JP2006142815A - Matt acrylic resin film for thermoforming, process of its production and laminated body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a matt acrylic resin film for thermoforming which develops an unprecedented design and is excellent in handleability and which does not cause cracking in the matt layer even when subjected to insert molding or in-mold molding to be deeply draw formed, and exhibits mar resistance, surface hardness, heat resistance, mattness, and a process of its production, and a laminate in which the matt acrylic resin film for thermoforming overlays a substrate. <P>SOLUTION: The matt acrylic resin film for thermoforming comprising an acrylic resin film substrate and a matt layer with a thickness of 0.1-5 μm containing a matting agent and a binder resin which is formed as an outermost layer on one side of the acrylic resin film substrate is used. The matt acrylic resin film for thermoforming is produced by forming the matt layer by a printing or coating method. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a matte acrylic resin film for thermoforming, a method for producing the same, and a laminate in which a matte acrylic resin film for thermoforming 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, a rubber-containing polymer having a specific composition and a thermoplastic polymer having a specific composition are in a specific ratio. The acrylic resin film which consists of a resin composition mixed by this is disclosed (for example, refer patent documents 1-4). Such an acrylic resin film not only imparts decorativeness to the molded product, but also has a function as an alternative material for clear coating.

  Also, an acrylic resin film containing a rubber-containing polymer having a specific composition and a thermoplastic polymer having a specific composition in a specific ratio, or a rubber-containing polymer having a specific composition and a specific composition An acrylic resin film containing a thermoplastic polymer and a matte material in a specific ratio is disclosed (for example, see Patent Documents 5 and 6). 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.

A thermoplastic resin composition comprising a rubber-containing multistage polymer having a specific structure and a linear polymer having a hydroxyl group having a specific composition as a thermoplastic resin composition giving an acrylic resin film having excellent matting properties The thing is disclosed (for example, refer patent document 7).
Also, a matte acrylic resin film obtained by forming a film by sandwiching a thermoplastic resin composition containing a specific matting crosslinked acrylic polymer and an acrylic resin with a roll set at a specific roll temperature is provided. (For example, refer to Patent Document 8).

Also disclosed is a matted acrylic resin film comprising a matte layer comprising a heat or photocurable resin and inorganic fine particles and an acrylic resin film substrate, which can maintain good matting performance after molding. (For example, refer to Patent Document 9).
Further, a matte acrylic insert film in which a matte layer is formed on one side of a transparent acrylic film and at least a picture layer is formed on the other side is disclosed (for example, see Patent Document 10).
In addition, a suede-like forming sheet is disclosed in which a coating film composed of a bead pigment having a specific particle diameter and an ionizing radiation curable resin is provided on a base film having good moldability (for example, Patent Document 11). reference.).

In recent years, a molded product having a matte acrylic resin film layer on a surface layer, which is molded by an insert molding method or an in-mold molding method, is used as a vehicle member.
The acrylic resin film described in Patent Document 5 is excellent in matte property, surface hardness, heat resistance, and moldability 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, and moldability.

  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 having a cross-linking structure whose main component is other than an acrylic resin or inorganic fine particles are used, the haze value of the matte acrylic resin film is increased although the matte state is obtained. 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 cross-linked structure are used, the matte acrylic resin film becomes brittle, and depending on the amount added, handling of the film in the film forming process may be difficult or in-mold. At the time of molding or insert molding, if the film is used under severe conditions such as deep drawing, the film may be broken or torn.

  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. In addition, Patent Document 7 has no description regarding the use of an acrylic resin film for insert molding or in-mold molding, and further does not describe 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 the case of using a heat or photocurable resin, the thickness of the matte layer and the composition of the heat or photocurable resin are important, but Patent Document 9 has no description about them.

  Further, when used for vehicle interior use, scratch resistance is required. Therefore, the matte acrylic resin film described in Patent Document 9 has reached a certain level of scratch resistance. However, since the surface wears over time, it may have a glossy appearance when used for a long period of time. In the matte acrylic resin film described in Patent Document 9, it is necessary to improve the scratch resistance by a method different from the conventionally known matte acrylic resin film. There is no description about the method.

  Further, in a matte acrylic resin film in which a matte layer is formed by a printing method or a coating method, the matte appearance may change due to heat during molding. Moreover, when insert molding or in-mold molding is performed using an acrylic resin film having a matte layer made of a thermosetting resin, it may turn yellow depending on the heating conditions of the film. However, Patent Document 9 does not describe a specific method for obtaining a matte acrylic resin film with little yellowing.

Moreover, insert molding may be performed using the laminated sheet which consists of an acrylic resin film and a base material sheet. At this time, if the thermal shrinkage rate of the acrylic resin film is large, the acrylic resin film peels off from the base sheet during insert molding. However, Patent Document 9 does not have a specific description regarding the thermal shrinkage rate of the acrylic resin film.
Moreover, when forming a mat layer by the printing method or the coating method, the physical property of the acrylic resin film used as a base material falls by a solvent attack. Therefore, although the solvent composition of the coating liquid to be used and the coating amount at the time of coating on the film are important, Patent Document 9 does not describe the optimum coating conditions.

  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 means for improving moldability when a curable resin is used as the binder resin. Moreover, there is no description of the optimum type and particle size of the matte material. Moreover, there is no specific description about the means for improving the scratch resistance. Moreover, although it is considered that the fluororesin-based spherical particles also serve as a wax, there may be a problem in productivity. Moreover, the curable resin used as binder resin is not specifically described. Further, in the examples, a thermoplastic resin is used as the binder resin, and the chemical resistance is poor.

Further, in a matte acrylic resin film in which a matte layer is formed by a printing method or a coating method, the matte appearance may change due to heat during molding. In addition, when insert molding or in-mold molding is performed using an acrylic resin film having a matte layer made of a thermosetting resin, it may turn yellow depending on the heating conditions of the film. However, Patent Document 10 does not describe a specific method for obtaining an acrylic resin film with little yellowing.
Further, Patent Document 10 does not specifically describe a transparent acrylic resin film 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 a mold having a dent or protrusion is used to obtain a molded product having a convex or concave design such as a letter, an acrylic resin film remains on the dent or convex part even after vacuum or pressure forming. Does not follow the mold, and since the base resin must be injection-molded with the acrylic resin film temperature below Tg, Once stretched whitening occurs, it cracked in some cases.

Thus, when the acrylic resin films described in Patent Documents 1 to 4 are used, it is necessary to remove the film protruding by hand instead of punching due to the problem of resistance to molding whitening. In some cases, the industrial utility value is low, for example, a work process for removing whiteness by reheating the whitened portion is required.
Moreover, insert molding may be performed using the laminated sheet which consists of an acrylic resin film and a base material sheet. At this time, if the heat shrinkage rate of the acrylic resin film is large, the acrylic resin film peels 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 forming into a deep drawing shape at the time of in-mold molding or insert molding, there is a possibility that molding defects such as cracking or tearing of the coating film may occur due to the insufficient stretching of the coating film. However, since there is no description regarding the optimal thickness of the coating film for solving this in Patent Document 11, the suede tone forming sheet described in Patent Document 11 has low industrial utility value. Although it has been described that a thermoplastic resin is mixed in order to improve moldability, this method has a problem that chemical resistance is lowered.

In addition, in the suede-like molding sheet in which a coating film is formed by a printing method or a coating method, the matte appearance may change due to heat during molding. However, Patent Document 11 does not describe means for solving this problem. Moreover, there is no description about the acrylic resin film suitable for a base film.
JP-A-8-323934 Japanese Patent Laid-Open No. 11-147237 JP 2002-80678 A JP 2002-80679 A Japanese Patent Laid-Open No. 10-237261 JP 2002-361712 A JP-A-7-238202 JP 2002-254495 A JP 2003-111598 A Japanese Patent Laid-Open No. 10-34703 Japanese Patent No. 2132254

  The present invention expresses a design that is difficult to realize when a matte material is added to a conventional acrylic resin film substrate, has good handleability, and is subjected to insert molding or in-mold molding to form a deep drawing shape. In this case, the matte layer does not crack, and has the scratch resistance, surface hardness, heat resistance, chemical resistance, heat yellowing, and matte properties required for decorative films for automotive parts. An object is to provide a matte acrylic resin film for thermoforming. It is another object of the present invention to provide an optimum manufacturing method for obtaining a matte acrylic resin film for thermoforming. Furthermore, an object of the present invention is to provide a laminate in which a matte acrylic resin film for thermoforming is laminated on a base material.

The matte acrylic resin film for thermoforming of the present invention comprises an acrylic resin film substrate, a matting material and a binder resin provided as an outermost layer on one surface of the acrylic resin film substrate, and has a thickness of 0 It has a mat layer of 1 to 5 μm.
The matte layer may further contain a polyolefin wax.

The yellowness (YI ′ (200 ° C.)) of the matte acrylic resin film for thermoforming after heating the matte surface temperature to 200 ° C. and the yellow of the matte acrylic resin film for thermoforming before heating The degree (YI) preferably satisfies the relationship of the following formula (i).
YI ′ (200 ° C.) − YI ≦ 1.3 (i)

The coefficient of dynamic friction on the surface of the matte layer is preferably 0.23 or less.
Moreover, you may have a pattern layer further on the surface of the acrylic resin film base | substrate on the opposite side to the surface in which the matte layer was provided.

The method for producing a matte acrylic resin film for thermoforming of the present invention comprises an acrylic resin film substrate, a matting material and a binder resin provided as an outermost layer on one surface of the acrylic resin film substrate. A method for producing a matte acrylic resin film for thermoforming having a matte layer having a thickness of 0.1 to 5 μm, wherein the matte layer is formed by a printing method or a coating method.
At this time, a matte layer is formed using a diagonal gravure roll having a number of lines of 150 or more per inch and engraved at an angle of 40 to 50 ° with respect to the roll axis direction. Is preferably formed.

The laminate of the present invention is obtained by laminating the matte acrylic resin film for thermoforming of the present invention on a substrate so that the surface opposite to the matte layer is in contact.
The coefficient of dynamic friction on the surface of the matte layer is preferably 0.23 or less.
The laminate of the present invention is preferably one obtained by laminating a matte acrylic resin film for thermoforming on a substrate by an in-mold molding method or an insert molding method.

The matte acrylic resin film for thermoforming of the present invention expresses a design that is difficult to realize when a matte material is added to a conventional acrylic resin film substrate, has good handleability, and is insert molded or in-mold. Even when molded into a deep-drawn shape, the matte layer does not crack, and scratch resistance, surface hardness, heat resistance, chemical resistance, heat resistance required for decorative films for automotive parts Has yellowing and matte properties.
Moreover, according to the manufacturing method of the matte acrylic resin film for thermoforming of this invention, such a matte acrylic resin film for thermoforming can be manufactured stably.
In addition, the laminate of the present invention has excellent design properties, scratch resistance, surface hardness, heat resistance, chemical resistance, heat yellowing, and matte properties, and the matte layer on the surface is cracked. There are no defects.

  In the matte acrylic resin film for thermoforming of the present invention, a matte layer containing a matting material and a binder resin is provided on one surface of an acrylic resin film substrate as an outermost layer with a thickness of 0.1 to 5 μm. It is a thing. “Thermoforming” refers to a molding method in which a film or sheet is set in a mold, etc., softened by heating and molded into a predetermined shape with vacuum pressure, compressed air, etc., and vacuum molding, pressure molding, press molding, etc. Can be mentioned.

<Acrylic resin film substrate>
Examples of the acrylic resin film substrate include known acrylic resin films. Examples of the acrylic resin film substrate that can be used for vehicles include scratch resistance, pencil hardness, heat resistance, and chemical resistance. Those described in JP-A-2002-80678, JP-A-2002-80679, and JP-A-2005-97351 are preferable. Moreover, the thing of Unexamined-Japanese-Patent No. 2005-163003 and Unexamined-Japanese-Patent No. 2005-139416 is preferable at the point of the shaping | molding whitening resistance at the time of performing insert molding or in-mold shaping | molding.

(Heat shrinkage)
As the acrylic resin film substrate, one that does not shrink as much as possible during heating is preferable. When a matte acrylic resin film for thermoforming is laminated on a thermoplastic resin layer to form a laminated film or sheet, if the acrylic resin film base has a large shrinkage ratio upon heating, the acrylic resin film base will be used during insert molding. May be peeled off from the thermoplastic resin layer.

  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 vehicle use, when the adhesion between the matte acrylic resin film for thermoforming and the laminate substrate is evaluated, it peels at the interface between the matte layer and the acrylic resin film substrate. A laminate is obtained. In addition, when a laminated sheet in which a matte acrylic resin film for thermoforming is laminated on a thermoplastic resin layer is used as a decorative film or sheet, the thermoplastic resin layer and Also from the viewpoint of suppressing peeling at the interface with the acrylic resin film substrate, it is preferable that the shrinkage rate of the acrylic resin film substrate upon heating is small. 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 of 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 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, the MD direction and the TD direction are specified as follows, for example. Draw a circle with a specific radius on the film, heat-treat the conditions described above, and determine the direction in which the shrinkage rate is maximized from the shape of the circle (or ellipse if there is anisotropy) on the film. The direction is the MD direction, and the direction perpendicular to the MD direction is the TD direction.

(Pencil hardness)
The pencil hardness (measured based on JIS K5400) of the acrylic resin film substrate is preferably 2B or more, more preferably HB or more in order to increase the pencil hardness of the matte acrylic resin film for thermoforming of the present invention. Preferably, it is F or more.

