JP2002361712A - Acrylic resin film, method for manufacturing the same and laminate using the acrylic resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acrylic resin film having good matte appearance and having good printability reducing printing omission or the like when printing is applied to. SOLUTION: The acrylic resin film is characterized in that 60 deg. surface glossiness difference between both surfaces of the film is not less than 5% and the thickness of the film is not more than 300 μm. This acrylic resin film is manufactured by extruding an acrylic resin composition in a molten state and holding the extrudate between a mirror surface roll and a rubber roll or an embossed roll to form the same into a film. A laminate (a molded product having the acrylic resin film laminated to the surface thereof) is obtained by laminating the acrylic resin film on a substrate so that the surface having higher 60 deg. surface glossiness of the acrylic resin film comes into contact with the substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is useful for decorating the surface of a substrate, etc., and has an excellent matte appearance and printability, an acrylic resin film, a method for producing the same, and a laminate having the film on the surface. About.

[0002]

2. Description of the Related Art There is an in-mold molding method as a surface decoration method for imparting a design property to a molded product at low cost. This method involves printing on the surface of a sheet or film of a polyester resin, a polycarbonate resin, an acrylic resin, etc., and molding this into a desired shape by a vacuum molding method or the like, or an injection molding die as it is without molding. This is a method in which a resin serving as a base material is injection-molded. According to this in-mold molding method, the sheet or film and the base material can be integrated with good productivity, or only the printed portion can be transferred.

Japanese Patent Application Laid-Open No. 9-263614 discloses an acrylic resin film which can be suitably used in the above-described in-mold molding method and has excellent printability. That is, in this publication, an acrylic composition containing a predetermined amount of a thermoplastic polymer and a rubber-containing polymer obtained by polymerizing a predetermined monomer mixture by a predetermined method, and having a diameter of 80 μm As described above, it is described that an acrylic resin film excellent in printability having a thickness of 300 μm or less can be manufactured with a foreign substance of 1 / m ² or less, and when the acrylic resin film is subjected to printing, printing caused by fish eyes is performed. It describes that omission is suppressed and excellent printability can be realized.

Further, in recent years, it has been demanded that the surface of a printed acrylic resin film be made in a matte state so as to add a design property such as a sense of quality and a sense of depth and a decorative property. Such a requirement can be realized by printing on the matte acrylic resin film.

In Japanese Patent Application Laid-Open No. Hei 10-237261, a rubber-containing polymer whose particle size is controlled to be within a specific range in the acrylic resin composition described in Japanese Patent Application Laid-Open No. Hei 9-263614 is used. It is disclosed that by adding an inorganic particle, an organic crosslinked particle, a hydroxyl group-containing linear polymer, or the like as a matting agent, a matte acrylic resin film in which matte is suppressed can be produced.

[0006]

SUMMARY OF THE INVENTION The above-mentioned Japanese Patent Application Laid-open No. Hei 10-2
Japanese Patent No. 37261 does not describe in detail the printing omission property when a matte acrylic resin film is printed. Then, the present inventors actually manufactured the matte acrylic resin film described in this publication and performed a printing test. As a result, more than 10 printing defects per 1 m ^{2 of} the printing surface occurred. That is, this acrylic resin film is
Although the mattability is excellent, there is still room for improvement in printability.

In general, when printing is performed on an acrylic resin film, a large number of print omissions not only impairs the design and appearance but also lowers the yield.

[0008] That is, an object of the present invention is to provide an acrylic resin film having a good matte appearance and good printability such as little print omission upon printing, a method for producing the same, and a method for producing the same. An object of the present invention is to provide a laminate having a surface.

[0009]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the surface gloss of the front and back surfaces of the film are different, and the difference in the surface gloss of the front and back surfaces is within a specific range. The present inventors have found that the acrylic resin film has a very good effect, and have completed the present invention.

That is, the present invention is an acrylic resin film having a difference of 60 ° surface gloss between the front and back of the film of 5% or more and a thickness of 300 μm or less.

Further, the present invention is a method for producing the above-mentioned acrylic resin film, wherein the acrylic resin composition is melt-extruded and then sandwiched between a mirror roll and a rubber roll or embossed roll to form a film. This is a method for producing an acrylic resin film.

Further, the present invention is an acrylic resin film laminate obtained by laminating the acrylic resin film on a substrate such that the surface of the acrylic resin film having a higher surface glossiness of 60 ° is in contact with the acrylic resin film.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As the resin constituting the acrylic resin film of the present invention, various conventionally known acrylic resins can be used. However, an acrylic resin composition (A) described below, an acrylic resin composition (B) containing a multilayer structure polymer described below, or an acrylic resin composition (C) containing a matting agent described below is used. Is preferred. These acrylic resin compositions (A)
(C) is in the range of 60 to 115 ° C.

First, the acrylic resin composition (A) will be described. The acrylic resin composition (A) is composed of 5.5 to 99.9 parts by mass of a rubber-containing polymer (A-1) and a thermoplastic polymer (A-2) 0 containing an alkyl methacrylate as a main component. 0.1 to 94.5 parts by mass [total 100 parts by mass of component (A-1) and component (A-2)].

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

Examples of the alkyl acrylate used for the elastic copolymer (a-1) include various conventionally known alkyl acrylates. Particularly, butyl acrylate, 2-ethylhexyl acrylate and the like are preferable. This alkyl acrylate is used as a main component of the monomers constituting the elastic copolymer (a-1). Specifically, the amount of the alkyl acrylate used is 35 to 99.9% by mass of all the monomers.
Is preferred. When the amount is 35% by mass or more, the film has good moldability. A more preferred amount is 5
0 mass% or more. Each range of these amounts indicates the amount of the alkyl acrylate used as the whole of the elastic copolymer (a-1) when the elastic copolymer (a-1) has a structure of two or more layers. Things. For example, when the elastic copolymer (a-1) has a hard core structure, the amount of the first layer (core) of the alkyl acrylate is set to 35.
It can be less than mass%.

As a monomer constituting the elastic copolymer (a-1), other vinyl monomers copolymerizable therewith can be used together with the alkyl acrylate.
When another vinyl monomer is used, its amount is preferably 64.9% by mass or less based on all monomers. As other vinyl monomers, for example, alkyl methacrylates such as methyl methacrylate, butyl methacrylate and cyclohexyl methacrylate, styrene, acrylonitrile and the like are preferable. These can be used alone or in combination of two or more.

It is preferable to use a crosslinkable monomer as a part of the monomer constituting the elastic copolymer (a-1).
Examples of the crosslinkable monomer include ethylene glycol dimethacrylate, butanediol dimethacrylate, allyl acrylate, allyl methacrylate, diallyl phthalate,
Triallyl cyanurate, triallyl isocyanurate, divinylbenzene, diallyl maleate, trimethylolpropane triacrylate, allyl cinnamate and the like. These can be used alone or in combination of two or more. The amount of the crosslinkable monomer used is
0.1 to 10% by mass of all monomers is preferred.

The rubber-containing polymer (A-1) is obtained by graft polymerization of a monomer containing an alkyl methacrylate as a main component in the presence of the above-mentioned elastic copolymer (a-1). It is a rubber-containing polymer having a multilayer structure of two or more layers formed by forming a united product (a-2). That is, the elastic copolymer (a-1) forms the inner layer, and the hard polymer (a-2) forms the outer layer.

In the graft polymerization for obtaining the hard polymer (a-2), an alkyl methacrylate is used as a main component. Specifically, the amount of the alkyl methacrylate used is preferably 50% by mass or more of all monomers used for graft polymerization. Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, and the like.

As the monomer used in the graft polymerization for obtaining the hard polymer (a-2), other vinyl monomers copolymerizable with the alkyl methacrylate can be used together with the alkyl methacrylate. When using other vinyl monomers,
The amount used is preferably 50% by mass or less based on all monomers.
As other vinyl monomers, for example, alkyl acrylates such as methyl acrylate, butyl acrylate and cyclohexyl acrylate, styrene and acrylonitrile are preferable. These can be used alone or in combination of two or more.

Each of these monomers is used as an elastic copolymer (a-
By performing graft polymerization in one or more stages in the presence of 1), a hard polymer (a-2) as an outer layer is formed, and a rubber-containing polymer (A-1) is obtained. Rubber-containing polymer (A
The amount of the hard polymer (a-2) in -1) is preferably from 10 to 4 based on 100 parts by mass of the elastic copolymer (a-1).
00 parts by mass, more preferably 20 to 200 parts by mass.

