned. If heat fusion is possible, lamination can be performed by a hot press laminating method.

  Moreover, the lamination | stacking method by coextrusion shaping | molding, such as the method of extruding simultaneously the raw material used as a matte layer, and the acrylic resin raw material used as an acrylic resin film base | substrate, is mentioned. Specific examples include a method of bonding before a die such as a feed block method, a method of bonding inside a die such as a multi-manifold method, a method of bonding outside a die such as a multi-slot method, and the like.

  Also, a matte layer can be formed on a pre-formed acrylic resin film substrate. For example, an extrusion laminating method in which a raw material to be a matte layer is laminated on one surface of an acrylic resin film substrate while being melt-extruded into a film shape by a T die or the like can be used.

  However, when a matte material having a mass average particle diameter larger than the thickness of the matte layer is used, it is preferable to form the matte layer by a printing method or a coating method. In this case, the matte layer material is dissolved or dispersed in a solvent to prepare a paint, which is applied to one surface of the acrylic resin film substrate, and heated and dried to remove the solvent, thereby matting. A layer is formed. This method is preferable because the adhesion between the matte layer and the acrylic resin film substrate is improved.

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

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

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

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

  In addition, as the doctor blade used in the gravure coating method, known blades such as steel, stainless steel, and ceramic can be used. However, it is preferable to use a stainless doctor blade from the viewpoint of doctor muscles.

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

  As the solvent, a solvent having a boiling point not higher than 80 ° C., preferably not higher than 30 ° C., higher than the Tg of the binder resin is preferable because the solvent hardly remains in the matte acrylic resin film. In particular, each component of the binder resin and the matting material can be dissolved or uniformly dispersed, and the physical properties (mechanical strength, transparency, etc.) of the acrylic resin film substrate are not adversely affected in practice. The acrylic resin composition (III) is extracted under reflux in an acetone solvent, and the treated solution is centrifuged to separate acetone-insoluble matter, and the acetone-soluble component is dried to obtain 80 ° C. from the Tg of the resin component obtained. A volatile solvent having a boiling point not higher than this, preferably not higher than 30 ° C. is preferable.

  Solvents include alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butanol, and ethylene glycol; aromatic hydrocarbon solvents such as xylene, toluene, and benzene; aliphatic hydrocarbon solvents such as hexane and pentane; chloroform, Halogenated hydrocarbon solvents such as carbon tetrachloride; phenol solvents such as phenol and cresol; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, acetone and cyclohexanone; diethyl ether, methoxytoluene, 1,2-dimethoxyethane, 1 Ether solvents such as 1,2-dibutoxyethane, 1,1-dimethoxymethane, 1,1-dimethoxyethane, 1,4-dioxane and tetrahydrofuran (THF); fatty acid solvents such as formic acid, acetic acid and propionic acid; No acid such as acetic acid Physical solvents; ester solvents such as ethyl acetate, n-propyl acetate, butyl acetate and butyl formate; nitrogen-containing solvents such as ethylamine, toluidine, dimethylformamide and dimethylacetamide; sulfur-containing solvents such as thiophene and dimethyl sulfoxide; Acetone alcohol, 2-methoxyethanol (methyl cellosolve), 2-ethoxyethanol (ethyl cellosolve), 2-butoxyethanol (butyl cellosolve), diethylene glycol, 2-aminoethanol, acetocyanohydrin, diethanolamine, morpholine, 1-acetoxy-2-ethoxy Examples of the solvent include two or more kinds of functional groups such as ethane and 2-acetoxy-1-methoxypropane; and various known solvents such as water. These can be used alone or in combination of two or more.

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

  When the coating liquid is applied onto the acrylic resin film substrate, the viscosity of the coating liquid is 25 according to a viscosity cup (manufactured by Anest Iwata Corporation, NK-2 model) from the viewpoint of the coating appearance of the matte layer. It is preferable that the flow time at 10 ° C. is in the range of 10 to 40 seconds. When the viscosity of the coating liquid is 10 seconds or more, the print pattern of the gravure roll at the time of coating by the gravure coating method is not noticeable, a good matte layer can be formed, and coating is performed for a long time. At this time, the constituent components of the coating liquid such as binder resin, matting material and polyolefin wax do not settle with time, and the production stability is excellent. On the other hand, when the viscosity of the coating liquid is 40 seconds or less, a good matte layer can be formed without reducing the transfer amount of the coating liquid to the acrylic resin film substrate.

  For paints, known additives for improving solution properties such as anti-skinning agents, thickeners, anti-settling agents, anti-sagging agents, antifoaming agents, leveling agents, etc .; light stabilizers, UV absorbers, oxidation Known additives for improving the coating film performance such as an inhibitor, an antibacterial agent, an antifungal agent and a flame retardant can be added.

  Usually, in order to form a coating film having a sufficient thickness on a molded product by coating, ten or more times of overcoating may be required. In this case, cost is high and productivity is not so good. On the other hand, since the matte acrylic resin film itself becomes a coating film, the laminate of the present invention can easily form a very thick coating film and has high industrial utility value.

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

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

(Print layer)
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 binder for printing layer, polyvinyl chloride such as vinyl chloride / vinyl acetate copolymer, polyamide resin, polyester resin, polyacrylic resin, polyurethane resin, polyvinyl acetal resin, polyester urethane resin, cellulose ester Resin such as olefin resin, alkyd resin, and chlorinated polyolefin resin. As the polyacrylic resin, for example, an acrylic resin composition (III) containing the above-mentioned rubber-containing multistage polymer (I) may be used.

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

  Examples of the pigment include the following. Examples of yellow pigments include azo pigments such as polyazo, organic pigments such as isoindolinone, and inorganic pigments such as yellow lead. Examples of red pigments include azo pigments such as polyazo, organic pigments such as quinacridone, and inorganic pigments such as petals. Examples of blue pigments include organic pigments such as phthalocyanine blue; 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.