(Rubber-containing polymer (I '))
In order to make the pencil hardness of the acrylic resin film substrate 2B or higher, the acrylic resin film substrate is preferably made of an acrylic resin composition (III) containing the following rubber-containing polymer (I ′).
The rubber-containing polymer (I ′) is a single polymer containing a methacrylic acid alkyl ester as the main component in the presence of an elastic polymer obtained by polymerizing the monomer (i) containing the acrylic acid alkyl ester as a main component. A polymer having an elastic polymer and a hard polymer formed by graft polymerization of the monomer (ii) to form a hard polymer. Here, the elastic polymer and the hard polymer may polymerize the respective monomers at once, or may be polymerized in two or more stages.

Examples of the alkyl acrylate ester that is the main component of the monomer (i) include various conventionally known alkyl acrylate esters. 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 the acrylic acid alkyl ester used is 35 to 35% in the total monomer (i) (100% by mass). What is necessary is just 99.9 mass%. For example, in the case of an elastic polymer obtained by polymerizing monomer (i) in two or more stages, the total use amount of 35 to 99.9% by mass of the total use amount of alkyl acrylate ester in each polymerization step is If there is, the use amount of the first stage alkyl acrylate may be arbitrarily set.

  As the monomer (i), together with an alkyl acrylate, other vinyl monomers copolymerizable therewith can also be used. When other vinyl monomers are used, the amount used is preferably 64.9% by mass or less 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 methacrylic acid alkyl ester that is the main component of the monomer (ii) used in 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 alkyl methacrylate. 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.

The amount of the monomer (ii) in producing the rubber-containing polymer (I ′) is preferably 10 to 400 parts by mass, more preferably 20 to 200, per 100 parts by mass of the monomer (i). Part 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 for thermoforming.

  As a production method of 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 conventionally known emulsion polymerization method is used. Can do. The optimum value of the polymerization temperature varies depending on the type and amount of the polymerization initiator used, and is usually preferably 40 ° C or higher, more preferably 60 ° C or higher, preferably 95 ° C or lower, more preferably 120 ° C or lower.

Various conventionally known polymerization initiators can be used. The polymerization initiator may be added to one or both of the aqueous phase and the monomer phase.
Examples of the emulsifier used in the emulsion polymerization include anionic, cationic and nonionic surfactants, and anionic surfactants are particularly preferable. Examples of the anionic surfactant include carboxylate surfactants such as potassium oleate, sodium stearate, sodium myristate, sodium N-lauroyl sarcinate and dipotassium alkenyl succinate; sulfuric acid such as sodium lauryl sulfate Ester salt surfactants; sulfonate surfactants such as sodium dioctylsulfosuccinate, sodium dodecylbenzenesulfonate, sodium alkyldiphenyl ether disulfonate; phosphate ester-based interfaces such as sodium polyoxyethylene alkylphenyl ether phosphate Active agents; and the like.

  The polymer latex obtained by emulsion polymerization is, for example, filtered through a filter having an opening of 100 μm or less, and then recovered by a known method such as acid precipitation coagulation method, salting out coagulation method, freeze drying method, spray drying method or the like. 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 preferably a rubber-containing multistage polymer (I) shown below from the viewpoint of resistance to molding whitening during in-mold molding and 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., and elasticity An intermediate polymer (IB) having a composition different from that of the polymer (IA) and (3) a hard polymer (IC) are formed 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 either a linear or branched alkyl group. Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. These can be used alone or in admixture of two or more. Of these, n-butyl acrylate is preferred.

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

  Examples of other monomers having a copolymerizable double bond (I-A3) include acrylic monomers such as lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, and methacrylic acid, styrene, alkyl-substituted styrene, Examples include 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 effective. These can be used alone or in admixture of two or more. Of these, 1,3-butylene glycol dimethacrylate is preferred. Even when the polyfunctional monomer (I-A4) does not act at all, as long as the graft crossing agent (I-A5) is present, a fairly stable rubber-containing multistage polymer (I) is obtained. The polyfunctional monomer (I-A4) can be arbitrarily added according to 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 allyl, methallyl, or crotyl ester of copolymerizable α, β-unsaturated carboxylic acid or dicarboxylic acid. Particularly preferred are allyl esters of acrylic acid, methacrylic acid, maleic acid, or fumaric acid. Of these, allyl methacrylate is preferable because of its excellent effect. In addition, triallyl cyanurate, triallyl isocyanurate and the like are also effective. These can be used alone or in admixture of two or more. Graft-crossing agent (I-A5) reacts and chemically bonds mainly with the conjugated unsaturated bond of its ester much faster than allyl, methallyl or crotyl groups.
The monomer component that is a raw material 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 monomer component (100% by mass) which is a raw material of the elastic polymer (IA). From the viewpoint of the resistance to whitening of the resulting matte acrylic resin film for thermoforming, 55% by mass or more is more preferable, and 60% by mass or more is particularly preferable. Further, from the viewpoint of the surface hardness and heat resistance of the resulting matte acrylic resin film for thermoforming, it is more preferably 79.9% by mass or less, and particularly preferably 69.9% by mass or less.

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

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

  The content of the graft crossing agent (I-A5) is preferably 0.1 to 10% by mass in the monomer component (100% by mass) which is a raw material of the elastic polymer (IA). By setting the content of the graft crossing agent (I-A5) to 0.1% by mass or more, the resulting matte acrylic resin film for thermoforming has good molding whitening resistance, and optical properties such as transparency are improved. It can be molded without lowering. More preferably, it is 0.5 mass% or more. Moreover, sufficient softness | flexibility and toughness can be provided to the matte acrylic resin film for thermoforming 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 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 (glass transition temperature) in the present invention is the polymer handbook [Polymer HandBook, J. et al. Tg calculated from the FOX equation using the values described in Brandrup, Interscience, 1989].

  The amount of the monomer component that is the raw material of the elastic polymer (IA) is 15 to 50% by mass in the total monomer component (100% by mass) that is the raw material of the rubber-containing multistage polymer (I). preferable. By setting the amount of the monomer component that is a raw material of the elastic polymer (IA) to 15% by mass or more, it is possible to impart molding whitening resistance to the resulting matte acrylic resin film for thermoforming, The film forming property and the toughness required for insert molding or in-mold molding can both be achieved. Moreover, the film which has the surface hardness and heat resistance required for the laminated body of a vehicle member by making the quantity of the monomer component which is a raw material of an elastic polymer (IA) into 50 mass% or less is obtained. It is done. More preferably, it is 35 mass% or less.

The monomer component that is the raw material of the elastic polymer (IA) may be polymerized in a lump or may be polymerized in two or more stages. Polymerization is preferably carried out in two or more stages. When polymerizing in two or more stages, the composition of the monomer component in each polymerization stage is preferably different.
In the case of polymerizing in two or more stages, the first obtained by the first stage polymerization from the viewpoint of molding whitening resistance, impact resistance, heat resistance and surface hardness of the matte acrylic resin film for thermoforming obtained. The Tg of the elastic polymer (IA-1) is preferably lower than the Tg of the second elastic polymer (IA-2) obtained by the second stage polymerization. Specifically, the Tg of the first elastic polymer (IA-1) is preferably less than −30 ° C. from the viewpoint of molding whitening resistance and impact resistance, and the second elastic polymer (I— The Tg of A-2) is preferably −15 ° C. to 10 ° C. from the viewpoints of surface hardness and heat resistance. In addition, from the viewpoint of surface hardness and heat resistance, the amount of the monomer component that is the raw material of the first elastic polymer (IA-1) is the total amount of the monomer component that is the raw material of the elastic polymer (IA). 1-20 mass% is preferable in a monomer component (100 mass%), and the quantity of the monomer component which is a raw material of a 2nd elastic polymer (IA-2) is elastic polymer (IA). 80-99 mass% is preferable in all the monomer components (100 mass%) which are the raw materials of).

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

  The methacrylic acid alkyl ester (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 alone or in admixture of two or more. Of these, methyl methacrylate is preferred.

  Other monomers (I-B3) having a double bond capable of copolymerization include acrylic monomers such as lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, methacrylic acid, styrene, alkyl-substituted styrene, Examples include acrylonitrile and methacrylonitrile. These can be used alone or in admixture of two or more.

  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 effective. Of these, 1,3-butylene glycol dimethacrylate is preferred. These can be used alone or in admixture of two or more. Even when the polyfunctional monomer (I-B4) does not act at all, as long as the graft crossing agent (I-B5) is present, a fairly stable rubber-containing multistage polymer (I) is obtained. The polyfunctional monomer (I-B4) can be arbitrarily added 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 allyl, methallyl, or crotyl ester of copolymerizable α, β-unsaturated carboxylic acid or dicarboxylic acid. Particularly preferred are allyl esters of acrylic acid, methacrylic acid, maleic acid, or fumaric acid. Of these, allyl methacrylate is preferable because of its excellent effect. In addition, triallyl cyanurate, triallyl isocyanurate and the like are also effective. These can be used alone or in admixture of two or more. Graft-crossing agent (I-B5) is chemically bonded, with the conjugated unsaturated bond of its ester reacting much faster than allyl, methallyl, or crotyl groups.
The monomer component that is a raw material of the intermediate polymer (IB) may be polymerized in the presence of a chain transfer agent.

  The content of the acrylic acid alkyl ester (I-B1) is preferably 9.9 to 90% by mass in the monomer component (100% by mass) which is a raw material of the intermediate polymer (IB). From the viewpoint of molding whitening resistance, surface hardness and heat resistance of the resulting matte acrylic resin film for thermoforming, 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 monomer component (100% by mass) which is a raw material of the intermediate polymer (IB). From the viewpoint of molding whitening resistance, surface hardness, and heat resistance of the resulting matte acrylic resin film for thermoforming, 39.9% by mass or more is more preferable, and 49.9% by mass or more is particularly preferable. Further, it is more preferably 80% by mass or less, particularly preferably 70% by mass or less.

The content of the other monomer (IB3) having a copolymerizable double bond is 0 to 20 in the monomer component (100% by mass) which is a raw material of the intermediate polymer (IB). Mass% is preferred. More preferably, it is 15 mass% or less.
As for content of a polyfunctional monomer (IB-4), 0-10 mass% is preferable in the monomer component (100 mass%) which is a raw material of an intermediate polymer (IB). From the viewpoint of imparting sufficient flexibility and toughness to the resulting matte acrylic resin film for thermoforming, 6% by mass or less is preferable, and 3% by mass or less is particularly preferable.

  The content of the graft crossing agent (I-B5) is preferably 0.1 to 10% by mass in the monomer component (100% by mass) which is a raw material for the intermediate polymer (IB). By setting the content of the graft crossing agent (I-B5) to 0.1% by mass or more, the resulting matte acrylic resin film for thermoforming has good molding whitening resistance, and optical properties such as transparency are improved. It can be molded without lowering. More preferably, it is 0.5 mass% or more. Moreover, sufficient softness | flexibility and toughness can be provided to the matte acrylic resin film for thermoforming 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 25 to 100 ° C. If Tg is 25 ° C. or higher, the surface hardness and heat resistance of the resulting matte acrylic resin film for thermoforming are at a level required for a vehicle member. More preferably, it is 40 degreeC or more, Most preferably, it is 50 degreeC or more. Moreover, if Tg is 100 degrees C or less, the matte acrylic resin film for thermoforming with favorable shaping | molding whitening-proof property and film forming property will be obtained. More preferably, it is 80 degrees C or less, Most preferably, it is 70 degrees C or less.
As described above, by providing the intermediate polymer (IB) having a specific composition and Tg, it has been difficult to realize so far. A matte acrylic resin film can be obtained.

The amount of the monomer component that is the raw material of the intermediate polymer (IB) is 5 to 35% by mass in the total monomer component (100% by mass) that is the raw material of the rubber-containing multistage polymer (I). preferable. Within this range, the function of the intermediate polymer (IB) important for achieving both the above-described whitening resistance to molding, surface hardness, and heat resistance can be exhibited, and the obtained thermoforming Other physical properties of the matte acrylic resin film for use, for example, film-forming properties, toughness required for insert molding or in-mold molding can be imparted. More preferably, it is 20 mass% or less.
The monomer component that is the raw material of the intermediate polymer (IB) may be polymerized in a lump or may be polymerized in two or more stages.

  The methacrylic acid alkyl ester (I-C1) may have either a linear or branched alkyl group. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate. These can be used alone or in admixture of two or more. Of these, methyl methacrylate is preferred.

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

  Other monomers having a copolymerizable double bond (I-C3) include acrylic monomers such as lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, methacrylic acid, styrene, alkyl-substituted styrene, Examples thereof include unsaturated dicarboxylic anhydrides such as acrylonitrile, methacrylonitrile, maleic anhydride and itaconic anhydride, N-phenylmaleimide, N-cyclohexylmaleimide and the like. These can be used 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 monomer component (100% by mass) which is a raw material of the hard polymer (IC). From the viewpoint of surface hardness and heat resistance of the resulting matte acrylic resin film for thermoforming, 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 monomer component (100% by mass) which is a raw material 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 in the monomer component (100% by mass) which is a raw material of the hard polymer (IC). Mass% is preferred. More preferably, it is 15 mass% or less.