The particle diameter of the rubber-containing polymer (A-1) is as follows:
0.01 to 0.5 μm is preferable, and 0.08 to 0.3 μm is more preferable. In particular, from the viewpoint of film forming properties, the particle size is
0.08 μm or more is preferable.

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

As the polymerization initiator, conventionally known various ones 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 preferred. Examples of the anionic surfactant include carboxylate surfactants such as potassium oleate, sodium stearate, sodium myristate, sodium N-lauroyl sarcosinate, and dipotassium alkenyl succinate;
Sulfate ester surfactants such as sodium lauryl sulfate; sulfonate surfactants such as sodium dioctyl sulfosuccinate, sodium dodecylbenzene sulfonate, sodium alkyldiphenyl ether disulfonate; sodium polyoxyethylene alkyl phenyl ether phosphate Phosphate ester-based surfactants; and the like.

The polymer latex obtained by emulsion polymerization is filtered, for example, with a filter having a mesh size of 100 μm or less, and then coagulated by a known coagulation method such as an acid coagulation method, a salt coagulation method, a freeze coagulation method, and a spray drying method. Just do it. In the acid coagulation method, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and organic acids such as acetic acid can be used. In the salt coagulation method, inorganic salts such as sodium sulfate, magnesium sulfate, aluminum sulfate, and calcium chloride, and organic salts such as calcium acetate and magnesium acetate can be used. The coagulated polymer is further washed, dehydrated, dried, etc., to obtain a rubber-containing polymer (A-1).

The thermoplastic polymer (A-2) used for the acrylic resin composition (A) is a polymer obtained by using an alkyl methacrylate as a main component, and various conventionally known polymers can be used. .

As the thermoplastic polymer (A-2), 50 to 99.9 parts by mass of an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms, 0.1 to 50 parts by mass of an alkyl acrylate, and It is obtained by polymerizing a total of 100 parts by mass of 0 to 49.9 parts by mass of another vinyl monomer copolymerizable therewith, and has a reduced viscosity (polymer 0.1).
g in 100 ml of chloroform and measured at 25 ° C.)
Is preferably 0.1 L / g or less from the viewpoint of film-forming properties.

As the alkyl methacrylate used to obtain the thermoplastic polymer (A-2), for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like are preferable, and among them, methyl methacrylate is most preferable.

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

The method for producing the thermoplastic polymer (A-2) is as follows.
There is no particular limitation, and for example, various polymerization methods such as suspension polymerization, emulsion polymerization, and bulk polymerization can be used. At the time of polymerization, a chain transfer agent, another polymerization aid, or the like may be used. Various types of chain transfer agents can be used, and mercaptans are particularly preferable.

The reduced viscosity of the thermoplastic polymer (A-2) is:
It is preferably 0.1 L / g or less, since an appropriate elongation occurs when the film raw material resin is melted, and the film forming property is improved. Further, the reduced viscosity is preferably 0.05 L / g or more in that the film is not brittle, so that the film is less likely to break during film formation and printing.

Next, the acrylic resin composition (B) will be described. The acrylic resin composition (B) includes an innermost layer polymer (Ba) shown below and a crosslinked elastic polymer (B
-B) and an outermost layer polymer (Bc) shown below as a basic structure, and a crosslinked elastic polymer (Bb)
And at least one intermediate layer (Bd) shown below between the layer composed of the outermost layer polymer (Bc) and the layer composed of the outermost layer polymer (Bc). This is a resin composition containing, as a main component, a multilayer structure polymer monotonically decreasing in the order of B-b), the intermediate layer (B-d), and the outermost layer polymer (B-c).

The innermost layer polymer (Ba) used in the acrylic resin composition (B) is an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms or a methacrylic acid having an alkyl group having 1 to 4 carbon atoms. Alkyl ester (B-
a1) 80 to 100 parts by mass, another monomer having a copolymerizable double bond (B-a2) 0 to 20 parts by mass, and
Polyfunctional monomer (B-a3) 0 to 10 parts by mass in total of 10
It is a polymer obtained by polymerizing a monomer composition in which 0.1 to 5 parts by mass of a graft crosslinking agent is added to 0 parts by mass.

(Meth) used for the innermost layer polymer (Ba)
Among the alkyl acrylates (B-a1), examples of the alkyl acrylate having an alkyl group having 1 to 8 carbon atoms include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and acrylic acid 2 -Ethylhexyl, n-octyl acrylate and the like are preferable, and particularly, an alkyl acrylate having a low Tg is preferable. These can be used alone or in combination of two or more.

(Meth) acrylic acid alkyl ester (B
Among -a1), examples of the alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. These can be used alone or in combination of two or more.

Alkyl (meth) acrylate (B)
-A1) is most preferably used afterwards in a unified manner in multiple stages, but depending on the purpose of the final product to be obtained,
Two or more kinds of monomers may be mixed, or another kind of alkyl (meth) acrylate may be used.

Other copolymerizable monomers having a double bond (B-a2) include, for example, higher alkyl acrylate, lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, methacrylic acid. Acrylic monomers such as acids are preferred.
In addition, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile, and the like can also be used.

Examples of the polyfunctional monomer (B-a3) include ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4 dimethacrylic acid.
-Alkylene glycol dimethacrylates such as butylene glycol and propylene glycol dimethacrylate are preferred. In addition, polyvinyl benzene such as divinyl benzene and trivinyl benzene, alkylene glycol diacrylate and the like can also be used. These monomers usually work effectively to bridge the layer in which they are contained, but do not affect the bonding between layers with other layers. Even if the polyfunctional monomer (B-a3) is not used at all, a considerably stable multilayer structure can be obtained as long as the graft crosslinking agent is present. For example, when hot strength is strictly required, a polyfunctional monomer (B-a3) may be arbitrarily used according to the purpose.

Examples of the above-mentioned graft crosslinking agent include, for example,
Allyl, methallyl or crotyl esters of copolymerizable α, β-unsaturated carboxylic acids or dicarboxylic acids are mentioned. Of these, allyl esters such as acrylic acid, methacrylic acid, maleic acid and fumaric acid are preferred, and allyl methacrylate in particular has an excellent effect. Also, triallyl cyanurate, triallyl isocyanurate and the like can be used. Such grafting agents primarily react and chemically bond to the conjugated unsaturated bond of the ester much faster than the allyl, methallyl or crotyl groups. And, a substantial portion of the slow reacting allyl, methallyl or crotyl groups work effectively during the polymerization of the next layer polymer to provide graft bonding between adjacent two layers.

The amount of the graft crossing agent used is extremely important, and is added within the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the total of components (B-a1) to (B-a3). .
When the amount is 0.1 parts by mass or more, the effective amount of graft bonding increases. When the amount is 5 parts by mass or less, the reaction amount with the crosslinked elastic polymer (Bb) polymerized and formed in the second stage is appropriately suppressed, and the two-layer crosslinked rubber elastic body having a two-layer elastic structure is obtained. The elasticity can be prevented from lowering. The addition amount is preferably 0.5 to 2 parts by mass.

The content of the innermost layer polymer (Ba) in the acrylic resin composition (B) is preferably from 5 to 35% by mass,
5 to 15 parts by mass are more preferred. Further, the content is preferably lower than the content of the crosslinked elastic polymer (Bb).

The crosslinked elastic polymer (Bb) used in the acrylic resin composition (B) is a main component for imparting rubber elasticity to the multilayer structure polymer, and is an acrylic acid having an alkyl group having 1 to 8 carbon atoms. Alkyl ester (B-b1) 80-1
00 parts by mass, 0 to 20 parts by mass of the other monomer having a copolymerizable double bond (B-b2), and 0 to 10 parts by mass of the polyfunctional monomer (B-b3). It is a polymer (Bb) obtained by polymerizing a monomer composition in which 0.1 to 5 parts by mass of a graft crosslinking agent is added to parts by mass.

The component (B-) used in the crosslinked elastic body (B-b)
As specific examples of b1) to (B-b3) and the graft crossing agent, the components (B-a1) to (B-a3) and the graft crossing agent described in the innermost layer polymer (Ba) described above are used. And the same.

The content of the crosslinked elastic polymer (Bb) in the acrylic resin composition (B) is preferably from 10 to 45% by mass. Further, it is preferable that the content is higher than the content of the innermost layer polymer (Ba).