  The thickness of the printing layer may be appropriately determined as necessary, and is usually 0.5 to 30 μm.

The number of missing prints in the print layer is preferably 10 pieces / m ² or less from the viewpoints of design properties and decorating properties. By setting the number of printing omissions to 10 pieces / m ² or less, the appearance of the laminate using the 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 thickness of the printed layer may be appropriately selected according to the degree of expansion during the insert or in-mold molding so that a desired surface appearance can be obtained in a laminate obtained by insert molding or in-mold molding.

(Deposition layer)
The vapor deposition layer is formed of at least one metal selected from the group consisting of aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead, zinc, 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 may be appropriately selected according to the degree of extension during the insert or in-mold molding so that a desired surface appearance can be obtained in a laminate obtained by insert molding or in-mold molding.

<Other layers>
(Adhesive layer)
If necessary, the matte acrylic resin film of the present invention may be provided with an adhesive layer. The adhesive layer is preferably formed on the surface opposite to the surface provided with the matte layer.

(Cover film)
Further, the matte acrylic resin film of the present invention may further be provided with a cover film. This cover film is effective for dust-proofing the surface of the matte acrylic resin film. The cover film can be provided on either the surface of the matte layer or the surface opposite to the surface on which the matte layer is provided. It is preferably provided at least on the surface of the matte layer.

  When the cover film is provided on the surface of the matte layer, the cover film adheres to the matte layer before in-mold molding or insert molding and immediately peels off when in-mold or insert molding. On the other hand, it is necessary to have appropriate adhesion 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.

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

  The thermoplastic resin layer is preferably a material capable of achieving adhesion to the acrylic resin film substrate, and particularly preferably a compatible material. In addition, the thermoplastic resin layer is preferably made of a material having compatibility with the base material, more preferably for the purpose of improving the adhesion with the base material on which the matte acrylic resin film of the present invention is laminated. It consists of the same material as the substrate. As such a thermoplastic resin layer, a known thermoplastic resin film or sheet can be used, for example, acrylic resin; ABS resin (acrylonitrile-butadiene-styrene copolymer); AS resin (acrylonitrile-styrene copolymer). Polyvinyl chloride resin; Polyolefin resins such as polyethylene, polypropylene, polybutene, and polymethylpentene; Polyolefin copolymers such as ethylene-vinyl acetate copolymer or a saponified product thereof, and ethylene- (meth) acrylate ester copolymer Polymer: Polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, etc .; Polyamide type such as 6-nylon, 6,6-nylon, 6,10-nylon, 12-nylon Fatty; polystyrene resin; fiber 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 types of copolymers or mixtures, composites, and laminates.

  Among these, as the thermoplastic resin layer, from the viewpoint of the formability of the pattern layer (when forming on the thermoplastic resin layer instead of forming on the matte acrylic resin film), and the secondary moldability of the laminated film or sheet. Acrylic resin, ABS resin, vinyl chloride resin, polyolefin or polycarbonate is preferred.

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

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

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

  By using the matte acrylic resin film of the present invention as a laminated film or sheet, strength sufficient for handling against external forces such as impact and deformation is exhibited. For example, cracks and the like are less likely to occur when the film is vacuum-molded by insert molding or the like and then removed from the mold, or when the vacuum-molded product is mounted on an injection mold. , Handling becomes good. Furthermore, for example, the surface defect of the injection-molded base material is minimized from being propagated to the matte acrylic resin film, or when the base material is injection-molded, the pattern layer is less likely to disappear. .

  If necessary, for example, corona treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, anchor treatment, primer treatment on one surface of a matte acrylic resin film, the surface of a thermoplastic resin layer of a laminated film or sheet A surface treatment such as the above may be applied. Adhesion between the matte acrylic resin film and the picture layer, between the thermoplastic resin layer and the picture layer, between the matte acrylic resin film and the thermoplastic resin layer, and the like can be improved.

<Laminate>
The laminate of the present invention is obtained by laminating the matte acrylic resin film of the present invention, the laminated film or sheet thereof on a substrate. At this time, the matte acrylic resin film is laminated on the base material so that the surface opposite to the surface on which the matte layer is provided is in contact with the base material.

  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. For example, polyolefin resins such as polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, olefinic thermoplastic elastomer; polystyrene resin, ABS resin (acrylonitrile-butadiene-styrene) Copolymer), AS resin (acrylonitrile-styrene copolymer), acrylic resin, urethane resin, unsaturated polyester resin, epoxy resin, and other general-purpose thermoplastic or thermosetting resins; polyphenylene oxide / polystyrene resin, polycarbonate General-purpose engineering resins such as resin, polyacetal, polycarbonate-modified polyphenylene ether, polyethylene terephthalate; polysulfone, polyphenylene sulfide, polyphenylene Super engineering resins such as oxides, polyetherimides, polyimides, liquid crystalline polyesters, polyallyl-based heat-resistant resins, etc .; reinforcing materials such as glass fibers or inorganic fillers (talc, calcium carbonate, silica, mica, etc.), modifiers such as rubber components And composite resins to which is added or various modified resins.

  Of these, the material of the base material is preferably a matte acrylic resin film, a laminated film or a sheet that can be melt bonded. 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 if it is a resin that is not heat-sealed, such as a polyolefin-based resin, by providing an adhesive layer, one selected from the group consisting of a matte acrylic resin film, a laminated film or a sheet thereof, and a base material are bonded at the time of molding. Is possible.

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

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

  The in-mold molding method involves heating a matte acrylic resin film, or its laminated film or sheet, and then vacuum forming it in a mold having a vacuuming function, and then applying a resin as a base material in the same mold. This is a method of obtaining a laminated body in which a matte acrylic resin film or a laminated film or sheet thereof and a substrate are integrated by injection molding. The in-mold molding method is preferable from the viewpoints of workability and economy because the film molding and 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 multistage 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. be able to.