  A chain transfer agent can be used at the time of the polymerization of the monomer component which is a raw material of the hard polymer (IC), and the molecular weight of the hard polymer (IC) can be adjusted. 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 alone or in admixture of two or more. As for content of a chain transfer agent, 0.01-5 mass parts is preferable with respect to 100 mass parts of monomer components which are the raw materials 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. If Tg is 60 ° C. or higher, a matte acrylic resin film for thermoforming 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.
The amount of the monomer component that is the raw material of the hard polymer (IC) is 15 to 80% by mass in the total monomer component (100% by mass) that is the raw material of the rubber-containing multistage polymer (I). preferable. When the amount of the monomer component that is a raw material of the hard polymer (IC) is 15% by mass or more, the surface hardness and heat resistance of the resulting matte acrylic resin film for thermoforming are good. More preferably, it is 45 mass% or more. If the amount of the monomer component that is the raw material of the hard polymer (IC) is 80% by mass or less, the resulting matte acrylic resin film for thermoforming can be used for whitening resistance, insert molding and in-mold molding. Necessary toughness can be imparted.
The monomer component that is the raw material of the hard polymer (IC) may be polymerized in a lump or may be polymerized in two or more stages.

The gel content of the rubber-containing multistage polymer (I) is preferably 50% or more, and more preferably 60% or more, from the viewpoint of obtaining better molding whitening resistance. From the viewpoint of molding whitening resistance, the larger the gel content, the more advantageous. However, from the viewpoint of easy moldability, the presence of a certain amount or more of free polymer is necessary, so the gel content should be 80% or less. preferable. The gel content means that a predetermined amount (mass before extraction) of the rubber-containing 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 after extraction (g) / mass before extraction (g) × 100

  The mass average particle diameter of the rubber-containing multistage polymer (I) is preferably 0.03 μm to 0.3 μm. From the viewpoint of mechanical properties of the resulting matte acrylic resin film for thermoforming, 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 resulting matte acrylic resin film for thermoforming, it is more preferably 0.15 μm or less, particularly preferably 0.13 μm or less. The mass average particle diameter is measured by a dynamic light scattering method using a light scattering photometer DLS-700 (trade name) manufactured by Otsuka Electronics Co., Ltd.

As 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 monomer component which is the raw material of the combined (IC) is converted into a suspension polymerization system.
When the rubber-containing multistage polymer (I) is produced by emulsion polymerization, the monomer component that is the raw material of the elastic polymer (IA) in the rubber-containing multistage polymer (I) is previously added with water and a surfactant. After the emulsion prepared by mixing with the polymer is supplied to the reactor and polymerized, the monomer component which is the raw material of the intermediate polymer (IB) and the raw material of the hard polymer (IC) A method in which the monomer components are sequentially supplied to the reactor and polymerized is preferable.

  The monomer component which is a raw material of the elastic polymer (IA) was dispersed in acetone by supplying an emulsion prepared by mixing water and a surfactant in advance to the reactor and polymerizing it. In this case, 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 for thermoforming 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 loss is particularly likely to occur. Even in the case where gravure printing with a light wood pattern with low pressure or solid gravure printing such as metallic tone or jet black tone is performed, 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-lauroyl sarcosinate, dipotassium alkenyl succinate; sulfate esters such as sodium lauryl sulfate Sulfonic acid salts such as sodium dioctyl sulfosuccinate, sodium dodecylbenzene sulfonate, sodium alkyldiphenyl ether disulfonate; phosphate esters such as polyoxyethylene alkylphenyl ether sodium phosphate; polyoxyethylene alkyl ether sodium phosphate And phosphoric acid ester salts. Of these, sodium phosphate esters such as sodium polyoxyethylene alkyl ether phosphates are preferred. Preferable specific examples of the surfactant include NC-718 manufactured by Sanyo Chemical Industries, Ltd., Phosphanol LS-529, Phosphanol RS-610NA, Phosphanol RS- manufactured by Toho Chemical Industry Co., Ltd. 620NA, Phosphanol RS-630NA, Phosphanol RS-640NA, Phosphanol RS-650NA, Phosphanol RS-660NA, Latemul P-0404, Latemul P-0405, Latemul P-0406 manufactured by Kao Corporation Latemul P-0407 (above, trade name) and the like.

As a method for preparing an emulsified liquid, a method in which a monomer component is charged in water and then a surfactant is added; a method in which a surfactant is charged in water and then a monomer component is charged; a monomer Examples thereof include a method in which water is added after a surfactant is charged into the components. 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 various forced emulsification devices such as a stirrer equipped with a stirring blade, a homogenizer, and a homomixer, a membrane emulsification device, and the like.
The emulsion may 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.

A well-known thing can be used as a polymerization initiator used when forming an elastic polymer (IA), an intermediate polymer (IB), and a hard polymer (IC). Examples of the polymerization initiator include a peroxide, an azo initiator, or a redox initiator in which an oxidizing agent and a reducing agent are combined. Among these, a redox initiator is preferable, and particularly ferrous sulfate. A sulfoxylate-based initiator in which ethylenediaminetetraacetic acid 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.
Examples of the method for adding a polymerization initiator include a method of adding to one or both of an aqueous phase and a monomer phase (oil phase).

As a method for synthesizing the rubber-containing multistage polymer (I), in particular, after raising the temperature of an aqueous solution containing ferrous sulfate, ethylenediaminetetraacetic acid disodium salt and Rongalite charged in a reactor to the polymerization temperature, an elastic polymer An emulsion prepared by mixing a monomer component and a polymerization initiator such as peroxide, which are raw materials of (IA), with water and a surfactant is supplied to the reactor for polymerization. A monomer component that is a raw material of the polymer (IB) is supplied to a reactor together with a polymerization initiator such as a peroxide for polymerization, and then a monomer that is a raw material of the hard polymer (IC) A method in which the components are supplied to a reactor together with a polymerization initiator such as a peroxide and polymerized is preferred.
The polymerization temperature varies depending on the type and amount of the polymerization initiator used, and is usually preferably 40 ° C. or higher, more preferably 60 ° C. or higher, preferably 120 ° C. or lower, 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 of ISP Filters PTA Ltd. using a bag-shaped mesh filter; a cylindrical filter medium is arranged on the inner surface of a cylindrical filter chamber, and the filter medium is stirred. A centrifugal type filtration device provided with blades; or a vibration type filtration device in which the filter medium performs a horizontal circular motion and a vertical amplitude motion with respect to the filter medium surface is preferable.

  The rubber-containing 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 or 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 using a metal salt having a strong affinity for water such as magnesium salt and sodium salt as a salting-out agent, the rubber-containing multistage polymer (I When a matte acrylic resin film for thermoforming made from) is immersed in boiling water, a whitening phenomenon occurs, which is a serious problem in practical use. 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 necessary 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, C1-C4 methacrylic acid alkyl ester (II-A) 50-100 mass%, acrylic acid alkyl ester (II-B) 0-50 mass%, and has a copolymerizable double bond The other monomer (II-C) is obtained by polymerizing a monomer component having a composition of 0 to 50% by mass, and reduced viscosity (0.1 g of polymer is dissolved in 100 mL of chloroform, Polymers having a (measured at 25 ° C.) of 0.15 L / g or less are preferred. By using together such a thermoplastic polymer (II), the surface hardness and heat resistance of the resulting matte acrylic resin film for thermoforming can be increased. Therefore, the glass transition temperature 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 alkyl acrylate 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.

  From the viewpoint of the surface hardness and heat resistance of the resulting matte acrylic resin film for thermoforming, the content of the methacrylic acid alkyl ester (II-A) is a monomer component that is a raw material for the thermoplastic polymer (II) ( 100-100 mass%), 50-100 mass% is preferable. More preferably, it is 80 mass% or more, and is 99.9 mass% or less.

The content of the acrylic acid alkyl ester (II-B) is selected from the viewpoint of imparting the toughness required for the matte acrylic resin film for thermoforming to be obtained and the toughness required for insert molding or in-mold molding. In the monomer component (100% by mass) which is a raw material of II), 0 to 50% by mass is preferable. More preferably, it is 0.1 mass% or more and 20 mass% or less.
The content of the other monomer (II-C) having a double bond capable of copolymerization is 0 to 50 mass in the monomer component (100 mass%) which is a raw material of the thermoplastic polymer (II). Is preferred.

The reduced viscosity (0.1 g of polymer is dissolved in 100 mL of chloroform and measured at 25 ° C.) of the thermoplastic polymer (II) is the insert moldability, in-mold moldability of the resulting matte acrylic resin film for thermoforming, And from a viewpoint of film forming 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 content of the rubber-containing polymer (I ′) in the acrylic resin composition (III) is 5 in the acrylic resin composition (III) (100% by mass) from the viewpoint of film forming property, pencil hardness, and moldability. -30 mass parts is preferable. 10 mass parts or more are more preferable from a viewpoint of film forming property and moldability, and 25 mass parts or less are more preferable from a viewpoint of pencil hardness.

  In the case of the acrylic resin composition (III) using the rubber-containing multistage polymer (I) and the thermoplastic polymer (II) in combination, the rubber-containing multistage polymer (100% by mass) in the acrylic resin composition (III) (100% by mass) I) 1-99 mass% and thermoplastic polymer (II) 1-99 mass% are preferable. From the viewpoint of molding whitening resistance of the matte acrylic resin film for thermoforming, 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.

The gel content of the acrylic resin composition (III) is preferably 10 to 80% from the viewpoints of molding whitening resistance and film forming property. More preferably, it is 20% or more, and particularly preferably 40% or more. Further, it is more preferably 75% or less, particularly preferably 70% 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, the 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 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 a composition of 50 to 100% by mass of methyl methacrylate and 0 to 50% by mass of another monomer having a double bond copolymerizable therewith. It is obtained by polymerizing the monomer component. 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 formability better. The thermoplastic polymer (IV) should be used in the range of more than 0 parts by mass and 20 parts by mass or less with respect to 100 parts by mass in total of the rubber-containing polymer (I ′) and the thermoplastic polymer (II). Is preferred. 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 trade name: Tinuvin 234 manufactured by Ciba Specialty Chemicals, and trade name: ADK STAB LA-31 manufactured by Asahi Denka Kogyo Co., Ltd. Specific examples of the triazine ultraviolet absorber include trade name: Tinuvin 1577 manufactured by Ciba Specialty Chemicals.

  The ultraviolet absorber is based on 100 parts by mass of the total of the rubber-containing polymer (I ′), the thermoplastic polymer (II), and the thermoplastic polymer (IV) (hereinafter referred to as “acrylic resin raw material”). It is preferable to use in the range of 0.1 to 10 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 a light stabilizer, a well-known thing can be used and 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, there are 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; and a method of kneading and mixing a mixture obtained by adding a compounding agent in advance to an acrylic resin raw material in various kneaders. Can be mentioned. 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 preferable 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 for thermoforming is improved, the coating is missing when the matte layer is formed on the acrylic resin film substrate, and the matte acrylic resin film for thermoforming is printed. Printing omission at the time of processing can be suppressed. As the metal roll, it is used in a sleeve touch method comprising a metal mirror surface touch roll; a metal sleeve (metal thin film pipe) described in Japanese Patent No. 2808251 or International Publication No. 97/28950, and a molding roll. 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-like material 10 μm or more, a 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 is more preferably 30 μm or more, and particularly preferably 50 μm or more. Further, the thickness of the acrylic resin film 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 surface of the acrylic resin film substrate needs to be 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 occurrence of cracks in the matte layer can be reduced even when insert molding or in-mold molding is performed to form a deep-drawn shape. Moreover, since the coating amount per unit area used in the coating is reduced, it is possible to reduce the physical property deterioration of the acrylic resin film substrate due to the solvent. 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 can be satisfactorily exhibited, so that the amount of the matte material per unit volume can be reduced, and the deterioration of physical properties of the matte layer can be reduced. Further, by reducing the thickness of the matte layer, the effect of adding the wax is enhanced, so that good scratch resistance is exhibited. The thickness of the matte layer is 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, organic or inorganic particles having a mass average particle diameter of 0.5 to 50 μm are preferably used. 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 is improved, but also the reflection of fluorescent lamps is reduced. For example, when combined with a metallic pattern, the appearance of scraping aluminum It becomes close to, and it looks like a 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 the thickness 10 μm or less, not only the moldability of the matte layer is improved, but the reflection of the fluorescent lamp is slightly visible. It has a luxurious appearance and high industrial utility value. Further, when a matte acrylic resin film for thermoforming is obtained by, for example, gravure coating or gravure reverse coating, the mass average particle diameter is more preferably 30 μm or less, and particularly preferably 10 μm or less from the viewpoint of reducing doctor lines. Moreover, it is preferable to use what does not contain a coarse particle of 20 micrometers or more from a viewpoint of coating omission generation | occurrence | production in the case of coating and a doctor stripe | line | muscle generation | occurrence | production.

  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 the organic particles, it is preferable to select a particle having a refractive index as close as possible to 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 inorganic particles can be used. Examples thereof include mica, talc, silica, calcium carbonate, titanium oxide, and iron oxide. In addition, inorganic particles surface-treated with an acrylic resin, a polyurethane resin, a surfactant or the like can be used. As the inorganic particles, it is preferable to use non-surface-treated inorganic particles from the viewpoint of yellowing during heating. The material to be surface-treated is appropriately selected from the viewpoint of yellowing during heating. Of these, silica is particularly preferred from the viewpoints of the appearance, physical properties, etc. of the resulting thermoformed matte acrylic resin film. As the silica, known ones that are commercially available can be used, and examples thereof include Mizusukasil manufactured by Mizusawa Chemical Co., Ltd., and Sicilia manufactured by Fuji Silysia Chemical Co., Ltd.