The outermost layer polymer (Bc) used in the acrylic resin composition (B) is an effective component for distributing film formability and moldability to the acrylic resin, and is a methacrylic having 1 to 4 carbon atoms. Obtained by polymerizing a monomer composed of 51 to 100 parts by mass of an acid alkyl ester (B-c1) and 0 to 49 parts by mass of another monomer (B-c2) having a copolymerizable double bond. Polymer having a glass transition temperature of 60 ° C. or higher.

The alkyl methacrylate (B-c1) and other monomer (B-c2) used in the outermost layer polymer (Bc) include methacrylic acid used in the innermost layer polymer (Ba). Examples thereof include those equivalent to the examples of the alkyl ester (B-a1) and the other monomer (B-a2).

The content of the outermost layer polymer (Bc) in the acrylic resin composition (B) is preferably from 10 to 80% by mass.

The intermediate layer (Bd) used in the acrylic resin composition (B) is composed of 10 to 90 parts by mass of an alkyl acrylate (Bd1) having an alkyl group having 1 to 8 carbon atoms, 90 to 10 parts by mass of a methacrylic acid alkyl ester (B-d2) having an alkyl group of 4; 0 to 20 parts by mass of a monomer (B-d3) having a copolymerizable double bond; With respect to a total of 100 parts by mass of 0 to 10 parts by mass of the monomer (B-d4), the graft crosslinking agent was added in an amount of 0.1 part by mass.
A layer comprising a polymer obtained by polymerizing the monomer composition to which 1 to 5 parts by mass is added, wherein the amount of alkyl acrylate is the outermost layer (B-) from the crosslinked elastic polymer (B-b).
This is a layer that monotonically decreases toward c).

Each component (Bd) used in the intermediate layer (Bd)
1) to (B-d4) and the respective components (B-a1) to (G-a1) used in the innermost layer polymer (Ba)
(B-a3) and those similar to the examples of the graft crosslinking agent can be mentioned. The content ratio (monomer composition ratio) of the alkyl acrylate in the intermediate layer (Bd) is determined by the crosslinked elastic polymer (B-d).
The content ratio of the alkyl acrylate in b) is set lower and the content ratio of the alkyl acrylate in the outermost layer (B-c) is set higher.

The intermediate layer (B) in the acrylic resin composition (B)
The content of -d) is preferably from 5 to 35% by mass. When the content is 5% by mass or more, the function as the intermediate layer is effectively exhibited, and when the content is 35% by mass or less, the balance of the final polymer becomes good.

The acrylic resin composition (B) comprises the innermost layer polymer (Ba) and the crosslinked elastic polymer (B-
b), the intermediate layer (Bd) and the outermost layer polymer (Bc)
Of which the main component is a multi-layered polymer composed of the respective layers. In order to produce this multilayer polymer,
The multi-stage polymerization for obtaining the above four kinds of polymers (Ba) to (Bc) may be sequentially performed in the same system. However, in this case, in addition to the multilayer polymer composed of the four types of polymers (Ba) to (Bc), homopolymer particles and polymer particles having a two- or three-layer structure tend to be formed. It is in. That is, the acrylic resin composition (B) according to the present invention contains such a 4
It means a resin composition that includes a case where a compound other than the multilayer structure polymer composed of the kinds of polymers (Ba) to (Bc) is mixed.

As the method for producing the acrylic resin composition (B), a sequential multi-stage polymerization method by an emulsion polymerization method is most suitable. However, the present invention is not particularly limited thereto. For example, it can also be produced by emulsion suspension polymerization in which the outermost layer polymer (Bc) is converted into a suspension polymerization system after the emulsion polymerization.

The polymer latex obtained by emulsion polymerization or the like is filtered through, for example, a filter having an opening of 100 μm or less, and then coagulated by a known coagulation method such as an acid coagulation method, a salt coagulation method, a freeze coagulation method, and a spray drying method. It should be done. In the acid coagulation method, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and organic acids such as acetic acid can be used. In the salt coagulation method, inorganic salts such as sodium sulfate, magnesium sulfate, aluminum sulfate, and calcium chloride, and organic salts such as calcium acetate and magnesium acetate can be used. The coagulated polymer may be further washed, dehydrated and dried.

Next, the acrylic resin composition (C) will be described. The acrylic resin composition (C) is the acrylic resin composition (A) or the acrylic resin composition (B) described above.
It is a resin composition obtained by further adding 0.1 to 40 parts by mass of a matting agent to 100 parts by mass. Here, by using the matting agent, it is possible to reduce the glossiness of the acrylic resin film due to heat during the secondary molding.

Examples of the matting agent used in the acrylic resin composition (C) include various matting agents conventionally known irrespective of organic or inorganic matting agents. In particular, from the viewpoint of matting properties, film forming properties, and moldability, it is preferable to use the following hydroxyl group-containing polymer (D) or (E) as a matting agent.

The hydroxyl group-containing polymer (D) is obtained by adding 1 to 80 parts by mass of a hydroxyalkyl acrylate or a hydroxyalkyl methacrylate having an alkyl group having 1 to 8 carbon atoms and an alkyl group having 1 to 13 carbon atoms. A polymer obtained by polymerizing a monomer consisting of 10 to 99 parts by mass of a methacrylic acid alkyl ester having a total of 100 parts by mass of 0 to 79 parts by mass of an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms It is.

Examples of the hydroxyalkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms used in the hydroxyl group-containing polymer (D) include 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate. , 2,3-dihydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 4-acrylic acid
Hydroxybutyl and the like. Among them, 2-hydroxyethyl methacrylate is preferred. The amount of the hydroxyalkyl (meth) acrylate used is 1 to 8
The range is 0 parts by mass. If the amount is at least 1 part by mass, the matting effect will be sufficient, and if it is at most 80 parts by mass, the dispersibility of the particles will be good, and the film forming property will be good. From the viewpoint of mattability and film forming property, this amount is 5 to 5.
50 parts by mass is preferable, and 20 to 50 parts by mass is more preferable.

On the other hand, in a vehicle interior application, since a fragrance, a hairdressing agent and the like may adhere to the interior parts,
Generally, the interior member is required to have chemical resistance.
In order for the film to exhibit resistance to these chemicals, the amount of the hydroxyalkyl (meth) acrylate is preferably 5 to 25 parts by mass. From the viewpoint of achieving a good matting property and chemical resistance, 10 to 20 parts by mass is preferable.

Examples of the alkyl methacrylate having an alkyl group having 1 to 13 carbon atoms used in the hydroxyl group-containing polymer (D) include lower alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate. Is preferable, and among them, methyl methacrylate is most preferable. The amount of the methacrylic acid alkyl ester used is 10 to 99 parts by mass, more preferably 30 to 90 parts by mass.

The alkyl acrylate having an alkyl group having 1 to 8 carbon atoms used for the hydroxyl group-containing polymer (D) is, specifically, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid 2 Lower alkyl acrylates such as -ethylhexyl are preferred. The amount of the alkyl acrylate used is from 0 to
79 parts by mass, preferably 0.5 to 40 parts by mass,
~ 25 mass parts is more preferable.

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

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

As the hydroxyalkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms used for the hydroxyl group-containing polymer (E), the same one as in the case of the hydroxyl group-containing polymer (D) can be used. Can be used.
The amount of hydroxyalkyl acrylate used is 5
It is in the range of ８０80 parts by mass. If the amount is at least 5 parts by mass, the matting effect will be sufficient, and if it is at most 80 parts by mass, the dispersibility of the particles will be good, and the film-forming properties of the film will be good. From the viewpoint of matting properties, film forming properties, and chemical resistance, the amount is preferably 5 to 50 parts by mass, more preferably 10 to 20 parts by mass.

As the alkyl methacrylate having an alkyl group having 1 to 13 carbon atoms used for the hydroxyl group-containing polymer (E), the same ones as in the case of the hydroxyl group-containing polymer (D) can be used. . The amount of the alkyl methacrylate used is 10 to 94 parts by mass, and more preferably 50 to 90 parts by mass.

As the aromatic vinyl monomer used for the hydroxyl group-containing polymer (E), specifically, known ones such as styrene and α-methylstyrene can be used. Among them, styrene is preferred. The use of the aromatic vinyl monomer can improve the chemical resistance of the film. The amount of the aromatic vinyl monomer to be used is 1 to 80 parts by mass, preferably 5 to 40 parts by mass, more preferably 5 to 20 parts by mass.