  A laminated film or sheet having a thermoplastic resin layer is preferred in that the disappearance of the pattern layer can be further reduced because of the presence of the thermoplastic resin layer.

  The heating temperature at the time of in-mold molding is preferably equal to or higher than the temperature at which the matte acrylic resin film or the laminated film or sheet thereof is softened. Specifically, it may be appropriately set depending on the thermal properties of the film or the shape of the laminate, 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. This may be set as appropriate depending on the thermal properties of the film or the shape of the laminate, and is usually 170 ° C. or lower. Furthermore, from the viewpoint of energy efficiency, it is preferable that the preheating temperature during vacuum forming is low. Specifically, 135 ° C. or lower is preferable. In addition, a film that can be molded even when the preheating temperature is low can shorten the preheating time instead of lowering the preheating temperature. In this case, high-cycle vacuum forming is possible, and the industrial utility value is high.

  When a three-dimensional shape is imparted to a film by vacuum forming, the matte acrylic resin film of 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 acrylic resin film, or its laminated film or sheet, warp of the laminate obtained by in-mold molding or insert molding, or film or sheet It is preferable because problems such as peeling off can be solved.

  The laminate of the present invention is particularly suitable for vehicle members and building materials. Examples include instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, dashboards and other automotive interior components; weather strips, bumpers, bumper guards, side mud guards, body panels , Spoilers, front grilles, strut mounts, wheel caps, center pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, windows, headlamp covers, tail lamp covers, windshield parts, and other automotive exterior components; AV equipment, Front panels of furniture products, buttons, emblems, surface decorative materials, etc .; housings for mobile phones, display windows, buttons, etc .; furniture exterior materials; walls, ceilings, floors, etc. Architectural interior materials; exterior walls for siding, fences, roofs, gates, windbreaks, etc .; exterior decorative 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 accessory cases; packaging materials; Miscellaneous goods such as prizes and accessories It can be suitably used for various other uses.

  The matte acrylic resin film of the present invention and the laminated film or sheet thereof have good handleability, and the matte layer has good crack resistance during insert molding and in-mold molding, and is resistant to tearing, whitening, etc. Excellent formability and satisfies the scratch resistance, surface hardness, heat resistance, and matte properties required for decorative films for automotive parts. Compared to conventional acrylic resin films, It can be expanded dramatically.

  The matte acrylic resin film of the present invention is particularly excellent in handleability, moldability such as matte layer cracking when subjected to insert molding or in-mold molding, and scratch resistance. By using a resin film, it is possible to develop a design that is difficult to achieve when a matte material is kneaded into an acrylic resin film substrate, and to improve the moldability of a conventional multi-layer matte acrylic resin film, Industrial value is extremely high.

  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 shown in Table 2.

[Measurement and evaluation method of physical properties]
Physical properties of rubber-containing polymer (I ′), rubber-containing multistage polymer (I), thermoplastic polymer (II), and thermoplastic polymer (IV), gel content of acrylic resin composition (III), preparation Properties of the acrylic resin film substrates (A) to (D), matte layer coating materials used in Examples and Comparative Examples, and the resulting matte acrylic resin film and laminates were measured and evaluated as follows. did.

  Evaluation of the laminated body was performed using the laminated body produced for the moldability evaluation shown in the following (12) or (13).

(1) Mass average particle diameter of rubber-containing multistage polymer (I) and rubber-containing polymer (I ′):
The polymer latex of the rubber-containing multistage 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. . It measured similarly about rubber-containing polymer (I ').

(2) Gel content of rubber-containing multistage polymer (I) and rubber-containing polymer (I ′):
A predetermined amount (mass before extraction) of rubber-containing multistage polymer (I) (coagulated powder obtained after polymerization) is extracted in acetone under reflux, and the treated solution is separated by centrifugation, dried, The mass of acetone insolubles was measured (mass after extraction) and calculated by the following formula. The rubber-containing polymer (I ′) was similarly calculated.
Gel content (%) = (mass after extraction (g) / mass before extraction (g)) × 100

(3) Tg of rubber-containing multistage polymer (I), rubber-containing polymer (I ′) and binder resin
It calculated from the formula of FOX using the value described in the polymer handbook [Polymer HandBook (J. Brandrup, Interscience, 1989)].

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

(5) Hydroxyl value of binder resin Measured according to JIS K0070: 1992.

(6) Mass average molecular weight of binder resin A Shimadzu LC-6A system (trade name, manufactured by Shimadzu Corporation) was used, and a GPC column connected with three KF-805L (manufactured by Showa Denko KK) was used. Measured in terms of polystyrene using THF as a solvent.

(7) Heat shrinkage rate of acrylic resin film substrate 5 cm intervals on the surface of the acrylic resin film substrate cut into A4 size in the MD direction (flow direction during film formation) and TD direction (direction perpendicular to the MD direction) Three parallel straight lines were drawn to each other, and the distance between them was accurately measured with calipers. The interval was measured at two locations, and the measured locations were marked. Then, after leaving for 60 minutes in 130 degreeC atmosphere and taking out, the space | interval of the same location as the location measured previously was measured once again. The heat shrinkage rate was calculated from the following formula using the average value of the distance between the two locations.
Heat shrinkage rate (%) = ((interval before heating−interval after heating) / interval before heating) × 100

(8) Viscosity of matting layer paint Viscosity cup (Anest Iwata Co., Ltd., NK-2 model) was used to measure the flow time at 25 ° C.

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

(10) Hardness of base of matte acrylic resin film and matte layer surface Pencil hardness was measured according to JIS K5600-5-4: 1999.