  When inorganic particles are used as a matting material, a unique whiteness can be imparted to a matte acrylic resin film for thermoforming. Is expensive. 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 matting material added is the matte acrylic resin film for thermoforming from the viewpoint of in-mold moldability and insert moldability, or by gravure coating, gravure reverse coating, kiss reverse coating, microgravure coating, etc. When obtaining, from a viewpoint of reducing doctor muscle, 30 mass parts or less are more preferable, and 20 mass parts or less are especially preferable.

(Binder resin)
As the binder resin, it is preferable to use a known thermosetting resin or photocurable resin from the viewpoint of scratch resistance. 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-based resin, known ones can be used. 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 thermosetting resin containing a containing acrylic resin and a polyisocyanate is preferred.

The hydroxyl value of the hydroxyl group-containing acrylic resin is preferably 20 mgKOH / g or more, more preferably 50 mgKOH / g or more, from the viewpoints of pencil hardness and scratch resistance. 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 glass transition temperature of the hydroxyl group-containing acrylic resin is preferably 50 ° C. or higher, and more preferably 60 ° C. or higher, from the viewpoints of heat resistance, film blocking properties, pencil hardness, and scratch resistance.

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

The polyisocyanate is preferably used so as to have an addition amount corresponding to a range of 0.5 to 1.5 times the molar amount of the isocyanate group with respect to the molar amount of the hydroxyl group in the hydroxyl group-containing acrylic resin. By setting it to 0.5 times or more, since the amount of isocyanate groups is sufficient with respect to the hydroxyl group, the curing is sufficiently advanced and the pencil hardness, scratch resistance, and chemical resistance are improved. Less than 1.5 times the added amount, sufficient pencil hardness, scratch resistance and chemical resistance are exhibited, the matte layer is less likely to crack during molding, and there are problems such as film blocking due to excess polyisocyanate. Less likely to occur.
In addition, when a thermoplastic resin is used for the binder resin, although the moldability is good, the chemical resistance tends to decrease. When used as a vehicle interior, if a fragrance component adheres, the matte layer melts, so that an appearance defect such as a matte return may occur.

(wax)
As the wax, known natural waxes such as carnauba wax, wax, montan wax, and paraffin wax; known synthetic waxes such as fatty acid amide, polyethylene, polypropylene, polytetrafluoroethylene; alkyl-modified silicone oil, polyether-modified silicone oil And known silicone waxes; block copolymers containing silicon and fluorine components, and the like. The wax is preferably a polyolefin wax such as polyethylene, polypropylene, or a composite of polyethylene and polypropylene.

  As the wax, a wax having a melting point of 120 ° C. or higher is preferable, and a wax having a melting point of 120 ° C. or higher is preferable, because the wax is less likely to bleed due to heat during molding as the melting point is higher, and mold contamination is less likely to occur during in-mold molding or insert molding. The wax is more preferable. In addition, regarding the block copolymer containing a silicon-type and a fluorine-type component, it is possible to express the outstanding bleed resistance even if melting | fusing point is 100 degrees C or less by selecting another copolymer component.

  Examples of the wax having a melting point of 120 ° C. or higher include polyethylene, polypropylene, a composite of polyethylene and polypropylene, and polytetrafluoroethylene. From the viewpoint of the melting point, a composite of polyethylene and polypropylene is more preferable, and polytetrafluoroethylene is particularly preferable. From the viewpoint of the effect of preventing scratches, polytetrafluoroethylene is more preferable, and polyethylene, polypropylene, and a composite of polyethylene and polypropylene are particularly preferable. Further, by using these in combination, it is possible to develop more excellent scratch resistance, and a combination of polyethylene and polytetrafluoroethylene is particularly preferable.

  On the other hand, a wax having a small specific gravity is preferable from the viewpoint of wax sedimentation during coating. For example, polytetrafluoroethylene having a specific gravity exceeding 2 is likely to settle, although it depends on the viscosity of the liquid at the time of coating. 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, as well as white streaks that are generated by rolling up the settled wax on the mat roll for thermoforming. Transferred as defects on the acrylic resin film.

From the above, the wax is preferably a polyolefin wax such as polyethylene, polypropylene, or a composite of polyethylene and polypropylene.
The polyolefin wax is usually in the form of ultrafine powder obtained by dry pulverization, but in the present invention, a polyolefin wax having a mass average particle diameter larger than the thickness of the matte layer is preferred. From the viewpoint of scratch resistance, polyolefin wax having a mass average particle diameter larger than the value obtained by doubling the thickness of the matte layer is more preferable. Further, from the viewpoint of occurrence of omission of coating at the time of coating and generation of doctor streaks, polyolefin wax that does not contain coarse particles of 20 μm or more is preferable.

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

(Method of forming matte layer)
The matte layer is preferably formed 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 the printing method include known printing methods such as gravure printing, screen printing, and offset printing.
Coating methods include flow coating, spray coating, bar coating, gravure coating, gravure reverse coating, kiss reverse coating, micro gravure coating, roll coating, blade coating, rod coating, and roll doctor. Known coating methods such as a coating method, an air knife coating method, a comma roll coating method, a reverse roll coating method, a transfer roll coating method, a kiss roll coating method, a curtain coating method, and a dipping coating method may be mentioned.

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, it is difficult to cause omission of coating due to film curling.
A well-known thing can be used as a gravure roll used by the gravure coating method. In particular, from the viewpoint of reducing the influence of the plate, it is preferable to use a slanted gravure roll having a plate of 150 lines or more per inch. When the plate is formed on the matte acrylic resin film for thermoforming, the design properties are impaired, and the industrial utility value is lowered. Further, it is preferable to use a slanted gravure roll in which a slanted plate is formed because the plate can be reduced as compared with the case of using a normal gravure roll having a lattice-shaped plate.

In addition, when an oblique gravure roll is used, the matte appearance of the molded product when thermoforming such as in-mold molding or insert molding is performed is close to the original matte film appearance. Specifically, since the reflection of a fluorescent lamp in a molded product is close to the reflection of a fluorescent lamp in a matte film, the design at the stage of a matte acrylic resin film or laminated sheet for thermoforming having a pattern layer Since a molded product can be obtained without impairing the feeling, the industrial utility value is high. For example, even if a gravure roll having a grid pattern is used, a very good appearance can be obtained at the stage of a matte acrylic resin film by using a roll having a small groove between the molds. A molded product obtained by thermoforming such as insert molding differs from the appearance at the film stage.
The plate is preferably engraved at an angle of 40 to 50 ° with respect to the roll axis direction. By using such a diagonal gravure roll, it is possible to obtain an acrylic resin film having a uniform matte coating surface free from coating spots.

As the material of the gravure roll, a known material such as copper hard chrome plated or ceramic can be used, and ceramic is preferable from the viewpoint of durability.
Moreover, as a doctor blade used by the gravure coating method, well-known things, such as steel, stainless steel, and ceramics, can be used, and it is preferable to use a stainless steel doctor blade from the viewpoint of doctor muscles. Or it is also preferable to use the doctor blade which coated the material which consists of a ceramic and a lubricating material to the stainless steel doctor blade, and improved sliding property. Also, a plastic doctor blade may be used.

In the case where a paint is applied on the acrylic resin film substrate, the amount of the solvent contained in the paint applied per 1 m ^{2 of the} acrylic resin fill substrate is 30 g from the viewpoint of reducing physical property deterioration of the acrylic resin fill substrate due to the solvent. The following is preferable, 20 g or less is more preferable, and 10 g or less is particularly preferable. In addition, the amount of the coating material to be applied needs to be an amount such that the thickness of the matte layer after drying is 0.1 to 5 μm. When the coating amount is such that the matte layer has a thickness of 0.1 μm or more, the surface physical properties in the case of a laminate can be expressed. Preferably it is 0.5 micrometer or more, More preferably, it is 0.8 micrometer or more. If the amount of paint is such that the thickness of the matte layer is 5 μm or less, the amount of paint per unit area used for 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 glass transition temperature of the binder resin is preferable because the solvent hardly remains in the matte acrylic resin film for thermoforming. 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. A volatile solvent having a boiling point not higher than 80 ° C., preferably not higher than 30 ° C., higher than the glass transition temperature of the resin component which is the main constituent of the acrylic resin film substrate is preferable.

  Solvents include alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butanol and ethylene glycol; aromatic solvents such as xylene, toluene and benzene; aliphatic hydrocarbon solvents such as hexane and pentane; Halogenated hydrocarbon solvents such as carbon chloride; 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 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; acetic anhydride Acid anhydride system such as Agents: Ester solvents such as ethyl acetate, n-propyl acetate, butyl acetate and butyl formate; Nitrogen-containing solvents such as ethylamine, toluidine, dimethylformamide and dimethylacetamide; Sulfur-containing solvents such as thiophene and dimethyl sulfoxide; Diacetone alcohol 2-methoxyethanol (methyl cellosolve), 2-ethoxyethanol (ethyl cellosolve), 2-butoxyethanol (butyl cellosolve), diethylene glycol, 2-aminoethanol, acetocyanohydrin, diethanolamine, morpholine, 1-acetoxy-2-ethoxyethane, A solvent having two or more kinds of functional groups such as 2-acetoxy-1-methoxypropane; various known solvents such as water can be used. 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, and methyl isobutyl ketone is preferable because it can reduce deterioration of physical properties of the acrylic resin fill substrate due to the solvent. Moreover, it is preferable to use butyl acetate and methyl isobutyl ketone together from the viewpoint of adhesion between the matte layer and the acrylic resin fill substrate. Also, from the viewpoint of gloss after coating, it is preferable to use a medium boiling solvent such as butyl acetate and methyl isobutyl ketone, and a high boiling solvent such as 2-acetoxy-1-methoxypropane and cyclohexanone.

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

Before using the paint, it is preferable to carry out filtration for the purpose of removing foreign substances and coarse particles of silica and wax from the viewpoint of reducing omission of coating and reducing the generation of doctor streaks. Filtration may be performed after preparation of the paint, or may be performed immediately before coating or while coating.
The paint can be filtered with a known filtration device, and for example, CPII-10, 03, 01 manufactured by Chisso Filter Co., Ltd. is preferably used.

  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, it may be necessary to apply several tens of times, and in this case, the cost is high and the productivity is not so good. On the other hand, since the matte acrylic resin film for thermoforming 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.

<Matte acrylic resin film for thermoforming>
(Pencil hardness)
The matte acrylic resin film for thermoforming of the present invention preferably has a pencil hardness (measured based on JIS K5400) of 2B or more.
By forming a matte acrylic resin film for thermoforming with a pencil hardness of 2B or more, the surface of the matte acrylic resin film for thermoforming is not easily damaged during the process of insert molding or in-mold molding, Abrasion resistance is also good.

Considering the case where it is used for a laminate such as a vehicle member, the pencil hardness of the matte acrylic resin film for thermoforming of the present invention is preferably HB or more.
In order to obtain a matte acrylic resin film for thermoforming having such a pencil hardness, the pencil hardness of the acrylic resin film substrate is important. The pencil hardness of the acrylic resin film substrate is preferably 2B or more, more preferably HB or more, and most preferably F or more.

(Heat resistant yellowing)
The matte acrylic resin film for thermoforming of the present invention has a yellowness (hereinafter referred to as YI) after heating the surface of the matte layer to 200 ° C at a heating rate of 20 to 25 ° C / second in an air atmosphere. It is preferable that “(200 ° C.)” and the yellowness (hereinafter referred to as YI) of the matte acrylic resin film for thermoforming before heating satisfy the relationship of the following formula (i).
YI ′ (200 ° C.) − YI ≦ 1.3 (i)

When YI ′ (200 ° C.)-YI is 1.3 or less, yellowing of a matte acrylic resin film for thermoforming is observed in a general pattern such as wood grain when insert molding and in-mold molding are performed. In other words, it is possible to obtain a laminated body having good design properties. YI ′ (200 ° C.)-YI is preferably 1.0 or less. In the case of 1.0 or less, the matte acrylic resin film for thermoforming has a yellowing discoloration even in a pattern with a strong whiteness or a metallic pattern that is easily noticeable in yellowing. Therefore, it is possible to obtain a laminate that maintains good design properties. YI ′ (200 ° C.)-YI is more preferably 0.5 or less, and particularly preferably 0.3 or less.
YI ′ (200 ° C.) − YI is preferably −2.0 or more from the viewpoint of retaining the design before molding when insert molding and in-mold molding are performed.

Furthermore, the yellowness of the matte acrylic resin film for thermoforming after heating the surface of the matte layer to 250 ° C. at a temperature increase rate of 20 to 25 ° C./second in an air atmosphere (hereinafter referred to as YI ′ ( 250 ° C.), the value obtained by subtracting the yellowness (YI) of the matte acrylic resin film for thermoforming before heating (YI ′ (250 ° C.) − YI) is preferably 2.0 or less. 5 or less is more preferable, 1.0 or less is more preferable, and 0.5 or less is particularly preferable. YI ′ (250 ° C.)-YI is preferably −2.0 or more.
In addition, from the viewpoint of design at the time of printing, the yellowness (YI) of the matte acrylic resin film for thermoforming before heating is preferably low. Specifically, YI is preferably 6.0 or less.