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

Polymer having hydroxyl group (D) or (E)
Is preferably adjusted in the range of 0.05 to 0.3 L / g from the viewpoint of matte appearance and appearance. More preferably, it is in the range of 0.06 to 0.15 L / g. Further, it is preferable to use a polymerization controlling agent such as mercaptan for controlling the molecular weight. As the mercaptan, for example, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and the like can be used. However, the present invention is not limited to these, and various types of conventionally known mercaptans can be used.

Polymer having hydroxyl group (D) or (E)
The production method of is not particularly limited, but suspension polymerization, emulsion polymerization and the like are preferable. As the initiator for suspension polymerization, various conventionally known initiators can be used, and specific examples thereof include organic peroxides and azo compounds. As the suspension stabilizer, various types of conventionally known suspension stabilizers can be used, and specific examples thereof include organic colloidal polymer substances, inorganic colloidal polymer substances, inorganic fine particles, and combinations of these with surfactants. Is mentioned. The suspension polymerization is usually carried out by aqueous suspension of monomers together with a polymerization initiator in the presence of a suspension stabilizer. In addition, suspension polymerization can also be performed by using a polymer soluble in a monomer dissolved in the monomer.

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

In particular, when a polymer (D) or (E) having a hydroxyl group is used as a matting agent, physical properties such as elongation of the film hardly deteriorate. Therefore, the film can be used satisfactorily even in the in-mold molding or the like that requires the vacuum forming of the film in advance without causing the film to break.

In the present invention, based on 100 parts by mass of the acrylic resin composition (A) or the acrylic resin composition (B),
It is also preferable to use the thermoplastic polymer (F) shown below in an amount of 0.1 to 20 parts by mass.

The thermoplastic polymer (F) is obtained by polymerizing a total of 100 parts by mass of 50 to 100 parts by mass of methyl methacrylate and 0 to 50 parts by mass of another vinyl monomer copolymerizable therewith, The reduced viscosity of the polymer (0.1 g of the polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) is 0.2 L /
g of a thermoplastic polymer. The use of the thermoplastic polymer (F) improves the film-forming properties, and is particularly effective when a high level of thickness accuracy and film-forming speed are required. In addition, thermoplastic polymer (F)
Has a reduced viscosity of more than 0.2 L / g, resulting in a film having good thickness accuracy. Its reduced viscosity is usually 0.2 L /
g and 2 L / g or less, preferably 1.2 L / g or less.

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

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

In the present invention, the preferred amount of the thermoplastic polymer (F) used as required is 0.1 parts by mass with respect to 100 parts by mass of the acrylic resin composition (A) or the acrylic resin composition (B). To 20 parts by mass. When the amount is 0.1 parts by mass or more, an effect of improving film forming properties is exhibited,
On the other hand, when the amount is 20 parts by mass or less, the viscosity of the resin composition becomes appropriate, and good film-forming properties can be obtained.

The acrylic resin film of the present invention may contain, if necessary, a general compounding agent such as a stabilizer, a lubricant, a processing aid, a plasticizer, an impact-resistant auxiliary, a foaming agent, a filler, a coloring agent, and an ultraviolet ray. An absorbent or the like can be included.

In particular, from the viewpoint of protecting the substrate, it is preferable to add an ultraviolet absorber to impart weather resistance. The molecular weight of the ultraviolet absorber is preferably 300 or more, more preferably 400 or more. When the molecular weight is 300 or more, it is difficult to volatilize when performing vacuum molding or pressure forming in an injection molding die, and it is unlikely to generate mold contamination. The type of the ultraviolet absorber is not particularly limited, but a benzotriazole-based ultraviolet absorber having a molecular weight of 400 or more, a molecular weight of 400
The above triazine-based ultraviolet absorbers are particularly preferred. The former commercially available products include, for example, Tinuvin 234 (trade name of Ciba Geigy) and Adecastab LA (trade name of Asahi Denka Kogyo Co., Ltd.).
-31, as the latter commercially available product, for example, Ciba Geigy's trade name Tinuvin 1577 and the like.

In particular, the polymer (D) containing a hydroxyl group
Or when using (E), it is preferable to mix a phosphorus compound in a ratio of 0.01 to 3 parts by mass from the viewpoint of mattability. The mattability is good with an addition amount of 0.01 parts by mass or more, and the use of 3 parts by mass or less is preferable from an economic viewpoint. A more preferred amount is in the range of 0.1 to 1 part by mass.

Specific examples of the phosphorus compound include phosphite compounds such as alkyl phosphite, alkyl aryl phosphite, aryl phosphite, nonylphenyl phosphite, and alkyl nonylphenyl phosphite; trialkyl phosphate, tripolyoxyethylene alkyl. Phosphate compounds such as ether phosphate, dialkyl phosphate and its metal salt, dipolyoxyethylene alkyl ether phosphate and its metal salt, alkyl phosphate and its metal salt, polyoxyethylene alkyl ether phosphate and its metal salt; dialkyl alkyl phosphonate, alkyl Phosphonate compounds such as alkyl phosphonates and metal salts thereof; and the like. Among them, a phosphite-based compound is preferable from the viewpoint of matte development.
Further, among the phosphite-based compounds, those having no bulky substituent around the phosphite group are more preferable from the viewpoint of matte development.

The present invention is preferably obtained by forming the above-mentioned various acrylic resins into a desired film shape. In the acrylic resin, the content of the gel insoluble in chloroform is preferably 5 to 75% by mass. When the gel content is 5% by mass or more, the content of the rubber-containing polymer in the acrylic resin is substantially 5% by mass.
As a result, the film does not become brittle, so that the film forming property is improved. When the content is 75% by mass or less, an appropriate melt tension is obtained at the time of forming a film, and the film forming property is improved. This gel content is more preferably from 10 to 60% by mass.

The heat deformation temperature of the acrylic resin is 60
It is preferable that it is 115 degreeC. This heat deformation temperature is 6
If it is 0 ° C. or higher, the melt viscosity of the film becomes moderately high during film formation, and the releasability from the mirror roll becomes good,
Problems such as winding around the mirror roll can be prevented. When the heat deformation temperature is 115 ° C. or lower, the followability to the rubber roll or the embossed roll is improved, and a good matting property is developed on the film surface in contact with the rubber roll or the embossed roll. The mirror surface transfer property of the mirror roll onto the acrylic resin film is improved, and the smoothness of the surface in contact with the mirror roll is increased, thereby reducing print omission. The heat deformation temperature is more preferably from 70 to 105 ° C, and from 80 ° C to
95 ° C. is particularly preferred.

As a method for producing the acrylic resin film of the present invention, various conventionally known methods can be used. In particular, a method in which the acrylic resin composition is formed into a film shape by a melt extrusion method such as a T-die method, and then sandwiched between a mirror roll and a rubber roll or a crimped roll to form a film. In particular, the method of sandwiching between the mirror roll and the rubber roll is more preferable in that a film having a relatively thin film thickness of about 50 μm can be manufactured as compared with the method of sandwiching between the mirror roll and the embossed roll. Further, in the calendering method, it is also possible to form a film by changing one side of the two mirror-finished rolls on which the film is finally sandwiched to a rubber roll or a roll having a texture. Alternatively, the acrylic resin film may be once formed into a film shape by a known method, heated again to a glass point transfer temperature or higher, and sandwiched between a mirror roll and a rubber roll or embossed roll.

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

In the production of the film, if the temperature of the mirror surface roll is high, the followability to the rubber roll or the embossed roll becomes good, and the film surface in contact with the rubber roll or the embossed roll develops a good matting property. As a result, the mirror surface transfer property of the mirror surface roll to the acrylic resin film is improved, and the smoothness of the surface which is in contact with the mirror surface roll is increased, and the printing omission is reduced. However, if the temperature is too high, the peelability of the acrylic resin film from the mirror roll becomes poor,
The acrylic resin film may be wound. On the other hand, if the temperature of the mirror roll is too low, the mirror roll of the mirror roll to the acrylic resin film becomes poor, and the effect of reducing print omission becomes insufficient or the film is easily wrinkled. Depending on the glass point transfer temperature of the acrylic resin, 2
It is necessary to control the temperature of the cooling roll within the range of 0 to 140 ° C. The temperature range is preferably from 50 to 120C, more preferably from 60 to 100C.