(11) Surface Gloss of Matte Acrylic Resin Film Using a gloss meter (GM-26D type (trade name) manufactured by Murakami Color Research Laboratory Co., Ltd.), the surface gloss at 60 ° of the matte surface was measured.

(12) Insert moldability of matte acrylic resin film A matte acrylic resin film having a thickness of about 75 μm was provided with a silver metallic layer as a pattern layer on the acrylic resin film substrate side by gravure printing. Further, an ABS sheet having a thickness of 1 mm having an adhesive layer was laminated on the matte acrylic resin film by thermal lamination so that the adhesive layer and the silver metallic layer were in contact with each other to obtain a laminate sheet of the matte acrylic resin film. Molding was performed using this laminated sheet.

Specifically, the obtained laminated sheet was placed in a mold having a vacuum drawing function so that the matte acrylic resin film side became the cavity side, and heated with a heater until the laminated sheet reached 190 ° C. Thereafter, vacuum forming was performed. Then, unnecessary parts were trimmed. Matte acrylic resin film with vacuum-formed laminated sheet on the bottom of the mold on the cavity side and on the bottom of the mold with a recess of 1 cm ² and depth of 1 mm at a position 3 cm laterally from the central gate The side was placed on the cavity side. Subsequently, an ABS resin (manufactured by UMG ABS Co., Ltd., trade name: Diapet ABS Bulk Sum TM25) as a base material was injection-molded on the ABS sheet side of the laminated sheet, and a laminate was obtained by insert molding.

  The detailed shape of the laminated body is a box shape with a length of 150 mm × width of 120 mm × thickness of 2 mm, and a depth of 10 mm. 3) A total of three locations, one each at a position of 40 mm, and the gate shape is a pinpoint gate with a diameter of 1 mm.

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

The state of the convex part of 1 cm ² and height of 1 mm formed on the obtained laminate was observed and evaluated as follows.

(About cracking)
○: No cracking.
Δ: Slight cracking occurred in the matte layer.
X: Large cracks occur in the matte layer.

(About whitening)
○: No whitening on the film.
X: The film has strong whitening.

(13) In-mold moldability of matte acrylic resin film A matte acrylic resin film having a thickness of about 125 μm was provided with a silver metallic layer as a pattern layer on the acrylic resin film substrate side by gravure printing. In-mold molding was performed using this matte acrylic resin film.

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

  The detailed shape of the laminated body is a box shape with a length of 150 mm × width of 120 mm × thickness of 2 mm, and a depth of 10 mm. 3) A total of three locations, one each at a position of 40 mm, and the gate shape is a pinpoint gate with a diameter of 1 mm.

  The matte acrylic resin film was vacuum-formed under the conditions of a heater temperature of 260 ° C., a heating time of 15 seconds, and a heater-film distance of 15 mm, and the non-pattern layer was in a direction in contact with the mold.

  In addition, the injection molding that is carried out in the same mold continues by injecting the base resin from the pattern layer side under the conditions of cylinder temperature 250 ° C, injection speed 30%, injection pressure 43%, mold temperature 50 ° C or 60 ° C. did. As the base resin, heat-resistant ABS resin (manufactured by UMG ABS, trade name: Bulk Sum TM25B) was used.

The state of the convex part of 1 cm ² and height of 1 mm formed on the obtained laminate was observed and evaluated as follows.

(About cracking)
○: No cracking.
Δ: Slight cracking occurred in the matte layer.
X: Large cracks occur in the matte layer.

(About whitening)
○: No whitening on the film.
X: The film has strong whitening.

(14) Scratch resistance of laminated body The laminated body is pressed onto a No. 60 broad No. 60 while applying a load of 0.01 MPa, and the laminated body has a stroke width of 100 mm and a speed of 30 reciprocations / minute. Now we made 1000 round trips. The appearance change of the laminate was observed and evaluated as follows.
A: No change in appearance.
○: Slightly damaged.
(Triangle | delta): There exists weak glossiness return.
×: Strong gloss return.

(15) Chemical resistance of the laminated body A polyethylene cylinder having an inner diameter of 38 mm and a height of 15 mm is placed on the surface of the laminated molded product, and is firmly attached to the test piece with a crimping device. Inject 5 ml of Chemical (trade name: Grace Mate Poppy Citrus). After the opening is covered with a glass plate, it is placed in a thermostat kept at 55 ° C. and left for 4 hours. After the test, the crimper was removed, the test piece was washed with water and air-dried, and the whitening state of the surface of the test part was observed and evaluated.
○: There is no peeling of the matte layer.
Δ: The matte layer is slightly peeled off.
X: There exists peeling of a matte layer.

(16) Appearance of laminate:
The appearance of the picture layer of the laminate under a fluorescent lamp was visually observed and evaluated as follows.
○: The pattern of the pattern layer is clearly visible and the reflection of the fluorescent light can be slightly confirmed. Furthermore, a slight whiteness is applied and the silver metallic feeling is good.
X: The pattern of the pattern layer can be seen as if it had a strong whiteness.

(17) Presence or absence of precipitation after application of matting layer paint:
After coating the matte layer for 3000 m, it was confirmed whether or not there was precipitation at the bottom of the paint reservoir, and the following evaluation was made.
○: No precipitation was observed at all.
Δ: Slightly confirmed but not problematic.
X: Precipitation is clearly confirmed.

[Production Example 1]
(Production of rubber-containing multistage polymer (I-1))
After charging 10.8 parts of deionized water into a vessel equipped with a stirrer, a monomer component consisting of 0.3 part of MMA, 4.5 parts of nBA, 0.2 part of 13BD, 0.05 part of AMA and 0.025 part of CHP is added. The mixture was stirred and mixed at room temperature. Subsequently, 1.3 parts of an emulsifier (manufactured by Toho Chemical Co., Ltd., trade name: Phosphanol RS610NA) was charged into the container while stirring, and stirring was continued for 20 minutes to prepare an emulsion.