When the film is heated, the yellowness of the matte acrylic resin film for thermoforming is cooled to room temperature, and then the snow white oily colored paper (Munsell symbol N9.5 on the acrylic resin substrate side of the film (standard) Color card 230, manufactured by Nippon Color Research Co., Ltd.), and using a spectroscopic color difference meter SE2000 (manufactured by Nippon Denshoku), the value obtained by measuring the matte layer side of the film under standard C light and reflection mode conditions. Use.
Setting the difference in yellowness of the matte acrylic resin film for thermoforming before and after heating within the above range can be achieved by constituting the matte layer from a specific component. Specifically, it is preferable to select components such as a matting material and a curing agent that are suitable from the viewpoint of heat-resistant yellowing.

(Dynamic friction coefficient)
The matte acrylic resin film for thermoforming of the present invention has a coefficient of dynamic friction (hereinafter referred to as matte layer) between the matte layer surface and Broad No. 60 under the test conditions of a test speed of 100 mm / min, a moving distance of 10 mm, and a load of 9.8 N. The surface friction coefficient is preferably 0.23 or less. The matte acrylic resin film for thermoforming with a kinetic friction coefficient of 0.23 or less on the matte layer surface is less likely to be scratched on the surface of the matte acrylic resin film for thermoforming during the process of insert molding or in-mold molding. Furthermore, the scratch resistance of the laminate is improved.

In a conventional matte acrylic resin film, pencil hardness is often used as an index of scratch resistance, but in a matte acrylic resin film for thermoforming in which a matte layer is formed on an acrylic resin film substrate, Besides the pencil hardness, the dynamic friction coefficient is also an important index. That is, the smaller the dynamic friction coefficient, the better the scratch resistance of the matte acrylic resin film for thermoforming. For example, a matte acrylic resin film for thermoforming does not exhibit good scratch resistance even if the pencil hardness is H unless the dynamic friction coefficient is 0.23 or less.
The laminated body using the matte acrylic resin film for thermoforming of the present invention can be suitably used for various vehicle members such as a door waist garnish, a front control panel, a power window switch panel, and an airbag cover. It is very useful industrially from the viewpoint of expanding applications.

(Haze value)
The haze value of the matte acrylic resin film for thermoforming varies depending on the type of matte material, the amount added, and the thickness of the matte layer. The haze value of the matte acrylic resin film for thermoforming is preferably 5% or less, more preferably 3% or less, from the viewpoint of design when the pattern layer is viewed through the matte acrylic resin film for thermoforming. Further, when a metallic pattern layer is combined, the haze value is preferably set in a range of 1 to 3%. If the matte acrylic resin film for thermoforming has a haze value of 1 to 3%, it becomes a design with a faint whiteness and close to the appearance as if the aluminum has been cut out. High utility value. The haze value was measured by a test method according to JIS K7136 for a film after the surface of the mirror-finished SUS plate heated to 130 ° C. was hot-pressed with a matte acrylic resin film for thermoforming under the condition of 3 MPa and the surface was mirror-finished. Value.

<Pattern layer>
In the matte acrylic resin film for thermoforming of the present invention, a pattern layer may be formed in order to impart design properties to various substrates. In this case, it is preferable to form a pattern layer 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 or in-mold molding. Examples of the print pattern include a pattern made of wood grain, stone grain, cloth grain, sand grain, geometric pattern, characters, full face, and the like.
As binders for the printing layer, polyvinyl resins such as vinyl chloride / vinyl acetate copolymers, polyamide resins, polyester resins, polyacrylic resins, polyurethane resins, polyvinyl acetal resins, polyester urethane resins, cellulose Examples of the resin include ester resins, alkyd resins, and chlorinated polyolefin resins. As the polyacrylic resin, for example, an acrylic resin composition (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 chrome lead. Examples of red pigments include azo pigments such as polyazo, organic pigments such as quinacridone, and inorganic pigments such as petals. Examples of the blue pigment include organic pigments such as phthalocyanine blue; inorganic pigments such as cobalt blue. Examples of the black pigment include organic pigments such as aniline black. Examples of the white pigment include inorganic pigments such as titanium dioxide.
As the dye, various known dyes can be used as long as the effects of the present invention are not impaired.

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

The number of missing prints in the print layer is preferably 10 pieces / m ² or less from the viewpoints of design properties and decorating properties. By setting the number of printing omissions to 10 pieces / m ² or less, the appearance of the laminate using the matte acrylic resin film for thermoforming 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 extension during the insert or in-mold molding so that a desired surface appearance can be obtained in the laminate obtained by the insert or in-mold molding.

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

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

(Cover film)
The matte acrylic resin film for thermoforming of the present invention may further be provided with a cover film. This cover film is effective for preventing dust on the surface of the matte acrylic resin film for thermoforming. 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 a cover film is provided on the surface of the matte layer, the cover film adheres to the matte layer before in-mold and insert molding, and immediately peels off when in-mold and insert molding. Therefore, 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 for thermoforming 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 for thermoforming is laminated on the thermoplastic resin layer is preferably laminated so 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 made of a material having compatibility with the base material for the purpose of improving the adhesion with the base material. More preferably, the thermoplastic resin layer is made of the same material as the base material. As the thermoplastic resin layer, a known thermoplastic resin film or sheet can be used. For example, acrylic resin; ABS resin (acrylonitrile-butadiene-styrene copolymer); AS resin (acrylonitrile-styrene copolymer); Vinyl resin; Polyolefin resin such as polyethylene, polypropylene, polybutene, polymethylpentene; Polyolefin copolymer such as ethylene-vinyl acetate copolymer or saponified product thereof, ethylene- (meth) acrylate copolymer; polyethylene Polyester resins such as terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, and polycarbonate; polyamide resins such as 6-nylon, 6,6-nylon, 6,10-nylon, and 12-nylon; Ren resin; Fibrin derivatives such as cellulose acetate and nitrocellulose; Fluorine resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, and ethylene-tetrafluoroethylene copolymer; or two selected from these, Or 3 or more types of copolymers or a mixture, a composite, a laminated body, etc. are mentioned.
Among these, as the thermoplastic resin layer, the formability of the pattern layer (can be formed on the thermoplastic resin layer instead of forming on the matte acrylic resin film for thermoforming), the secondary of the laminated film or sheet From the viewpoint of moldability, acrylic resin, ABS resin, vinyl chloride resin, polyolefin, and polycarbonate are preferable.

For the thermoplastic resin layer, if necessary, general compounding agents such as stabilizers, antioxidants, lubricants, processing aids, plasticizers, impact agents, foaming agents, fillers, antibacterial agents, fungicides 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 has a thickness such that the appearance of the matte acrylic resin film for thermoforming exhibits a completely smooth upper surface, absorbs surface defects of the base material, or does not disappear the pattern layer during injection molding. It is preferable.

  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 for thermoforming and a thermoplastic resin layer can be laminated by extrusion lamination.

  By using the matte acrylic resin film for thermoforming of the present invention as a laminated film or sheet, a sufficient strength 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 to be transmitted to the matte acrylic resin film for thermoforming, or the pattern layer is not easily lost when the base material is injection-molded. Give an advantage.

  If necessary, for example, corona treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromate treatment, anchor on the surface of the thermoplastic resin layer of the matte acrylic resin film for thermoforming, laminated film or sheet, Surface treatment such as primer treatment may be performed. Improve adhesion between matte acrylic resin film for thermoforming and pattern layer, between thermoplastic resin layer and pattern layer, between matte acrylic resin film for thermoforming and thermoplastic layer, etc. Can do.

<Laminated body>
The laminate of the present invention is obtained by laminating the matte acrylic resin film for thermoforming of the present invention, the laminated film or sheet thereof on a substrate. At this time, it is preferable to laminate the matte acrylic resin film for thermoforming 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 base material include: resin; wood board such as wood veneer, wood plywood, particle board, medium density fiber board (MDF); water quality board such as wood fiber board; metal such as iron and aluminum.

  As the resin, any known resin can be used regardless of the type. Examples of the resin include polyolefin resins such as polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, olefin thermoplastic elastomer; polystyrene resin, ABS resin (acrylonitrile) -Butadiene-styrene copolymer), AS resin (acrylonitrile-styrene copolymer), general-purpose thermoplastic or thermosetting resin such as acrylic resin, urethane resin, unsaturated polyester resin, epoxy resin; polyphenylene oxide polystyrene General-purpose engineering resins such as resin, polycarbonate resin, polyacetal, polycarbonate-modified polyphenylene ether, polyethylene terephthalate; polysulfone, polyphenylene sulfide, Super engineering resins such as rephenylene oxide, polyetherimide, polyimide, liquid crystalline polyester, polyallyl heat-resistant resin, etc .; reinforcing materials such as glass fiber or inorganic fillers (talc, calcium carbonate, silica, mica, etc.), modification of rubber components, etc. Examples thereof include a composite resin to which a quality agent is added or various modified resins.

Of these, the material for the substrate is preferably a matte acrylic resin film for thermoforming, a laminate 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 when a resin that is not thermally fused, such as a polyolefin-based resin, by providing an adhesive layer, one selected from the group consisting of a matte acrylic resin film for thermoforming, a laminated film or a sheet thereof and a base material are formed during molding. It is possible to bond them.

  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 for thermoforming, or a laminated film or sheet thereof, and then performing vacuum forming in a mold having a vacuuming function, and then in the same mold, This is a method of obtaining a laminated body in which a matte acrylic resin film for thermoforming, or a laminated film or sheet thereof and a base material are integrated by injection molding a resin. 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 the 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, and 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 for thermoforming of the present invention containing the rubber-containing multistage polymer (I) is used, the pattern layer disappears as compared with the case of using a conventionally known acrylic resin film. Can be reduced.
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 for thermoforming, 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, it is possible to increase the cycle of vacuum forming, 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 for thermoforming of the present invention, or a laminated film or sheet thereof, is rich in 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. Making the shrinkage rate of the resin after injection molding approximate the shrinkage rate of the matte acrylic resin film for thermoforming, or its laminated film or sheet, warping of the laminate obtained by in-mold molding, insert molding, or This is preferable because problems such as film or sheet peeling 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 for thermoforming of the present invention, and the laminated film or sheet thereof exhibit a design that is difficult to realize when a matte material is added to a conventional acrylic resin film substrate, and has good handleability. Yes, even when insert molding or in-mold molding is performed to form a deep-drawn shape, the matte layer does not crack, and scratch resistance, surface hardness, and heat resistance required for decorative films for automotive parts A matte acrylic resin film for thermoforming having heat resistance, chemical resistance, heat yellowing, and matting properties, and a laminate in which a matte acrylic resin film for thermoforming is laminated on a substrate can be provided. Moreover, the matte acrylic resin film for thermoforming of the present invention can be stably produced. According to this invention, compared with the conventional acrylic resin film, it is possible to expand the use application of the matte acrylic resin film for thermoforming remarkably.

  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), produced acrylic resin film substrates (A) to (C) The physical properties of the matte acrylic resin film for thermoforming obtained in Examples 1 to 32 and Comparative Examples 1 to 3, and laminates were measured and evaluated as follows.
Evaluation of the laminated body was performed using the laminated body produced for the moldability evaluation shown in the following (13) or (14).

(1) Mass average particle diameter of rubber-containing polymer (I ′) and rubber-containing multistage polymer (I):
For the polymer latex of the rubber-containing polymer (I ′) or rubber-containing multistage polymer (I) obtained by emulsion polymerization, a light scattering photometer DLS-700 (trade name) manufactured by Otsuka Electronics Co., Ltd. was used. , Measured by dynamic light scattering.
(2) Gel content of rubber-containing polymer (I ′) and rubber-containing multistage polymer (I):
A predetermined amount (mass before extraction) of the rubber-containing polymer (I ′) or the rubber-containing multistage polymer (I) (coagulated powder obtained after polymerization) is subjected to extraction treatment in an acetone solvent under reflux, and this treatment liquid Was separated by centrifugation, and after drying, the mass of acetone-insoluble matter was measured (mass after extraction) and calculated by the following formula.
Gel content (%) = mass after extraction (g) / mass before extraction (g) × 100

(3) Glass transition temperature (Tg) of rubber-containing polymer (I ′), rubber-containing multistage 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:
It measured according to JIS K0070.
(6) Mass average molecular weight of binder resin:
Using Shimadzu LC-6A system (manufactured by Shimadzu Corporation), three KF-805L (manufactured by Showa Denko KK) connected as a GPC column, THF as a solvent, and measurement in terms of polystyrene. .

(7) Heat shrinkage rate of acrylic resin film substrate:
Draw three parallel straight lines at 5 cm intervals 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. The interval 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) Thickness of matte layer of matte acrylic resin film for thermoforming:
A sample obtained by cutting a matte acrylic resin film for thermoforming to a thickness of 70 nm in the cross-sectional direction is observed with a transmission electron microscope (J100S manufactured by JEOL Ltd.), and the thickness is measured at five locations. The thickness of the matte layer was determined by averaging. 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.
(9) Pencil hardness of matte acrylic resin film for thermoforming:
It was measured according to JIS K5400, and the pencil hardness of the surface of the matte layer was measured.