As the rubber roll, various kinds of conventionally known rubber rolls can be used. Particularly, from the viewpoint of heat resistance, silicone rubber is preferable. In order to obtain good matting properties, silicone rubber containing sand is preferable. Since the preferred matte appearance differs depending on the use of an acrylic resin film, the particle size and amount of sand added to the silicone rubber vary depending on the use. Specifically, for example, a silicone rubber roll or the like to which 50% by mass of sand having an average particle size of 40 μm is added can be used. In addition, instead of the rubber roll, a roll with a grain may be used. Various types of conventionally known rolls can be used.

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

“(60 ° surface glossiness of film surface in contact with mirror roll side) − (60 ° surface glossiness of film surface not in contact with mirror roll side)” of acrylic resin film obtained by the above method Can be controlled by the film forming conditions and the type of non-specular roll such as a rubber roll or a roll having a texture. It is necessary that the difference in the surface glossiness is 5% or more from the viewpoints of print omission and matting. Further, the difference in the surface glossiness is preferably 10% or more,
15% or more is more preferable.

Since the mirror surface is transferred to the film surface which has been in contact with the mirror surface roll side, surface projections due to foreign matter which causes printing omission can be significantly reduced. Therefore,
When printing is performed on the surface that has been in contact with the mirror roll side, printing omissions can be significantly reduced. On the other hand, the 60 ° surface glossiness of the surface that is not in contact with the mirror surface roll side can be controlled by the type of non-mirror surface roll such as a rubber roll or a textured roll. The surface glossiness is preferably adjusted to 50% or less from the viewpoint of design and matte appearance. Further, it is preferably at most 20%, more preferably at most 10%.

When heated at 120 ° C. for 48 hours,
An acrylic resin film having a 60 ° surface glossiness of one film surface of 50% or less is preferable. The surface gloss after heating is more preferably 20% or less, and particularly preferably 10% or less. In order to obtain such an acrylic resin film, it is preferable to add a polymer (D) or (E) containing a hydroxyl group. When insert molding or in-mold molding is performed using such an acrylic resin film, gloss return after molding can be reduced.

Further, when compared among films having the same degree of surface gloss, the higher the heat deformation temperature of the acrylic resin film is, the less the gloss return property during insert molding or in-mold molding is reduced.

Therefore, from the viewpoint of the luster at the time of insert molding or in-mold molding, it is advantageous that the thermal deformation temperature of the acrylic resin is higher. The heat deformation temperature is from 85 ° C. to 1 from the viewpoints of the above-mentioned releasability from the mirror roll, followability with a rubber roll or a roll having a texture, and gloss return during molding.
It is preferably in the range of 05 ° C, more preferably in the range of 90 to 100 ° C.

It is particularly useful to use the acrylic resin film of the present invention after printing a picture by an appropriate printing method. For example, by laminating a printed acrylic resin film on a desired substrate (molded product or the like) as a coating substitute film or the like, it is possible to easily obtain a laminate (laminate molded product) with a design property. it can.

When printing on an acrylic resin film, it is preferable to perform printing on one side of the film.
In particular, it is preferable to perform a printing process on the surface of the film having a higher surface glossiness of 60 ° from the viewpoint of reducing print omission. When the acrylic resin film is laminated on the substrate, it is preferable to laminate the film so that the printed surface is in contact with the substrate from the viewpoint of protecting the printed surface and imparting a sense of quality. As a printing method, various conventionally known printing methods such as a gravure printing method, a flexographic printing method, and a silk screen printing method can be used. Moreover, coloring processing can be performed as needed.

The number of print omissions on the printed surface is preferably 10 / m ² or less from the viewpoint of design and decorativeness. When the number of missing prints is 10 / m ² or less, the appearance of the laminated molded product of the film becomes good. The number of missing prints is preferably 5 / m ² or less, more preferably 1 / m ² or less.

In the case of a conventionally known matte film, the number of missing prints when printing is performed is 10 pieces / m ^2.
Tend to exceed. When such a film is subjected to, for example, wood-grain printing, printing omissions appear as worm-like holes in the wood-grain, so that the appearance is not significantly reduced. However, for example, in the case of performing printing in metallic tone, it can be recognized as a clear defect, so that the design property and the appearance are reduced, and those with printing omission become defective and the production yield is reduced. On the other hand, when the acrylic resin film of the present invention is used, printing omission can be reduced. That is, its industrial value is remarkably high.

The thickness of the acrylic resin film is 300 μm.
m or less. When used as a paint substitute film,
The thickness is preferably 50 μm to 300 μm. When the thickness is 50 μm or more, a sufficient depth can be obtained in the appearance of the molded product. Also, especially when molding into complex shapes,
A sufficient thickness is obtained by stretching. On the other hand, when the thickness is 30
When the thickness is 0 μm or less, it has an appropriate rigidity, so that laminating property, secondary workability, and the like are improved. In addition, it is economically advantageous in terms of mass per unit area. Further, the film-forming properties are stable and the production of the film is facilitated.

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

When the acrylic resin film is laminated on the substrate, the film may be laminated such that the surface having a higher surface gloss of 60 ° (the surface on which printing is performed as desired) is in contact with the substrate. It is preferable from the viewpoint of protection of a printing surface and imparting a sense of quality.

Examples of the substrate include a resin molded product. The resin constituting the molded article may be any resin that can be melt-bonded to an acrylic resin film, and may be, 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 Resins containing these as main components are exemplified. Above all, ABS resin, A
S resin, polycarbonate resin, vinyl chloride resin or a resin containing these as a main component is preferable.
S resin, polycarbonate resin, or a resin containing these as a main component is more preferable. However, even with a non-heat-fusible base resin such as a polyolefin resin, an acrylic resin film and a base can be laminated and formed by interposing an adhesive layer.

When the acrylic resin film of the present invention is laminated on a two-dimensional substrate, a known method such as thermal lamination can be used for a substrate that can be heat-sealed. In addition, it is also possible to bond to a substrate that is not heat-sealed via an adhesive. When laminating and molding on a three-dimensional base material, a known molding method such as an insert molding method or an in-mold molding method can be used. Among them, the in-mold molding method is particularly preferable from the viewpoint of productivity.

In the in-mold molding method, after the acrylic resin film is heated, vacuum molding is performed in a mold having a vacuuming function. According to this in-mold molding method, film molding and injection molding can be performed in one step, which is preferable in terms of workability and economy. The heating temperature is preferably equal to or higher than the temperature at which the acrylic resin film softens. The heating temperature is usually 70 ° C. or more, although it depends on the thermal properties of the film or the shape of the molded product. However, if the temperature is too high, matte occurs and mattability is impaired.
The temperature at which delustering occurs also depends on the thermal properties of the film or the shape of the molded product.
It is preferable that the temperature is lower than or equal to ° C.

In general, when a three-dimensional shape is imparted to a film by vacuum forming, it is important that no whitening occurs at the corners of the mold and that the corners can be traced. This is a processing method that maximizes the characteristics of the acrylic resin film. That is, the acrylic resin film has high elongation at high temperatures, and is very advantageous in a vacuum forming method.

It is preferable that the mold to be brought into contact with the acrylic resin film during vacuum forming has been subjected to embossing. By this embossing processing, gloss return during in-mold molding is reduced.

According to the in-mold molding method, the acrylic resin film and the base resin are melted and integrated by injection molding after the three-dimensional shape is formed by vacuum molding as described above. Can be obtained.

The use of this acrylic laminated molded product is as follows.
Although not particularly limited, for example, console interior parts such as a console box and a shift lever box, vehicle exterior parts such as a cowling of a motorcycle, home electric appliances, furniture, building materials, etc. It can be used for members. Further, the acrylic resin film of the present invention using the hydroxyl group-containing polymer (D) or (E) having a glass transition temperature of 80 ° C. or higher is excellent in chemical resistance and the like, and is particularly suitable for a laminate for a vehicle interior. Very useful as a surface layer.

[0108]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In the examples, “parts” means “parts by mass”. Abbreviations in the examples are as follows. Methyl methacrylate MMA methyl acrylate MA butyl acrylate BA styrene St α-methylstyrene αM-ST cyclohexylmaleimide CHMI hydroxyethyl methacrylate HEMA allyl methacrylate AMA 1,3-butylene glycol dimethacrylate 1,3BD t-butyl hydroperoxide tBH t-hexylhydro Peroxide tHH lauryl peroxide LPO n-octyl mercaptan nOM

The measurement of various physical properties in the examples was carried out according to the following methods.