  Next, 139.2 parts of deionized water was charged into a polymerization vessel equipped with a condenser, and the temperature was raised to 75 ° C. Further, a mixture prepared by adding 0.20 part of sodium formaldehyde sulfoxylate, 0.0001 part of ferrous sulfate and 0.0003 part of EDTA to 5 parts of ion-exchanged water was put into the polymerization vessel at once. Next, while stirring under nitrogen, the prepared emulsion was dropped into the polymerization vessel over 8 minutes, and then the reaction was continued for 15 minutes to complete the polymerization of the inner layer (I-1-A-1) of the elastic polymer. did. Subsequently, a monomer component consisting of 9.6 parts of MMA, 14.4 parts of nBA, 1.0 part of 13BD, and 0.25 part of AMA was added dropwise to the polymerization vessel over 90 minutes together with 0.016 part of CHP, and then reacted for 60 minutes. The elastic polymer (I-1-A) including the outer layer (I-1-A-2) of the elastic polymer was obtained. The Tg of the elastic polymer inner layer (I-1-A-1) alone was −48 ° C., and the Tg of the elastic polymer outer layer (I-1-A-2) alone was −10 ° C.

  Subsequently, a monomer component consisting of 6 parts of MMA, 4 parts of MA and 0.075 part of AMA was added dropwise to 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- 1-B) was formed. The intermediate polymer (I-1-B) alone had a Tg of 60 ° C.

  Thereafter, a monomer component consisting of 57 parts of MMA, 3 parts of MA, 0.264 part of nOM and 0.075 part of tBH was dropped into the polymerization vessel over 140 minutes, and then the reaction was continued for 60 minutes to obtain a hard polymer (I-1-C ) To obtain a polymer latex of a rubber-containing multistage polymer (I-1). The Tg of the hard polymer (I-1-C) alone was 99 ° C. Moreover, the mass average particle diameter of the rubber-containing multistage polymer (I-1) measured after polymerization was 0.11 μm.

  The polymer latex of the obtained rubber-containing multistage polymer (I-1) was filtered using a vibration type filtration device equipped with a SUS mesh (average opening: 62 μm) as a filter medium, and then calcium acetate 3. After salting out in an aqueous solution containing 5 parts, washing with water and recovering, it was dried to obtain a powdery rubber-containing multistage polymer (I-1). The gel content of the rubber-containing multistage polymer (I-1) was 70%.

  Further, 214.3 g of the obtained rubber-containing multistage polymer (I-1) was added to 1500 ml of acetone filtered through a nylon mesh having an opening of 25 μm, and stirred for 3 hours to obtain a rubber-containing multistage polymer (I-1). Acetone dispersion was prepared. Next, the dispersion was filtered through a nylon mesh having a mesh size of 32 μm, and the nylon mesh was washed with chloroform for 15 minutes to wash the captured matter on the mesh with chloroform. Then, the captured substance after ultrasonic cleaning is put into 150 ml of acetone filtered through a nylon mesh having an opening of 25 μm together with the nylon mesh, and this liquid is subjected to ultrasonic treatment for 15 minutes. 150 ml of an acetone dispersion of the trapped material was prepared. Next, 70 ml of this dispersion was measured at 25 ° C. with an automatic liquid particle counter (model: KL-01) manufactured by Rion Co., Ltd., and the number of particles having a diameter of 55 μm or more was determined. It was a piece.

[Production Example 2]
(Production of rubber-containing polymer (I′-2))
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 3 was added, and with stirring, 1/15 of the raw material (b) for the inner layer (I′-2-A1) of the elastic polymer shown in Table 3 was charged for 15 minutes. Retained. Next, the remaining raw material (b) is continuously added at a rate such that the rate of increase of the monomer component [raw material (b)] with respect to water is 8% / hour, and then held for 60 minutes to obtain an elastic polymer. The latex of the inner layer (I′-2-A-1) was obtained. The Tg of the elastic polymer inner layer (I′-2-A-1) alone was 24 ° C.

  Subsequently, 0.6 parts of sodium formaldehyde sulfoxylate was added to the latex and held for 15 minutes. Then, while stirring at 80 ° C. in a nitrogen atmosphere, the raw material (c) for the outer layer (I′-2-A-2) of the elastic polymer shown in Table 3 was added to the monomer component [raw material (raw material) C)] is continuously added at a rate of 4% / hour and then held for 120 minutes to form an outer layer (I′-2-A-2) of an elastic polymer. A latex of coalesced (I′-2-A) was obtained. The Tg of the elastic polymer outer layer (I′-2-A-2) alone was −38 ° C.

  Thereafter, 0.4 parts of sodium formaldehyde sulfoxylate was added to the latex and held for 15 minutes. Then, while stirring at 80 ° C. in a nitrogen atmosphere, the raw material (d) for the hard polymer (I′-2-C) shown in Table 3 was increased in the monomer component [raw material (d)] with respect to water. After the continuous addition at a rate of 10% / hour, the polymer is held for 60 minutes to form a hard polymer (I′-2-C) and a rubber-containing polymer (I′-2) latex Got. 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 0.28 μm.

  Calcium acetate is added to the polymer latex of the obtained rubber-containing polymer (I′-2), coagulation, aggregation, and solidification reaction are performed, followed by filtration, washing with water, drying, and rubber-containing polymer (I′- 2) was obtained. The gel content of the rubber-containing polymer (I′-2) was 90%.

[Production Example 3]
(Production of thermoplastic polymer (IV))
A reaction vessel was charged with 200 parts of ion-exchanged water substituted with nitrogen, and further charged with 1 part of an emulsifier (trade name: Latemulu ASK, manufactured by Kao Corporation) and 0.15 part of potassium persulfate, and MMA 40 parts, nBA2 And 0.004 part of nOM were charged and stirred at 65 ° C. for 3 hours under a nitrogen atmosphere to complete the polymerization.