(10) Surface gloss of matte acrylic resin film for thermoforming:
Using a gloss meter (manufactured by Murakami Color Research Laboratory, GM-26D type (trade name)), the surface gloss at 60 ° of the matte layer surface was measured.
(11) Haze of matte acrylic resin film for thermoforming:
After a matte acrylic resin film for thermoforming is sandwiched between two mirror-finished SUS plates having a thickness of about 3 mm and a surface roughness of 0.5 s, and held for 3 minutes under conditions of 130 ° C. and 3 MPa, press molding is performed. Cooled below room temperature. Subsequently, the haze (internal haze) was evaluated according to JIS K7136.

(12) Heat-resistant yellowing of matte acrylic resin film for thermoforming:
A vacuum / pressure forming machine (manufactured by Asano Laboratories) equipped with a far-infrared heater panel with a matte acrylic resin film for thermoforming of about 75 μm thickness set on top; 350 ° C, bottom; 500 ° C. Fixed to the clamp frame. In addition, the far-infrared heater panel was installed in both surfaces of the place 100 mm above and below the matte acrylic resin film for thermoforming set in the clamp.
The surface temperature of the matte acrylic resin film for thermoforming before heating was 25 ° C. From here, it heated until the surface temperature of the mat layer of the mat acrylic resin film for thermoforming reached a predetermined temperature. The time required for the surface temperature of the matte layer to reach 250 ° C. was about 11 seconds, and the temperature raising speed was about 20 ° C./second. The time required for the surface temperature of the matte layer to reach 200 ° C. was about 7 seconds, and the heating rate was about 25 ° C./second. The surface temperature of the matte layer was measured with a non-contact type thermometer arranged above the clamp.
Then, after cooling until the surface temperature of the matte acrylic resin film for thermoforming reaches room temperature again, a snow white oil colored paper having a Munsell symbol of N9.5 (standard color card 230, Japan) on the acrylic resin film substrate side of the film. Measure the yellowness YI 'using the spectroscopic color difference meter SE2000 (Nippon Denshoku) with the matte layer side of the film as the measurement surface under the conditions of standard C light and reflection mode. did.
On the other hand, the yellowing degree YI was measured in the same manner for the matte acrylic resin film for thermoforming before heating, and the heat-resistant yellowing was evaluated by the value obtained by subtracting YI from YI ′.

(13) Insert moldability of matte acrylic resin film for thermoforming:
A silver metallic layer as a pattern layer was provided on the acrylic resin film substrate side by gravure printing on a matte acrylic resin film for thermoforming having a thickness of about 75 μm. Further, a 1 mm thick ABS sheet having an adhesive layer is laminated on the matte acrylic resin film for thermoforming so that the adhesive layer and the silver metallic layer are in contact with each other, and the matte acrylic resin film for thermoforming is laminated. A laminated sheet was obtained. Molding was performed using this laminated sheet.
Specifically, the obtained laminated sheet is placed in a mold having a vacuuming function so that the matte acrylic resin film side for thermoforming is the cavity side, and a heater is used until the laminated sheet reaches 190 ° C. Then, vacuum forming was performed. Then, unnecessary parts were trimmed. A mat formed by vacuum forming a mat for vacuum forming 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. It arrange | positioned so that the acrylic resin film side might become a cavity side. Subsequently, an ABS resin (trade name “Diapet ABS Bulk Sum TM25” manufactured by UMG ABS Co., Ltd.) serving 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 corner corner R connecting the bottom surface and the side surface on the cavity side of the mold is about 3. That is, the corner R of the laminate edge portion on the side where the matte acrylic resin film for thermoforming is laminated is about 3. The corner R was measured with RADIUS GAGE manufactured by FUJI TOOL.
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 1 cm ² formed on the obtained laminate, a convex portion with a height of 1 mm, or the vicinity of the corner of the laminate edge was observed and evaluated as follows.
(About cracking of convex part)
○: No crack,
Δ: Slight cracking in the matte layer,
X: Large cracks occur in the matte layer.
(About cracks near corners)
○: No crack,
Δ: Slight cracking in the matte layer,
X: Large cracks occur in the matte layer.
(Regarding whitening of convex parts)
○: No film whitening
X: There is strong whitening of the film.
(About whitening near the corner)
○: No film whitening
X: There is strong whitening of the film.

(14) In-mold formability of matte acrylic resin film for thermoforming:
In-mold molding was performed using a matte acrylic resin film for thermoforming having a thickness of about 75 μm.
Specifically, using a mold having a vacuum 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, J85ELII 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 corner corner R connecting the bottom surface and the side surface on the cavity side of the mold is about 3. That is, the corner R of the laminate on which the matte acrylic resin film for thermoforming is laminated is about 3. The corner R was measured with RADIUS GAGE manufactured by FUJI TOOL.

Vacuum forming of matte acrylic resin film for thermoforming is performed under the conditions of a heater temperature of about 330 ° C, a heating time of 12 seconds, and a distance between the heater and the film of 15 mm, and the matte layer is in a direction in contact with the mold. did.
In addition, the injection molding performed in the same mold continues by injecting the base resin from the opposite side of the matte layer under the conditions of a cylinder temperature of 250 ° C, an injection speed of 30%, an injection pressure of 43%, and a mold temperature of 60 ° C. did. As the base resin, heat-resistant ABS resin (trade name “Bulksum TM25B” manufactured by UMG ABS Co., Ltd.) was used.

The state of 1 cm ² formed on the obtained laminate, a convex portion with a height of 1 mm, or the vicinity of the corner of the laminate edge was observed and evaluated as follows.
(About cracking of convex part)
○: No crack,
Δ: Slight cracking in the matte layer,
X: Large cracks occur in the matte layer.
(About cracks near corners)
○: No crack,
Δ: Slight cracking in the matte layer,
X: Large cracks occur in the matte layer.
(Regarding whitening of convex parts)
○: No film whitening
X: There is strong whitening of the film.
(About whitening near the corner)
○: No film whitening
X: There is strong whitening of the film.

(15) Coefficient of dynamic friction of laminate:
Dynamic friction on the matte layer surface of a laminate of matte acrylic resin films when Broad No. 60 is used as the material to be rubbed under the test conditions of a test speed of 100 mm / min, a moving distance of 10 mm, and a load of 9.8 N The coefficient was measured. In addition, the sample used what was shape | molded by (14), and the dynamic friction coefficient used the average value of five measurement points.

(16) Scratch resistance of the laminate:
(Condition 1)
While applying a load of 0.01 MPa on one Broad No. 60, the laminate formed in (14) is pressed, and the laminate is reciprocated 200 times at a stroke of 100 mm and at a speed of 30 reciprocations / minute. It was. The appearance of the laminate was evaluated as follows.
A: No change in appearance,
○: Slightly damaged,
Δ: There is a weak gloss return,
×: Strong gloss return.

(Condition 2)
The laminate formed in (14) was pressed on a five-layer gauze while applying a load of 0.049 MPa, and the laminate was reciprocated 200 times at a stroke of 100 mm and at a speed of 30 reciprocations / minute. . The appearance of the laminate was evaluated as follows.
A: No change in appearance,
○: Slightly damaged,
Δ: Weak gloss return
×: Strong gloss return.

(17) Chemical resistance (fragrance resistance) of the laminate:
A polyethylene cylinder having an inner diameter of 38 mm and a height of 15 mm is placed on the surface of the test piece of the laminate molded in (14), and is firmly attached to the test piece with a crimping machine, and an air freshener for automobile (Dia Chemical Co., Ltd.) Made, Grace Mate Poppy Citrus). After the opening was covered with a glass plate, it was placed in a thermostatic bath maintained at 55 ° C. and left for 4 hours. After the test, the crimper was removed, the test piece was washed with water and then air-dried, and the whitening state of the surface of the test part was observed.
○: The matte layer does not peel off (no gloss return),
Δ: There is slight peeling of the matte layer (there is a slight gloss return),
X: The matte layer is peeled off (there is glossy return).

(18) Appearance of laminate:
The appearance of the picture layer of the laminate under the light of a fluorescent lamp was visually evaluated as follows.
○: Reflection of the fluorescent lamp can be confirmed slightly. In the insert molded product, the pattern of the pattern layer is clearly visible and slightly white, so the silver metallic feeling is good.
Δ-1: The pattern of the pattern layer is clearly visible, the reflection of the fluorescent lamp is large, and the silver metallic feeling is poor.
Δ-2: The pattern of the pattern layer is clearly visible, the reflection of the fluorescent light cannot be confirmed, and the silver metallic feeling is poor.
X: Reflection of fluorescent light can be confirmed, but the undulation of the matte layer on the surface of the laminate is larger than the state of the matte acrylic resin film for thermoforming before molding, so the reflection is blurred .
XX: The pattern of the pattern layer can be seen as if a strong whiteness was applied.

(19) Appearance of laminate (evaluation of yellowing resistance):
The appearance of the picture layer of the laminate was visually evaluated as follows.
○: No change from the pattern layer before molding.
X: The yellowish color is more conspicuous than the pattern layer before molding, and the design looks different.

[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, MMA 0.3 part, n-BA 4.5 part, 1,3-BD 0.2 part, AMA 0.05 part and CHP 0 A monomer component consisting of 0.025 parts was added and stirred and mixed at room temperature. Next, 1.3 parts of an emulsifier (manufactured by Toho Chemical Co., Ltd., trade name “Phosphanol RS610NA”) was charged into the container while stirring, and stirring was continued for 20 minutes to prepare an emulsion.
Next, 139.2 parts of deionized water was put into a polymerization vessel equipped with a cooler, and the temperature was raised to 75 ° C. Further, a mixture prepared by adding 0.20 part of sodium formaldehyde sulfoxylate, 0.0001 part of ferrous sulfate and 0.0003 part of EDTA to 5 parts of ion-exchanged water was put into the polymerization vessel at once. Next, the prepared emulsion was dropped into the polymerization vessel over 8 minutes while stirring under nitrogen, and then the reaction was continued for 15 minutes to complete the formation of the first elastic polymer (I-1-A1). Subsequently, a monomer component consisting of 9.6 parts of MMA, 14.4 parts of n-BA, 1.0 part of 1,3-BD and 0.25 part of AMA is added over 90 minutes together with 0.016 part of CHP. After dropping into the polymerization vessel, the reaction was continued for 60 minutes to obtain an elastic polymer (I-1-A) containing the second elastic polymer (I-1-A2). The Tg of the first elastic polymer (I-1-A1) alone was −48 ° C., and the Tg of the second elastic polymer (I-1-A2) 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. A union (I-1-B) was formed. The intermediate polymer (I-1-B) alone had a Tg of 60 ° C.
Subsequently, after dropping a monomer component consisting of 57 parts of MMA, 3 parts of MA, 0.264 part of n-OM and 0.075 part of t-BH over 140 minutes, the reaction is continued for 60 minutes, A hard polymer (I-1-C) was formed 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. Salting out was carried out in an aqueous solution containing 5 parts, washed with water, recovered, and 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 first elastic polymer (I′-2-A1) 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. A latex of an elastic polymer (I′-2-A1) was obtained. The Tg of the first elastic polymer (I′-2-A1) 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 second elastic polymer (I′-2-A2) shown in Table 3 was added to the monomer component [raw material (c) for water]. ] Is continuously added at a rate of 4% / hour, and then held for 120 minutes to form the second elastic polymer (I′-2-A2), and the elastic polymer (I ′ A latex of -2-A) was obtained. The Tg of the second elastic polymer (I′-2-A2) alone was −38 ° C.

Subsequently, 0.4 parts of sodium formaldehyde sulfoxylate was added to the latex and held for 15 minutes. Then, while stirring at 80 ° C. in a nitrogen atmosphere, the raw material (d) for the hard polymer (I′-2-C) shown in Table 3 was increased in the amount of the monomer component [raw material (d)] with respect to water. After the continuous addition at a rate of 10% / hour, the mixture is held for 60 minutes to form a hard polymer (I′-2-C), and the weight of the rubber-containing polymer (I′-2) A combined latex was obtained. 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, and drying to obtain a 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))
The reaction vessel was charged with 200 parts of ion-exchanged water substituted with nitrogen, and as an emulsifier, 1 part of trade name “Latemul ASK” and 0.15 part of potassium persulfate were added.
Next, 40 parts of MMA, 2 parts of n-BA and 0.004 part of n-OM were charged and stirred at 65 ° C. for 3 hours in a nitrogen atmosphere to complete the polymerization.
Subsequently, a monomer component consisting of 44 parts of MMA and 14 parts of n-BA 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) was added to a 0.25% aqueous sulfuric acid solution, and the polymer was acidified, 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 ηsp / c = 0.06 L / g)] 25 parts, Ciba Specialty Chemicals Co., Ltd., trade name “Tinubin 234” 1.4 parts, Asahi Denka Kogyo Co., Ltd., trade name “Adeka Stub AO-50” 0.1 part, and Asahi After adding 0.3 part of a product name “ADK STAB LA-67” manufactured by Denka Kogyo Co., Ltd., the mixture was mixed using a Henschel mixer. This mixture [acrylic resin composition (III-1)] was supplied to a degassing type extruder (Ikegai Iron Works Co., Ltd., PCM-30 (trade name)) heated to 230 ° C., kneaded, and 300 mesh. Extruding while removing foreign matter with a screen mesh of No. 1 to obtain pellets (A).