1) Reduced viscosity and intrinsic viscosity: The reduced viscosities of the thermoplastic polymers (A-2) and (F) and the intrinsic viscosities of the hydroxyl group-containing polymers (D) and (E) are manufactured by Sun Electronics Co., Ltd. Using an AVL-2C automatic viscometer, chloroform was used as a solvent, and the measurement was performed at 25 ° C. In the measurement of the reduced viscosity, a solution prepared by dissolving 0.1 g of a sample in 100 ml of chloroform was used.

2) Particle diameter: The particle diameters of the rubber-containing polymer (A-1) and the multilayer structure polymer [acrylic resin composition (B)] were determined based on the final polymer latex of those polymers obtained by emulsion polymerization. The particle diameter was measured by a dynamic light scattering method using a light scattering photometer DLS-700 manufactured by Otsuka Electronics Co., Ltd.

3) 60 ° Surface Gloss The 60 ° surface gloss was measured using a gloss meter (Model GM-26D, manufactured by Murakami Color Research Laboratory).

4) Thermal Deformation Temperature of Acrylic Resin Composition Acrylic resin pellets before being formed into a film are
Injection molding was performed on a heat deformation temperature measurement specimen according to STM D648, and this was annealed at 80 ° C. for 24 hours. Under a low load (0.45 MPa) condition, the heat deformation temperature of the test specimen was measured according to ASTM D648. It was measured.

5) Gel Content of Acrylic Resin Composition Acrylic resin pellets before being formed into a film were dissolved in chloroform to prepare a 1% by mass chloroform solution, which was allowed to stand at 25 ° C. for 24 hours. p.
centrifuged at 90 m for 90 minutes, and the supernatant was removed.
The mass% of the insoluble matter after drying was defined as the gel content.

[0115] 6) on the side of the surface that was in contact with the mirror surface cooling roll white dots number acrylic resin film, a pattern was gravure printing, perform visual inspection of 5 m ^2, per 1 m ² by measuring the number of missing print Converted.

7) Chemical resistance A polyethylene cylinder having an inner diameter of 38 mm and a height of 15 mm was placed on the surface of the laminated molded product, and was tightly adhered to the test piece with a crimping machine.
5 ml of an air freshener for car [Gracemate Poppy Citrus System, manufactured by Diamond Chemical Co., Ltd.] was injected into the opening.
After the opening was covered with a glass plate, it was placed in a thermostat kept at 55 ° C. and left for 4 hours. After the test, remove the crimper,
The test piece was washed with water, air-dried, and the whitening state of the surface of the test portion was observed and evaluated according to the following criteria. ×-Strong whitening is observed △-Weak whitening is observed ○-Very slight whitening is observed ◎-No whitening is observed

8) Glass transition temperature of polymers (D) and (E) having a hydroxyl group The glass transition temperature was determined according to the formula of FOX.

9) Evaluation of gloss return property at the time of forming an acrylic resin film [0118] Lamination was carried out using an epoxy adhesive so that the surface which had been in contact with the mirror roll was in contact with the polycarbonate plate. After the laminate was left in an atmosphere at 120 ° C. for 48 hours, the surface gloss of the laminate at 60 ° was measured.

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

Subsequently, 0.4 part of sodium formaldehyde sulfoxylate was added to the latex of the elastic copolymer (a-1), and the mixture was kept for 15 minutes and stirred at 80 ° C. under a nitrogen atmosphere. Raw materials shown below (d)
[Raw material for hard polymer (a-2)] was continuously added at an increase rate of the monomer mixture to water of 10% / hour. After that, polymerization was carried out by holding for 1 hour, and the rubber-containing polymer (A-
The latex of 1) was obtained. The particle diameter of the rubber-containing polymer (A-1) was 0.28 μm.

The latex of the rubber-containing polymer (A-1) was filtered through a filter having a mesh size of 50 μm.
Coagulation, aggregation and solidification using calcium acetate,
After filtration, washing with water and drying, a rubber-containing polymer (A-1) was obtained.

(A) Sodium formaldehyde sulfoxylate 0.6 part Ferrous sulfate 0.00012 parts Ethylenediaminetetraacetic acid disodium 0.0003 part (b) MMA 18.0 parts BA 20.0 parts St 2.0 Part AMA 0.4 part 1.3BD 0.14 part tBH 0.18 part Mono (polyoxyethylene nonyl phenyl ether) phosphoric acid 40% and di (polyoxyethylene nonyl phenyl ether) phosphoric acid 60% of sodium hydroxide Partial neutralized product of mixture 1.0 part (c) BA 50.0 parts St 10.0 parts AMA 0.4 parts 1.3BD 0.14 parts tHH 0.2 parts Mono (polyoxyethylene nonylphenyl ether) phosphorus Partial neutralized product of a mixture of 40% acid and 60% di (polyoxyethylene nonylphenyl ether) phosphoric acid in sodium hydroxide 1.0 part (d) MM 57.0 parts MA 3.0 parts nOM 0.3 parts tBH 0.06 parts

The rubber-containing polymer (A-
1) 23 parts and MMA which is a thermoplastic polymer (A-2)
/ MA copolymer (MMA / MA = 99/1, reduced viscosity 0.06 L / g) was mixed with 77 parts to obtain an acrylic resin composition (A).

<Production Example 2: Production of acrylic resin composition (B)> In a polymerization vessel equipped with a cooler, 250 parts of ion-exchanged water,
2 parts of an ester soda salt of sulfosuccinic acid and 0.05 part of sodium formaldehyde sulfoxylate were charged and stirred under nitrogen, and then 1.6 parts of MMA, 8 parts of BA, and 1,3 BD
A mixture consisting of 0.4 part, 0.1 part AMA and 0.04 part cumene hydroperoxide was charged. After the temperature was raised to 70 ° C., the reaction was continued for 60 minutes and the innermost layer polymer (B-
The polymerization of a) was completed. Subsequently, the crosslinked elastic polymer (B-
1.5 parts of MMA, 22.5 parts of BA to form b)
A mixture consisting of 1.0 part of 1.3BD, 0.25 part of AMA and 0.05 part of cumene hydroperoxide was added in 60 minutes, polymerized, and polymerized as the innermost layer polymer (Ba) and the crosslinked elastic polymer (B). -B) to obtain a two-layer crosslinked rubber elastic body.

Subsequently, a mixture of 5 parts of MMA, 5 parts of BA and 0.1 part of AMA is reacted in the presence of the two-layer crosslinked rubber elastic body to form an intermediate layer (Bd).
A mixture comprising 52.25 parts of MMA and 2.75 parts of BA was reacted to form an outermost layer polymer (Bc), thereby obtaining a latex of a multilayer structure polymer.

The particle size of the multilayer polymer is 0.12 μm.
m. The obtained polymer latex was passed through a mesh opening 75
After filtration through a μm filter, 100 parts of the polymer was salted out using 5 parts of calcium acetate, washed, and dried to obtain an acrylic resin composition (B).

<Production Example 3: Production of acrylic resin composition (C)> The following mixture was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, and the like.

MA 10 parts MMA 60 parts HEMA 30 parts n-OM 0.15 parts LPO 0.5 parts Methyl methacrylate / methacrylate / ethyl methacrylate sulfonate copolymer 0.05 part Sodium sulfate 0.5 part Part 250 parts of ion exchange water

The inside of the vessel was sufficiently purged with nitrogen gas, and then heated to 75 ° C. with stirring, and the polymerization was advanced in a stream of nitrogen gas. Two hours later, the temperature was raised to 90 ° C., and the temperature was further maintained for 45 minutes to complete the polymerization. The obtained polymer beads were dehydrated and dried to obtain a polymer (D) -1 having a hydroxyl group.
The intrinsic viscosity of the polymer (D) -1 is 0.069 L /
g, the glass transition temperature was 77 ° C. Using 10 parts of the polymer (D) -1 having a hydroxyl group as a matting agent, 100 parts of the acrylic resin composition (A) obtained in Production Example 1, or 100 parts of the acrylic resin composition (B) obtained in Production Example 2 By mixing with 100 parts, two types of acrylic resin compositions (C) were obtained.

<Production Example 4: Polymer having hydroxyl group (D)>
Production of -2> The following mixture was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, and the like.