  Subsequently, a monomer component consisting of 44 parts of MMA and 14 parts of nBA was added dropwise over 2 hours and then held for 2 hours to complete the polymerization.

  The polymer latex of the obtained thermoplastic polymer (IV) is added to a 0.25% aqueous sulfuric acid solution to cause acid precipitation of the polymer, and then dehydrated, washed with water and dried to obtain a powdery thermoplastic polymer. (IV) was recovered. The reduced viscosity of the obtained thermoplastic polymer (IV) was 0.38 L / g.

[Production Example 4]
(Manufacture of acrylic resin film substrate (A))
75 parts of rubber-containing multistage polymer (I-1) and thermoplastic polymer (II) [MMA / MA copolymer (MMA / MA = 99/1 (mass ratio), reduced viscosity 0.06 L / g)] 25 In part, 1.4 parts of Tinuvin 234 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), 0.1 part of Adeka Stub AO-50 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.) and Adeka Stub LA-67 (Asahi) After adding 0.3 part of Denka Kogyo Co., Ltd., trade name), the mixture was mixed using a Henschel mixer. This mixture [acrylic resin composition (III-1)] was supplied to a degassing extruder PCM-30 (Ikenai Iron Works Co., Ltd., (trade name)) heated to 230 ° C., kneaded, and 300 mesh. Extruding while removing foreign matter with a screen mesh of Pellets (A) was obtained.

  The produced pellets (A) were dried at 80 ° C. for a whole day and night, and using a 40 mmφ non-vent screw type extruder (L / D = 26) equipped with a 300 mm wide T-die, at a cylinder temperature of 180 to 240 ° C. , Extruding while removing foreign matter with a screen mesh of 500 mesh, passing the molten acrylic resin film extruded under the conditions of a T die temperature of 240 ° C. and a slit width of the T die of 0.3 mm between two metal cooling rolls, The resin is sandwiched without a bank (resin pool), surface-transferred without rolling, and then wound on a paper roll with a winder, and an acrylic resin film substrate (A) having a thickness of 75 μm or 125 μm Was formed. The hardness of the obtained acrylic resin film substrate (A) was H.

[Production Example 5]
(Manufacture of acrylic resin film substrate (B))
16 parts of rubber-containing polymer (I′-2) and thermoplastic polymer (II) [MMA / MA copolymer (MMA / MA = 99/1 (mass ratio), reduced viscosity 0.06 L / g)] 84 Parts, thermoplastic polymer (IV) 1 part, tinuvin 234 (trade name) 1.4 parts, Adeka Stub AO-50 (trade name) 0.1 part and Adeka Stub LA-67 (trade name) 0. After adding 3 parts, it was mixed using a Henschel mixer. This mixture [acrylic resin composition (III-2)] is supplied to a degassing extruder PCM-30 (trade name) heated to 230 ° C., kneaded, and extruded while removing foreign matter with a 300 mesh screen mesh. A pellet (B) was obtained.

  An acrylic resin film substrate (B) having a thickness of 125 μm was formed in the same manner as in the production of the acrylic resin film substrate (A) in Production Example 4 except that this pellet (B) was used. The resulting acrylic resin film substrate (B) had a hardness of 2H.

[Production Example 6]
(Manufacture of acrylic resin film substrate (C))
The pellet (B) obtained in Production Example 4 was dried overnight at 80 ° C., and a cylinder temperature of 180 to 240 was used using a 40 mmφ non-vented screw type extruder (L / D = 26) equipped with a 300 mm wide T-die. Extruded while removing foreign matters with a 500 mesh screen mesh under the condition of ℃, extruded two chilled rolls of acrylic resin film extruded under the conditions of T die temperature of 240 ℃ and slit width of T die of 0.5 mm An acrylic resin film substrate (C) having a thickness of 75 μm is formed by sandwiching the resin with the bank (resin pool) always in between, transferring the surface while rolling, and then winding it around a paper roll with a winder Was formed. The resulting acrylic resin film substrate (C) had a hardness of 2H.

[Production Example 7]
(Manufacture of acrylic resin film substrate (D))
16 parts of rubber-containing polymer (I′-2) and thermoplastic polymer (II) [MMA / MA copolymer (MMA / MA = 90/10 (mass ratio), reduced viscosity ηsp / c = 0.06 L / g)] 84 parts, thermoplastic polymer (IV) 1 part, tinuvin 234 (trade name) 1.4 parts, ADK STAB AO-50 (trade name) 0.1 parts, and ADK STAB LA-67 ( (Product name) After adding 0.3 part, it mixed using the Henschel mixer. This mixture [acrylic resin composition (III-3)] is supplied to a degassing extruder PCM-30 (trade name) heated to 230 ° C., kneaded, and extruded while removing foreign matter with a 300 mesh screen mesh. A pellet (D) was obtained.

  An acrylic resin film substrate (D) having a thickness of 125 μm was formed in the same manner as in the production of the acrylic resin film substrate (A) in Production Example 4 except that this pellet (D) was used. The resulting acrylic resin film substrate (D) had a hardness of 2H.

[Example 1]
27.5 parts of a hydroxyl group-containing acrylic resin (a) (hydroxyl value 80 mg KOH / g, Tg 90 ° C., mass average molecular weight of about 80,000), which is a copolymer of MMA 85%, HEMA 12% and nBA 3%, and hexamethylene diisocyanate as polyisocyanate 8 parts of a trimer, 6 parts of amorphous silica having a mass average particle diameter of 6 μm, 1 part of amorphous silica having a mass average particle diameter of 0.1 μm as a precipitation inhibitor and polyethylene wax S-395 having a mass average particle diameter of 5 μm ( 1 part of a trade name, manufactured by SHAMROCK, melting point 126 ° C.) was dispersed in a solvent consisting of 22 parts of MEK, 43 parts of MIBK and 40 parts of butyl acetate to obtain a paint. The viscosity (flowing time) of this paint was 18 seconds (25 ° C.).