  The pellets (A) produced by the above method were dried at 80 ° C. all day and night, and a cylinder temperature of 180 to 240 was used using a 40 mmφ non-vent screw type extruder (L / D = 26) equipped with a 300 mm wide T die. Extruded while removing foreign matter with a 500 mesh screen mesh under the condition of ℃, the molten acrylic resin film extruded under the conditions of T die temperature of 240 ℃ and slit width of T die of 0.3 mm, two metal cooling rolls An acrylic resin film substrate (A) having a thickness of 75 μm is formed by sandwiching the resin without any bank (resin pool), transferring the surface without rolling, and winding it around a paper roll with a winder. Was formed. The pencil hardness of the 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 = 90/10 (mass ratio), reduced viscosity ηsp / c = 0.06 L / g)] 84 parts, thermoplastic polymer (IV) 1 part as a compounding agent, Ciba Specialty Chemicals Co., Ltd., trade name “Tinubin 234” 1.4 parts, Asahi Denka Kogyo Co., Ltd., trade name “ADK STAB AO” After adding 0.1 part of “-50” and 0.3 part of “Adeka Stab LA-67” manufactured by Asahi Denka Kogyo Co., Ltd., the mixture was mixed using a Henschel mixer. This mixture [acrylic resin composition (III-2)] was supplied to a degassing extruder (Ikegai Iron Works Co., Ltd., PCM-30 (trade name)) heated to 230 ° C., kneaded, and 300 mesh. Extruding while removing foreign matters with a screen mesh of No. 1 to obtain pellets (B).
An acrylic resin film substrate (B) having a thickness of 75 μm was formed in the same manner as in the formation of the acrylic resin film substrate (A) except that the pellet (B) produced by the above method was used. The pencil hardness of the acrylic resin film substrate (B) was 2H.

[Production Example 6]
(Manufacture of acrylic resin film substrate (C))
In Production Example 5, [MMA / MA copolymer (MMA / MA = 99/1 (mass ratio), reduced viscosity ηsp / c = 0.06 L / g)] was used as the thermoplastic polymer (II). Similarly, an acrylic resin film substrate (C) having a thickness of 75 μm was formed. The pencil hardness of the acrylic resin film substrate (C) was 2H.

[Production Example 7]
(Manufacture of acrylic resin film substrate (D))
The pellet (A) was dried at 80 ° C. all day and night, and a 40 mmφ non-vent screw type extruder (L / D = 26) equipped with a 300 mm wide T-die was used. Extruded while removing foreign matter with a screen mesh mesh, passed through a molten acrylic resin film extruded under the conditions of a T die temperature of 240 ° C. and a T die slit width of 0.5 mm between two metal cooling rolls, The resin was sandwiched in a state where there was always a resin reservoir), surface transfer was performed while rolling, and this was wound around a paper roll with a winder to form an acrylic resin film substrate (D) having a thickness of 75 μm.

[Example 1]
23 parts of a hydroxyl group-containing acrylic resin (hydroxyl value 80 mg KOH / g, glass transition temperature 90 ° C., mass average molecular weight about 80,000), which is a copolymer of MMA 85%, HEMA 12%, n-BA 3%, hexamethylene diisocyanate 4 parts of (isocyanurate type) trimer and 4 parts of amorphous silica having a mass average particle diameter of 6 μm are dispersed in a solvent consisting of 48 parts of ethyl acetate, 16 parts of n-propyl acetate and 10 parts of butyl acetate. I got paint. The paint was diluted with ethyl acetate using a Iwata cup viscometer so that the viscosity was 14 seconds.

  Next, after applying a diluted paint with a gravure coater using a slanted gravure roll having a line number of 200 lines per inch on one side of an acrylic resin film substrate (A) having a thickness of 75 μm, The solvent was volatilized under an atmosphere of 85 ° C. to obtain a matte acrylic resin film for thermoforming. The matte acrylic resin film for thermoforming was wound around a paper tube and aged for 2 days in an atmosphere at 40 ° C. to cure the matte layer. The thickness of the matte layer was 1.1 μm.

[Example 2]
The same procedure as in Example 1 was carried out except that 5.6 parts of a trimer of hexamethylene diisocyanate (isocyanurate type) was used. The thickness of the matte layer was 1.1 μm.

Example 3
The same operation as in Example 1 was conducted except that 7.5 parts of a trimer of hexamethylene diisocyanate (isocyanurate type) was used. The thickness of the matte layer was 1.1 μm.

Example 4
Hydroxyl group-containing acrylic resin (hydroxyl value 60 mgKOH / g, glass transition temperature 65 ° C., mass average molecular weight about 30,000), which is a copolymer of MMA 68%, HEMA 9%, n-BA 9%, and n-butyl methacrylate 14% ) 32 parts, 5.6 parts of hexamethylene diisocyanate (isocyanurate type) trimer, 4.8 parts of amorphous silica having a mass average particle diameter of 6 μm, 33 parts of ethyl acetate, 15 parts of npropyl acetate And a paint obtained by dispersing in a solvent comprising 15 parts of butyl acetate. The paint was diluted with ethyl acetate using a Iwata cup viscometer so that the viscosity was 14 seconds. The same operation as in Example 1 was performed except that this diluted paint was used. The thickness of the matte layer was 1.3 μm.

Example 5
36 parts of a hydroxyl group-containing acrylic resin (hydroxyl value 110 mg KOH / g, glass transition temperature 60 ° C., mass average molecular weight about 25,000), which is a copolymer of MMA 44%, HEMA 21%, and n-butyl methacrylate 35% , 5.6 parts of hexamethylene diisocyanate (isocyanurate type) trimer, 4.8 parts of amorphous silica having a mass average particle size of 6 μm, 33 parts of ethyl acetate, 15 parts of npropyl acetate, and butyl acetate A paint was obtained by dispersing in 15 parts of solvent. The paint was diluted with ethyl acetate using a Iwata cup viscometer so that the viscosity was 14 seconds. The same operation as in Example 1 was performed except that this diluted paint was used. The thickness of the matte layer was 1.3 μm.

Example 6
The same operation as in Example 1 was performed except that 0.1 part of a trimer of hexamethylene diisocyanate (isocyanurate type) was used. The thickness of the matte layer was 1.1 μm.

Example 7
The same procedure as in Example 1 was performed except that 1.5 parts of a trimer of hexamethylene diisocyanate (isocyanurate type) was used. The thickness of the matte layer was 1.1 μm.

Example 8
The same operation as in Example 1 was carried out except that 8 parts of hexamethylene diisocyanate (isocyanurate type) trimer was used. The thickness of the matte layer was 1.1 μm.

Example 9
The same procedure as in Example 1 was performed except that 13 parts of hexamethylene diisocyanate (isocyanurate type) trimer was used. The thickness of the matte layer was 1.1 μm.

Example 10
It implemented similarly to Example 1 except having changed the ratio of MMA and HEMA of a hydroxyl-containing acrylic resin, and having set the hydroxyl value of the hydroxyl-containing acrylic resin to 10 mgKOH / g. The thickness of the matte layer was 1.3 μm.

Example 11
It implemented similarly to Example 1 except having changed the ratio of MMA and HEMA of a hydroxyl-containing acrylic resin, and having set the hydroxyl value of the hydroxyl-containing acrylic resin to 140 mgKOH / g. The thickness of the matte layer was 1.3 μm.

Example 12
It implemented similarly to Example 4 except having changed the ratio of MMA and n-BA of a hydroxyl-containing acrylic resin, and having set the glass transition temperature of the hydroxyl-containing acrylic resin to 40 degreeC. After aging, an attempt was made to unwind the matte acrylic resin film for thermoforming from the paper tube. However, since the matte acrylic resin film for thermoforming partially blocked, film breakage occurred. The thickness of the matte layer was 1.3 μm.

Example 13
The same procedure as in Example 5 was conducted, except that the amounts of ethyl acetate, npropyl acetate, and butyl acetate were changed to 10 parts of ethyl acetate, 10 parts of npropyl acetate, and 43 parts of butyl acetate. The thickness of the matte layer was 1.3 μm.

Example 14
It implemented like Example 2 except having used the reverse roll coater instead of the gravure coater. The thickness of the matte layer was 3 μm.

Example 15
It implemented similarly to Example 2 except having used the kiss reverse coater instead of the gravure coater. The coating omission partially occurred at the slightly loosened portion of the original fabric wound shape of the acrylic resin film substrate. The thickness of the matte layer was 1 μm.

Example 16
It implemented similarly to Example 2 except having used the 75-micrometer-thick acrylic resin film base | substrate (C) instead of the acrylic resin film base | substrate (A).

Example 17
It implemented similarly to Example 2 except having used the acrylic resin film base | substrate (D) instead of the acrylic resin film base | substrate (A). In some cases, the matte acrylic resin film for thermoforming and the ABS sheet may be peeled off by heating during insert molding.

Example 18
It implemented similarly to Example 2 except having used the 125-micrometer-thick acrylic resin film base | substrate (A) instead of the 75-micrometer-thick acrylic resin film base | substrate (A). In-mold molding was performed by changing the heater set temperature to 260 ° C. and the heating time to 15 seconds.

Example 19
The same operation as in Example 18 was performed except that an acrylic resin film substrate (C) having a thickness of 125 μm was used.

Example 20
The same operation as in Example 2 was performed except that amorphous silica having a mass average particle diameter of 1.5 μm was used.

Example 21
The same operation as in Example 2 was performed except that amorphous silica having a mass average particle diameter of 14 μm was used. In addition, it was confirmed that the obtained matte acrylic resin film for thermoforming had doctor streaks.

[Example 22]
The same operation as in Example 2 was carried out except that the amount of ethyl acetate when diluting the paint was 1.5 mass times. The thickness of the matte layer was 0.7 μm.

[Comparative Example 1]
75 parts of rubber-containing multistage polymer (I-1) and thermoplastic polymer (II) [MMA / MA copolymer (MMA / MA = 99/1 (mass ratio), reduced viscosity ηsp / c = 0.06 L / g)] In 25 parts, 10 parts by mass of amorphous silica having a mass average particle diameter of 6 μm as a compounding agent, manufactured by Ciba Specialty Chemicals Co., Ltd., 1.4 parts of the trade name “Tinubin 234”, manufactured by Asahi Denka Kogyo Co., Ltd. After adding 0.1 part of product name “Adeka Stub AO-50” and 0.3 part of product name “Adekastab LA-67” manufactured by Asahi Denka Kogyo Co., Ltd., they were mixed using a Henschel mixer. This mixture [acrylic resin composition (III-3)] was supplied to a degassing type extruder (Ikegai Iron Works Co., Ltd., PCM-30 (trade name)) heated to 230 ° C., kneaded, and 100 mesh. Extrusion was carried out while removing foreign matter with a screen mesh to obtain pellets.

  The pellets produced by the above method were dried at 80 ° C. all day and night, and a cylinder temperature of 180 to 240 ° C. was used using a 40 mmφ non-vent screw extruder (L / D = 26) equipped with a 300 mm wide T-die. Then, extruding while removing foreign matter with a screen mesh of 100 mesh, passing the molten acrylic resin film extruded under the conditions of T-die temperature of 240 ° C and T-die slit width of 0.5 mm through a metal cooling roll and winding it A matte acrylic resin film for thermoforming with a thickness of 125 μm was formed by winding it on a paper roll with a take-off machine. This matte acrylic resin film for thermoforming has a single layer structure.

[Comparative Example 2]
The same operation as in Example 2 was carried out except that the amount of ethyl acetate at the time of diluting the paint was 10 mass times. The thickness of the matte layer was 0.03 μm. When the obtained film was confirmed, there was a part where the matte layer was not coated partially.

[Comparative Example 3]
The same procedure as in Example 14 was performed except that the roll clearance of the coated portion of the reverse coater was increased to about three times the width set in Example 14. The thickness of the matte layer was 8 μm. During coating, the film was frequently cut due to a decrease in physical properties of the acrylic resin film substrate, so that it could not be collected as a wound sample.

Example 23
As a polyisocyanate, 23 parts of a hydroxyl group-containing acrylic resin (hydroxyl value 80 mg KOH / g, glass transition temperature 90 ° C., mass average molecular weight about 80,000), which is a copolymer of MMA 85%, HEMA 12%, n-BA 3% 5.6 parts of a trimer of hexamethylene diisocyanate (isocyanurate type), 4 parts of amorphous silica having a mass average particle diameter of 6 to 7 μm, 48 parts of ethyl acetate, 16 parts of npropyl acetate and 10 parts of butyl acetate A paint was obtained by dispersing in a solvent consisting of parts. This paint was diluted with ethyl acetate, and the viscosity was adjusted so that the flow time by a Iwata cup viscometer was 14 seconds. After adjusting the viscosity, the paint was filtered using CPII-10 manufactured by Chisso Filter Co., Ltd.

Next, a slanted gravure roll having a line number of 200 lines per inch on one side of an acrylic resin film substrate (A) having a thickness of 75 μm (the slanted line angle with respect to the roll axis direction is about 45 °, 116 μm opening width, 13 μm plate bottom width, 33 μm plate depth, cell capacity 16.9 cm ³ / m ² , diameter 120 mm), with a gravure coater using a steel doctor blade at a coating speed of 20 m / min. After applying the viscosity-adjusted paint, the solvent was volatilized at 85 ° C. to obtain a matte acrylic resin film for thermoforming. The appearance of the resulting matte acrylic resin film for thermoforming was free of faint or noticeable grain due to a decrease in the transfer amount, and a good matte layer could be formed. The matte acrylic resin film for thermoforming was wound around a paper tube and aged for 2 days in an atmosphere at 40 ° C. to cure the matte layer.