MA 1 part MMA 79 parts HEMA 20 parts n-OM 0.14 parts LPO 0.5 part Methyl methacrylate / methacrylate / ethyl methacrylate sulfonate copolymer 0.05 part Sodium sulfate 0.5 part Part 250 parts of ion exchange water

The inside of the vessel was sufficiently purged with nitrogen gas, and then heated to 75 ° C. with stirring, and the polymerization was advanced in a nitrogen gas stream. Two hours later, the temperature was raised to 90 ° C., and the temperature was further maintained for 45 minutes to complete the polymerization. The obtained polymer beads were dehydrated and dried to obtain a polymer (D) -2 having a hydroxyl group.
The intrinsic viscosity of the polymer (D) -2 is 0.076 L /
g, glass transition temperature was 93 ° C.

<Production Example 5: Polymer having hydroxyl group (D)
Production of -3> The following mixture was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, and the like.

MA 1 part MMA 89 parts HEMA 10 parts n-OM 0.11 parts LPO 0.5 parts Copolymer of methyl methacrylate / methacrylate / ethyl methacrylatesulfonate 0.05 part Sodium sulfate 0.5 part Part 250 parts of ion exchange water

The inside of the vessel was sufficiently replaced with nitrogen gas, and then heated to 75 ° C. with stirring, and the polymerization was advanced in a nitrogen gas stream. Two hours later, the temperature was raised to 90 ° C., and the temperature was further maintained for 45 minutes to complete the polymerization. The obtained polymer beads were dehydrated and dried to obtain a polymer (D) -3 having a hydroxyl group.
The intrinsic viscosity of the polymer (D) -3 is 0.09 L / g,
The glass transition temperature was 98 ° C.

<Production Example 6: Polymer having a hydroxyl group (E)
Production> The following mixture was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, and the like.

ST 20 parts MMA 60 parts HEMA 20 parts n-OM 0.1 part LPO 0.5 part Copolymer of methyl methacrylate / methacrylate / ethyl methacrylate sulfonate 0.05 part Sodium sulfate 0.5 part Part 250 parts of ion exchange water

The inside of the vessel was sufficiently replaced with nitrogen gas, and then heated to 75 ° C. with stirring, and the polymerization was advanced in a nitrogen gas stream. Two hours later, the temperature was raised to 90 ° C., and the temperature was further maintained for 45 minutes to complete the polymerization. The obtained polymer beads were dehydrated and dried to obtain a polymer (E) having a hydroxyl group. This polymer (E) had an intrinsic viscosity of 0.11 L / g and a glass transition temperature of 93 ° C.

<Production Example 7: Polymer having hydroxyl group (D)
Production of -4> The following mixture was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, and the like.

MA 20 parts MMA 60 parts HEMA 20 parts n-OM 0.08 parts LPO 0.5 parts Copolymer of methyl methacrylate / methacrylate / ethyl methacrylate sulfonate 0.05 part Sodium sulfate 0.5 part Part 250 parts of ion exchange water

The inside of the vessel was sufficiently replaced with nitrogen gas, and then heated to 75 ° C. with stirring, and the polymerization was advanced in a stream of nitrogen gas. Two hours later, the temperature was raised to 90 ° C., and the temperature was further maintained for 45 minutes to complete the polymerization. The obtained polymer beads were dehydrated and dried to obtain a polymer (D) -4 having a hydroxyl group.
The intrinsic viscosity of this polymer (D) -4 is 0.11 L / g,
Glass transition temperature was 71 ° C.

<Production Example 8: Polymer having hydroxyl group (D)
Production of -5> The following mixture was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, and the like.

MA 1 part MMA 69 parts HEMA 30 parts n-OM 0.15 parts LPO 0.5 part Copolymer of methyl methacrylate / methacrylate / ethyl methacrylate sulfonate 0.05 part Sodium sulfate 0.5 part Part 250 parts of ion exchange water

The inside of the vessel was sufficiently replaced with nitrogen gas, and then heated to 75 ° C. with stirring, and the polymerization was advanced in a stream of nitrogen gas. Two hours later, the temperature was raised to 90 ° C., and the temperature was further maintained for 45 minutes to complete the polymerization. The obtained polymer beads were dehydrated and dried to obtain a polymer (D) -5 having a hydroxyl group.
The intrinsic viscosity of the polymer (D) -5 is 0.072 L /
g, glass transition temperature was 87 ° C.

<Production Example 9: Production of thermoplastic polymer (F)> A reaction vessel was charged with 200 parts of nitrogen-exchanged ion-exchanged water, and 1 part of an emulsifier, potassium oleate, and 0.3 parts of potassium persulfate were charged. Next, 40 copies of MMA, BA10
Parts, 0.005 part of nOM, 65 ° C under nitrogen atmosphere
For 3 hours to complete the polymerization. Subsequently, M
A monomer mixture composed of 48 parts of MA and 2 parts of BA was added dropwise over 2 hours, and the mixture was maintained for 2 hours after completion of the dropwise addition to complete the polymerization. The obtained latex was added to a 0.25% aqueous sulfuric acid solution, and the polymer was subjected to acid coagulation, followed by dehydration, washing and drying to recover the polymer in powder form. The reduced viscosity ηsp / c of the obtained copolymer [thermoplastic polymer (F)] is 0.38.
L / g.

Example 1 100 parts of the acrylic resin composition (A) of Production Example 1 and the thermoplastic polymer (F) 1 of Production Example 9
1 part of Tinuvin 1577 (manufactured by Ciba-Geigy) as an ultraviolet absorber, and PEP8 as a phosphite-based antioxidant
0.6 parts of F (manufactured by Asahi Denka Co., Ltd.) was mixed using a Henschel mixer. Then, screw type 2 of 40 mmφ
Using a screw extruder (L / D = 26), cylinder temperature 2
The mixture was melt-kneaded under conditions of 00 ° C. to 260 ° C. and a die temperature of 250 ° C., and pelletized to obtain pellets of the film composition.

The pellets were dried at 80 ° C. for 24 hours,
Using a 40 mmφ non-vent screw extruder (L / D = 26) equipped with a 00 mm T die and a 400 mesh screen mesh, the cylinder temperature was 2
Under conditions of 00 ° C to 240 ° C and T die temperature of 250 ° C, T
Melt extrusion was performed through a die. The extruded resin is 7
Cooling mirror roll (rolled with chrome-plated surface roughness 0.2S) cooled to 5 ° C, average particle size 40μ
An acrylic resin film having a thickness of 200 μm was formed by sandwiching the same with a silicone rubber roll containing 50 parts of sand.

Further, the surface of the acrylic resin film which was in contact with the mirror roll was subjected to gravure printing. Next, this film was heated at 140 ° C. for 1 minute, and vacuum-molded with a mold having a vacuuming function. An ABS resin (Diapet ABS Bulk Sum TM20, manufactured by Mitsubishi Rayon Co., Ltd.) with the formed film placed in a mold
Was injection molded on the printing surface side of the film to obtain a laminated molded product.

<Example 2> Acrylic resin composition (A) 1
Example 1 was repeated except that 100 parts of the acrylic resin composition (B) of Production Example 2 was used instead of 00 parts.

<Example 3> Acrylic resin composition (A) 1
Except that 10 parts of the hydroxyl group-containing polymer (D) -1 of Production Example 3 was further added to 00 parts [that is, one acrylic resin composition (C) of Production Example 3 was used], It carried out similarly to Example 1.

<Example 4> Acrylic resin composition (B) 1
Except that 10 parts of the hydroxyl group-containing polymer (D) -1 of Production Example 3 was further added to 00 parts [that is, the other acrylic resin composition (C) of Production Example 3 was used]. The operation was performed in the same manner as in Example 2.

<Example 5> The same procedure as in Example 4 was carried out except that the temperature of the mirror roll for cooling was set to 50 ° C.

<Example 6> As a matting agent, instead of 10 parts of polymer (D) -1 having a hydroxyl group, PMMA crosslinked particles (MR-2G, Soken Chemical Co., Ltd.) having an average particle size of about 2 µm were used instead of 10 parts. The procedure was performed in the same manner as in Example 3 except for using a part.

<Example 7> As a matting agent, instead of 10 parts of polymer (D) -1 having a hydroxyl group, PMMA crosslinked particles (MR-2G, manufactured by Soken Chemical Co., Ltd.) 10 having an average particle size of about 2 μm were used. Example 4 was carried out except that parts were used.