  Next, paint is applied at a coating speed of 20 m / min with a gravure coater using a 200-line diagonal gravure roll and a ceramic doctor blade on one side of an acrylic resin film substrate (A) having a thickness of 75 μm. Then, the solvent was volatilized at 90 ° C. to obtain a matte acrylic resin film. The appearance of the resulting matte acrylic resin film was free of faint or noticeable prints due to a decrease in the transfer amount, and a good matte layer could be formed. The matte acrylic resin film was wound around a paper tube and aged at 40 ° C. for 2 days to cure the matte layer. The thickness of the matte layer was 1 μm.

[Example 2]
In place of polyethylene wax S-395 (trade name), polytetrafluoroethylene wax SST-3 (trade name, manufactured by SHAMROCK, melting point 321 ° C.) having a mass average particle diameter of 5 μm was used in the same manner as in Example 1, A matte acrylic resin film was obtained. The matte layer had a thickness of 1 μm. The viscosity (flowing time) before application of the matting layer coating material was 18 seconds (25 ° C.).

  While performing the coating, the appearance defect (white streaks are intermittently transferred in the flow direction) generated by rolling up the wax in which the gravure roll settled is sometimes confirmed, and after the coating of about 3000 m, Precipitates were observed at the bottom of the paint reservoir.

Example 3
A matte acrylic resin film was obtained in the same manner as in Example 2 except that the amount of polytetrafluoroethylene wax SST-3 (trade name) was increased to 2 parts. The matte layer had a thickness of 1.1 μm. The viscosity (flowing time) before application of the matting layer coating material was 18 seconds (25 ° C.).

  During the coating process, the appearance defect generated by rolling up the wax in which the gravure roll settled was sometimes confirmed, and after about 3000 m of coating, a considerable amount of deposit was confirmed at the bottom of the paint reservoir. .

Example 4
A matte acrylic resin film was obtained in the same manner as in Example 1 except that 0.5 part of polytetrafluoroethylene wax SST-3 (trade name) was used together with 1 part of polyethylene wax S-395 (trade name). The matte layer had a thickness of 1.1 μm. The viscosity (flowing time) before application of the matting layer coating material was 18 seconds (25 ° C.).

  While the coating was being carried out, no appearance defect was generated by rolling up the wax on which the gravure roll had settled, but there was a precipitate at the bottom of the paint reservoir after coating of about 3000 m.

Example 5
Instead of polyethylene wax S-395 (trade name), wax S-363 (trade name, manufactured by SHAMROCK, melting point 142 ° C.) made of polyethylene and polypropylene having a mass average particle diameter of 5 μm was used in the same manner as in Example 1. A matte acrylic resin film was obtained. The matte layer had a thickness of 1 μm. The viscosity (flowing time) of the paint was 19 seconds (25 ° C.).

Example 6
A matte acrylic resin film was obtained in the same manner as in Example 5 except that wax S-363 (trade name) made of polyethylene and polypropylene was increased to 2 parts. The matte layer had a thickness of 1 μm. The viscosity (flowing time) before application of the matting layer coating was 19 seconds (25 ° C.).

Example 7
A matte acrylic resin film was obtained in the same manner as in Example 5 except that the acrylic resin film substrate (A) having a thickness of 125 μm was used as the acrylic resin film substrate. The matte layer had a thickness of 1 μm.

Example 8
A matte acrylic resin film was obtained in the same manner as in Example 5 except that the acrylic resin film substrate (B) having a thickness of 125 μm was used as the acrylic resin film substrate. The matte layer had a thickness of 1.1 μm.

Example 9
A matte acrylic resin film was obtained in the same manner as in Example 5 except that an acrylic resin film substrate (C) having a thickness of 75 μm was used as the acrylic resin film substrate. The matte layer had a thickness of 1.1 μm. In some cases, the matte acrylic resin film and the ABS sheet may be peeled off by heating during insert molding.

Example 10
A matte acrylic resin film was obtained in the same manner as in Example 5 except that the acrylic resin film substrate (D) having a thickness of 125 μm was used as the acrylic resin film substrate. The matte layer had a thickness of 1.1 μm.

Example 11
Example 2 except that polytetrafluoroethylene wax SST-1MG (trade name, manufactured by SHAMROCK, melting point 321 ° C.) having a mass average particle size of 1.5 μm was used instead of polytetrafluoroethylene wax SST-3 (trade name). In the same manner, a matte acrylic resin film was obtained. The matte layer had a thickness of 1 μm. The viscosity (flowing time) before application of the matting layer coating was 19 seconds (25 ° C.).

  While the coating was carried out, almost no appearance defects were generated by rolling up the wax on which the gravure roll settled, but after the coating of about 3000 m was completed, there was a slight precipitation at the bottom of the paint reservoir. Things were confirmed.

Example 12
A matte acrylic resin film was obtained in the same manner as in Example 1 except that polyethylene wax S-395 (trade name) having a mass average particle diameter of 18 μm was used instead of a mass average particle diameter of 5 μm. The matte layer had a thickness of 0.9 μm. The viscosity (flowing time) before application of the matting layer coating material was 18 seconds (25 ° C.).

Example 13
Matte acrylic in the same manner as in Example 1 except that polyethylene wax S-390C (trade name, manufactured by SHAMROCK, melting point: 98 ° C.) having a mass average particle diameter of 5 μm is used instead of polyethylene wax S-395 (trade name). A resin film was obtained. The matte layer had a thickness of 1 μm. When vacuum forming is carried out, there is a concern about mass productivity because weak mold contamination occurs. The viscosity (flowing time) before application of the matting layer coating material was 18 seconds (25 ° C.).