Example 24
Hydroxyl group-containing acrylic resin (hydroxyl value 60 mgKOH / g, glass transition temperature 65 ° C., mass average molecular weight about 30,000), which is a copolymer of MMA 68%, HEMA 9%, n-BA 9%, and n-butyl methacrylate 14% ) 32 parts, 5.6 parts of hexamethylene diisocyanate (isocyanurate type) trimer as polyisocyanate, and 4.8 parts of amorphous silica having a mass average particle diameter of 6 to 7 μm, 33 parts of ethyl acetate, A paint was obtained by dispersing in a solvent consisting of 15 parts of n-propyl acetate and 15 parts of butyl acetate. This paint was diluted with ethyl acetate, and the viscosity was adjusted so that the flow time by a Iwata cup viscometer was 14 seconds. After adjusting the viscosity, the paint was filtered using CPII-10 manufactured by Chisso Filter Co., Ltd.
It implemented similarly to Example 23 except apply | coating this dilution coating material to an acrylic resin film base | substrate (B). The appearance of the resulting matte acrylic resin film for thermoforming was free of faint or noticeable grain due to a decrease in the transfer amount, and a good matte layer could be formed.

Example 25
It implemented similarly to Example 23 except having used the 75-micrometer-thick acrylic resin film base | substrate (C) instead of the acrylic resin film base | substrate (A). The appearance of the resulting matte acrylic resin film for thermoforming was free of faint or noticeable grain due to a decrease in the transfer amount, and a good matte layer could be formed.

Example 26
27.5 parts of a hydroxyl group-containing acrylic resin (hydroxyl value 80 mg KOH / g, glass transition temperature 90 ° C., mass average molecular weight about 80,000), which is a copolymer of MMA 85%, HEMA 12%, n-BA 3%, 6.8 parts of hexamethylene diisocyanate (isocyanurate type) trimer as isocyanate, 6 parts of amorphous silica having a mass average particle diameter of 5 to 6 μm, and amorphous silica 1 having a mass average particle diameter of 0.1 μm as a suspending agent 5 parts and 1 part of polytetrafluoroethylene wax SST-3 (trade name, manufactured by SHAMROCK, melting point 321 ° C.) having a mass average particle diameter of 5 μm are composed of 22 parts of methyl ethyl ketone, 43 parts of methyl isobutyl ketone and 40 parts of butyl acetate. A paint was obtained by dispersing in a solvent. In addition, when this paint was measured with the Iwata cup viscometer immediately before coating, the flow-down time was 18 seconds. After adjusting the viscosity, the paint was filtered using CPII-10 manufactured by Chisso Filter Co., Ltd.

Next, a slanted gravure roll having a line number of 200 lines per inch on one side of an acrylic resin film substrate (A) having a thickness of 75 μm (the slanted line angle with respect to the roll axis direction is about 45 °, 116 μm opening width, 13 μm plate bottom width, 33 μm plate depth, cell capacity of 16.9 cm ³ / m ² , diameter 120 mm), with a gravure coater using a ceramic doctor blade at a coating speed of 20 m / min After applying the paint, the solvent was volatilized at 90 ° C. to obtain a matte acrylic resin film for thermoforming. The appearance of the resulting matte acrylic resin film for thermoforming was free of faint or noticeable grain due to a decrease in the transfer amount, and a good matte layer could be formed. The matte acrylic resin film for thermoforming was wound around a paper tube and aged at 40 ° C. for 2 days to cure the matte layer.
When coating was carried out on an acrylic resin film substrate for about 3000 m, an external appearance defect (white streaks were intermittently transferred in the flow direction) sometimes occurred during the gravure roll. did it. Moreover, when the bottom of the bread | pan which stored the coating material was confirmed after completion | finish of coating, the deposit was confirmed.

Example 27
In Example 26, instead of polytetrafluoroethylene wax SST-3 (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 is used. A matte acrylic resin film for thermoforming was obtained in the same manner as in Example 26 except that. Note that. When this paint was measured with an Iwata cup viscometer immediately before coating, the flow-down time was 19 seconds. 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.
When the coating was carried out on the acrylic resin film substrate for about 3000 m, no appearance defects were generated during that time when the wax on which the gravure roll settled was rolled up. Moreover, when the bottom of the bread | pan which stored the coating liquid was confirmed after completion | finish of coating, the deposit was not able to be confirmed.

Example 28
A matte acrylic resin film for thermoforming was obtained in the same manner as in Example 27 except that the wax S-363 (trade name) made of polyethylene and polypropylene was increased to 2 parts. In addition, when this paint was measured with the Iwata cup viscometer immediately before coating, the flow-down time was 19 seconds. The appearance of the resulting matte acrylic resin film for thermoforming was free of faint or noticeable grain due to a decrease in the transfer amount, and a good matte layer could be formed.

Example 29
A matte acrylic resin film for thermoforming was obtained in the same manner as in Example 26 except that polyethylene wax S-395 (trade name) was not used. In addition, when this paint was measured with the Iwata cup viscometer immediately before coating, the flow-down time was 19 seconds. The appearance of the resulting matte acrylic resin film for thermoforming was free of faint or noticeable grain due to a decrease in the transfer amount, and a good matte layer could be formed.

Example 30
27.4 parts of a hydroxyl group-containing acrylic resin (hydroxyl value 80 mg KOH / g, glass transition temperature 90 ° C., mass average molecular weight about 80,000), which is a copolymer of MMA 85%, HEMA 12%, n-BA 3%, 6.8 parts of hexamethylene diisocyanate (isocyanurate type) trimer as isocyanate, 7 parts of amorphous silica having a mass average particle diameter of 5 to 6 μm, and amorphous silica 1 having a mass average particle diameter of 0.1 μm as a suspending agent 0.5 part and 1 part of wax S-363 (trade name, manufactured by SHAMROCK, melting point 142 ° C.) made of polyethylene and polypropylene having a mass average particle diameter of 5 μm, 22.3 parts of methyl ethyl ketone, 49.6 parts of methyl isobutyl ketone, and A paint was obtained by dispersing in a solvent consisting of 45.8 parts of butyl acetate. In addition, when this paint was measured with the Iwata cup viscometer immediately before coating, the flow-down time was 15 seconds and the liquid temperature was 21 ° C. Immediately before coating, the coating solution was filtered using CPII-10 manufactured by Chisso Filter Co., Ltd.

Next, a slanted gravure roll having a line number of 200 lines per inch on one side of an acrylic resin film substrate (A) having a thickness of 75 μm (the slanted line angle with respect to the roll axis direction is about 45 °, 116 μm opening width, 13 μm bottom width of plate, 33 μm plate depth, cell capacity of 16.9 cm ³ / m ² , 120 mm diameter), using a ceramic doctor blade with a gravure coater at a coating speed of 30 m / min After applying the paint, the solvent was volatilized at 80 ° C. to obtain a matte acrylic resin film for thermoforming. The appearance of the resulting matte acrylic resin film for thermoforming was free of faint or noticeable grain due to a decrease in the transfer amount, and a good matte layer could be formed. The matte acrylic resin film for thermoforming was wound around a paper tube and aged at 40 ° C. for 2 days to cure the matte layer.
The thickness of the matte layer was 1 μm. Further, the obtained matte acrylic resin film for thermoforming had a good appearance with reflection of a fluorescent light and no grain.

Example 31
In Example 30, instead of a slanted gravure roll having a line number of 200 lines per inch, a slanted gravure roll having a line number of 250 lines per inch (a slant angle relative to the roll axis direction) Is about 45 °, the opening width of the plate is 80 μm, the bottom width of the plate is 11 μm, the plate depth is 35 μm, the cell capacity is 15.6 cm ³ / m ² , and the diameter is 120 mm, and the coating speed is 40 m / min. This was carried out in the same manner as in Example 30.
The thickness of the matte layer was 1 μm. Further, the obtained matte acrylic resin film for thermoforming had a good appearance with reflection of a fluorescent light and no grain.

[Example 32]
In Example 30, instead of a diagonal gravure roll having a line number of 200 lines per inch, a Rotoflo grid type gravure roll having a line number of 250 lines per inch (plate depth 34 μm, cell The same procedure as in Example 30 was performed except that a capacity of 13.2 cm ³ / m ² and a diameter of 120 mm was used.
The thickness of the matte layer was 0.8 μm. Further, the obtained matte acrylic resin film for thermoforming had a good appearance with reflection of a fluorescent light and no grain.

[Reference Example 1]
In Example 30, instead of a slanted gravure roll having a line number of 200 lines per inch, a slanted gravure roll having a line number of 250 lines per inch (a slant angle relative to the roll axis direction) Was carried out in the same manner as in Example 30 except that a plate opening width of 90 μm, a plate bottom width of 8 μm, a plate depth of 32 μm, a cell capacity of 15.4 cm ³ / m ² and a diameter of 120 mm was used.
The matte acrylic resin film obtained had a surface glossiness of 19.4% and good matteness, but there were places where the coating liquid was not applied in some places, and it had a uniform matte layer A matte acrylic resin film for thermoforming was not obtained.

  The evaluation results of the acrylic resin film substrate, the matte acrylic resin film for thermoforming, and the laminate obtained above are summarized in Tables 4-7.

From Examples 1 to 32, the matte acrylic resin film for thermoforming having a matte layer thickness of 0.1 to 5 μm does not generate a crack in the matte layer during molding and exhibits good moldability. Recognize.
Moreover, from Examples 23-32, it turns out that favorable chemical resistance is shown by using a curable binder resin. Further, a matte acrylic resin film for thermoforming having a difference between the yellowness (YI ′ (200 ° C.)) when heated to 200 ° C. and the yellowness (YI) before heating is 1.3 or less at the time of molding It can be seen that there is no change in appearance.
From Examples 26 to 28 and 30 to 32, it is found that the matte acrylic resin film for thermoforming to which wax is added exhibits good scratch resistance.

From Examples 26 to 28 and 30 to 32, it can be seen that a laminate having a matte acrylic resin film for thermoforming and having a dynamic friction coefficient of 0.23 or less exhibits good scratch resistance.
From Examples 30 to 32 and Reference Example, a diagonal gravure roll having a number of lines of 150 or more lines per inch and having the pattern engraved at an angle of 40 to 50 ° with respect to the roll axis direction It can be seen that a matte acrylic resin film for thermoforming with a good appearance can be obtained by using and that a matte acrylic resin film for thermoforming with a small change in appearance can be obtained even after thermoforming.

  As described above, by adopting the matte acrylic resin film for thermoforming according to the present invention, when a matte material is simply added to the acrylic resin film substrate (Comparative Example 1), it exhibits a design that is difficult to realize. In addition, even when insert molding or in-mold molding is performed to form a deep-drawn shape, the matte layer does not crack, and the scratch resistance, surface hardness, heat resistance, and chemical resistance required for vehicle components , Heat-resistant yellowing, and matte acrylic resin film for thermoforming, and a laminate obtained by laminating these on a base material can be provided. Moreover, by adopting the production method of the present invention, it is possible to stably produce a matte acrylic resin film for thermoforming.

The laminate having the matte acrylic resin film for thermoforming of the present invention is particularly suitable for a vehicle member and a building material. Specific examples include automotive interior components such as instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, dashboards, weather strips, bumpers, bumper guards, side mud guards, body panels. , Spoilers, front 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 (10)

An acrylic resin film substrate;
A matte acrylic resin film for thermoforming having a matte layer having a thickness of 0.1 to 5 μm and containing a matte material and a binder resin provided as an outermost layer on one surface of the acrylic resin film substrate .   The matte acrylic resin film for thermoforming according to claim 1, wherein the matte layer further contains a polyolefin wax. The yellowness (YI '(200 ° C)) of the matte acrylic resin film for thermoforming after heating the matte surface temperature to 200 ° C, and the yellowness of the matte acrylic resin film for thermoforming before heating The matte acrylic resin film for thermoforming according to claim 1 or 2, wherein the degree (YI) satisfies the relationship of the following formula (i).
YI ′ (200 ° C.) − YI ≦ 1.3 (i)   The matte acrylic resin film for thermoforming according to any one of claims 1 to 3, wherein the surface of the matte layer has a dynamic friction coefficient of 0.23 or less.   The matte acrylic resin film for thermoforming according to any one of claims 1 to 4, further comprising a pattern layer on the surface of the acrylic resin film substrate opposite to the surface on which the matte layer is provided. Thermoforming having an acrylic resin film base and a matte layer having a thickness of 0.1 to 5 μm containing a matting material and a binder resin provided as an outermost layer on one surface of the acrylic resin film base A method for producing a matte acrylic resin film for
A method for producing a matte acrylic resin film for thermoforming, wherein a matte layer is formed by a printing method or a coating method.   A matte layer is formed using a diagonal gravure roll having 150 or more lines per inch and engraved at an angle of 40 to 50 ° with respect to the roll axis direction. A method for producing a matte acrylic resin film for thermoforming according to claim 6.   The laminated body which laminated | stacked the matte acrylic resin film for thermoforming of Claim 1 or Claim 2 on the base material so that the surface on the opposite side to a matte layer may contact | connect.   The laminate according to claim 8, wherein the surface of the matte layer has a dynamic friction coefficient of 0.23 or less. The laminate according to claim 8 or 9, wherein a matte acrylic resin film for thermoforming is laminated on a substrate by an in-mold molding method or an insert molding method.