Example 14
A matte acrylic resin film was obtained in the same manner as in Example 5 except that an inch-width 200-line oblique gravure roll was used instead of an inch-width 250-line oblique gravure roll. The matte layer had a thickness of 0.07 μm.

Example 15
A matte acrylic resin film was obtained in the same manner as in Example 5 except that a 300-line diagonal gravure roll having an inch width was used instead of the 200-line diagonal gravure roll. The matte layer had a thickness of 0.04 μm.

Example 16
A matte acrylic resin film was obtained in the same manner as in Example 5 except that a reverse roll coater was used instead of the gravure coater. The matte layer had a thickness of 4 μm.

Example 17
A matte acrylic resin film was obtained in the same manner as in Example 16 except that the roll clearance of the coated portion of the reverse roll coater was increased to about 3 times the setting of Example 16. The matte layer had a thickness of 11 μm. During coating, film breakage occurred frequently due to deterioration of the physical properties of the acrylic resin film substrate, so it could not be collected as a wound sample, but the molded product using the film has good scratch resistance. It is necessary to consider. In addition, since a large crack has occurred in the convex portion of the molded product, it is necessary to consider a molding method when there is a possibility of forming into a deep drawing shape.

Example 18
A matte acrylic resin film was obtained in the same manner as in Example 5 except that the ratio of MMA to HEMA was changed to use a hydroxyl group-containing acrylic resin (I) having a hydroxyl value of 10 mgKOH. The coating thickness of the matte layer was 1 μm. The viscosity (flowing time) before application of the matting layer coating was 19 seconds (25 ° C.).

Example 19
A matte acrylic resin film was obtained in the same manner as in Example 5 except that the ratio of MMA to HEMA was changed and a hydroxyl group-containing acrylic resin (U) having a hydroxyl value of 140 mgKOH was used. The coating thickness of the matte layer was 1 μm. The viscosity (flowing time) before application of the matting layer coating was 19 seconds (25 ° C.).

Example 20
A matte acrylic resin film was obtained in the same manner as in Example 5 except that the hydroxyl group-containing acrylic resin (d) having a Tg of 40 ° C. was used by changing the ratio of MMA and nBA. The coating thickness of the matte layer was 1 μm. The viscosity (flowing time) before application of the matting layer coating was 19 seconds (25 ° C.).

[Comparative Example 1]
A matte acrylic resin film was obtained in the same manner as in Example 1 except that polyethylene wax S-395 (trade name) was not used. The viscosity (flowing time) before application of the matting layer coating material was 17 seconds (25 ° C.).

[Comparative Example 2]
A matte acrylic resin film was obtained in the same manner as in Example 8 except that wax S-363 (trade name) made of polyethylene and polypropylene was not used. The viscosity (flowing time) before application of the matting layer coating material was 18 seconds (25 ° C.).

[Comparative Example 3]
A matte acrylic resin film was obtained in the same manner as in Example 10 except that wax S-363 (trade name) made of polyethylene and polypropylene was not used. The viscosity (flowing time) before application of the matting layer coating was 19 seconds (25 ° C.).

  Table 4 summarizes the acrylic resin film substrate and the matte layer coating material, and Table 5 summarizes the evaluation results of the matte acrylic resin film prepared above and the evaluation results of the laminate.

  As described above, by adopting the matte acrylic resin film of the present invention, it is difficult to realize when the matte layer made of the matte material and the binder resin is simply formed on the acrylic resin film substrate (Comparative Example 1). Even if it has excellent scratch resistance, insert molding or in-mold molding, and molding into a deep-drawn shape, the matte layer does not crack, and the surface hardness and resistance required for automotive parts It is possible to provide a matte acrylic resin film having chemical properties, heat resistance, and matting properties, and a laminate in which these are laminated on a base material. Moreover, it becomes possible to manufacture a matte acrylic resin film stably by employ | adopting the manufacturing method of this invention.

  The matte acrylic resin film of the present invention has sufficient surface hardness and excellent design by being laminated on the surface layer of the base material when producing various molded products having a matte surface. It is useful for the production of laminate molded articles.

  Moreover, the laminated body which has this matte acrylic resin film in a surface layer is especially suitable for the member for vehicles, and a building material. Examples include instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, dashboards and other automotive interior components; weather strips, bumpers, bumper guards, side mud guards, body panels , Spoilers, front grilles, strut mounts, wheel caps, center pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, windows, headlamp covers, tail lamp covers, windshield parts, and other automotive exterior components; AV equipment, Front panels of furniture products, buttons, emblems, surface decorative materials, etc .; housings for mobile phones, display windows, buttons, etc .; furniture exterior materials; walls, ceilings, floors, etc. Architectural interior materials; exterior walls for siding, fences, roofs, gates, windbreaks, etc .; exterior decorative 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 accessory cases; packaging materials; Miscellaneous goods such as prizes and accessories It can be suitably used for various other uses.

Claims (5)

  A matte acrylic resin film having an acrylic resin film substrate and a matte layer containing a matting material, an anti-scratch agent and a binder resin provided on the substrate.   The matte acrylic resin film according to claim 1, wherein the matte acrylic resin film has a pattern layer on a surface opposite to the surface on which the matte layer of the acrylic resin film substrate is provided.   Manufacture of matte acrylic resin film that forms matte layer on the surface of acrylic resin film substrate by applying paint with matte material, anti-scratch agent and binder resin as essential components by printing or coating method Method.   4. The method for producing a matte acrylic resin film according to claim 3, wherein the scratch preventing agent is a polyolefin wax.   A laminate in which the matte acrylic resin film according to claim 1 or 2 is laminated on a substrate.