Example 8 The same operation as in Example 3 was carried out except that a roll with a texture was used instead of the silicone rubber roll containing sand.

Example 9 As the thermoplastic resin (A-2), an MMA / MA copolymer (MMA / MA = 99/1,
(Reduced viscosity 0.06 L / g) Instead of 77 parts, MMA /
Except that an acrylic resin composition (A) was prepared using 77 parts of a BA copolymer (MMA / BA = 80/20, reduced viscosity 0.08 L / g), and this acrylic resin composition (A) was used. Was carried out in the same manner as in Example 3.

<Example 10> As a thermoplastic resin (A-2), an MMA / MA copolymer (MMA / MA = 99 /
1, reduced viscosity 0.06 L / g) Instead of 77 parts, MM
A / αM-ST / CHMI copolymer (MMA / αM-S
T / CHMI = 85/5/10, reduced viscosity 0.06 L /
g) Acrylic resin composition (A) was prepared using 77 parts, and the same procedure as in Example 3 was carried out except that this acrylic resin composition (A) was used.

Example 11 Production Example 3 as a matting agent
Instead of 10 parts of the polymer (D) -1 having a hydroxyl group, the polymer (D) -2 10 having a hydroxyl group of Production Example 4
The procedure was performed in the same manner as in Example 3 except for using a part.

Example 12 Production Example 3 as a matting agent
Instead of 10 parts of the polymer (D) -1 having a hydroxyl group, the polymer (D) -3 10 having a hydroxyl group of Production Example 5
The procedure was performed in the same manner as in Example 3 except for using a part.

Example 13 As a matting agent, Production Example 3
The procedure was performed in the same manner as in Example 3 except that 10 parts of the polymer (E) having a hydroxyl group of Production Example 6 was used instead of 10 parts of the polymer (D) -1 having a hydroxyl group.

Example 14 Production Example 3 as a matting agent
Instead of 10 parts of the polymer (D) -1 having a hydroxyl group, the polymer (D) -4 10 having a hydroxyl group of Production Example 7
The procedure was performed in the same manner as in Example 3 except for using a part.

Example 15 The same operation as in Example 14 was performed except that PEP8F was not used.

Example 16 The same operation as in Example 4 was carried out except that PEP8F was not used.

Example 17 Production Example 3 as a matting agent
Instead of 10 parts of the polymer (D) -1 having a hydroxyl group, the polymer (D) -5 10 having a hydroxyl group of Production Example 8 was used.
The procedure was performed in the same manner as in Example 3 except for using a part.

<Comparative Examples 1 to 4> Films were prepared, printed and laminated in the same manner as in Examples 1 to 4 except that a film was formed using only a mirror-finished roll without using a silicone rubber roll containing sand. Molding was performed. In Comparative Examples 1 to 4, the difference in the 60 ° surface gloss between the front and back of the obtained film was 5
%.

<Evaluation> The evaluation results of the examples and comparative examples are shown in Table 1 below.

[0167]

[Table 1]

[0168]

As described above, according to the present invention,
It is possible to provide an acrylic resin film having a good matte appearance and good printability such as little print omission when performing printing, a method for producing the same, and a laminate having the film on the surface. it can. In addition, by using a matting agent having a specific glass transition temperature, a laminate that can be used for vehicle interior applications can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 5/18 CEY C08J 5/18 CEY 4J026 C08L 33/06 C08L 33/06 33/14 33/14 51 / 00 51/00 // B29K 33:00 B29K 33:00 B29L 7:00 B29L 7:00 (72) Inventor Kazuhiko Nakagawa 4-1-1, Ushikawa-dori, Toyohashi-shi, Aichi F in Toyohashi Works, Mitsubishi Rayon Co., Ltd. Terms (Reference) 3D023 BA01 BB01 BD00 BE04 4F071 AA33 AA77 AF30 AF32 AH19 BA01 BB04 BB06 BC01 4F100 AK25A AK74 AL01A AL04A AL05A AT00B BA02 BA07 CA30A GB90 HB00 HB31A JA04A JK07A JN21AA01 GW01 AJA4 KA4 AC09 BA27 BB01 DB04 GA01 GA02 GA08

Claims (16)

[Claims] 1. An acrylic resin film having a difference of 60 ° surface gloss between the front and back of the film of 5% or more and a thickness of 300 μm or less. 2. The acrylic resin film according to claim 1, wherein at least one of the film surfaces has a 60 ° surface glossiness of 50% or less. 3. The heat deformation temperature shown below is 60 to 115 ° C.
The acrylic resin film according to claim 1, comprising an acrylic resin composition (A) within the range of (1). Acrylic resin composition (A) 5.5 to 99.9 parts by mass of a rubber-containing polymer (A-1) shown below and a thermoplastic polymer (A-2) obtained by using an alkyl methacrylate as a main component 0.1 to 94.5 parts by mass [total 10 of component (A-1) and component (A-2)
0 parts by mass]. Rubber-Containing Polymer (A-1) In the presence of an elastic copolymer (a-1) as an inner layer having one or more layers obtained by using an alkyl acrylate as a main component, an alkyl methacrylate is used. One layer or 2
Hard polymer (a-
2. A rubber-containing polymer having a multilayer structure of two or more layers, which is obtained by forming 2). 4. The heat deformation temperature shown below is 60 to 115 ° C.
The acrylic resin film according to claim 1, comprising an acrylic resin composition (B) within the range of (1). Acrylic resin composition (B) 80 to 100 parts by mass of an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms or an alkyl methacrylate (B-a1) having an alkyl group having 1 to 4 carbon atoms, copolymerizable Other monomers having a double bond (B-
a2) 0 to 20 parts by mass and a polyfunctional monomer (B-
a3) Innermost layer polymer (Ba) obtained by polymerizing a monomer composition obtained by adding 0.1 to 5 parts by mass of a graft-linking agent to a total of 100 parts by mass of 0 to 10 parts by mass; 80 to 100 parts by mass of acrylic acid alkyl ester (B-b1) having an alkyl group of Formulas 1 to 8, 0 to 20 parts by mass of another monomer (B-b2) having a copolymerizable double bond, and , The graft-linking agent 0.1 with respect to a total of 100 parts by mass of the polyfunctional monomer (B-b3) 0 to 10 parts by mass.
A crosslinked elastic polymer (Bb) obtained by polymerizing a monomer composition to which 5 to 5 parts by mass has been added, and a methacrylic acid alkyl ester having 1 to 4 carbon atoms (Bc)
1) A glass transition temperature obtained by polymerizing a monomer comprising 51 to 100 parts by mass and 0 to 49 parts by mass of another monomer (B-c2) having a copolymerizable double bond. 60
An outermost layer polymer (B-c) having a basic structure of (C) or higher, and further comprising a crosslinked elastic polymer (B-b). As an intermediate layer between the layer and the layer composed of the outermost layer polymer (B-c), 10 to 90 parts by mass of an alkyl acrylate (B-d1) having an alkyl group having 1 to 8 carbon atoms, 4
90 to 10 parts by mass of a methacrylic acid alkyl ester having an alkyl group (B-d2), 0 to 20 parts by mass of a monomer (B-d3) having a copolymerizable double bond, and
Polyfunctional monomer (B-d4) 0 to 10 parts by mass in total of 10
Acrylic acid having at least one intermediate layer (B-d) made of a polymer obtained by polymerizing a monomer composition to which 0.1 to 5 parts by mass of a graft crosslinking agent is added based on 0 parts by mass. The content ratio of the alkyl ester is such that the crosslinked elastic polymer (Bb), the intermediate layer (Bd), and the outermost layer polymer (B
An acrylic resin composition containing, as a main component, a multilayer structure polymer monotonically decreasing in the order of -c). 5. The acrylic resin composition (A) according to claim 3, or the acrylic resin composition (B) according to claim 4.
An acrylic resin composition (C) having a heat distortion temperature in the range of 60 to 115 ° C, which is obtained by further adding 0.1 to 40 parts by mass of a matting agent to 100 parts by mass. 2. The acrylic resin film according to 1. 6. The acrylic resin film according to claim 5, wherein the matting agent is a polymer (D) having a hydroxyl group shown below. Hydroxyl-containing polymer (D) 1 to 80 parts by mass of hydroxyalkyl acrylate or hydroxyalkyl methacrylate having an alkyl group having 1 to 8 carbon atoms, alkyl methacrylate having an alkyl group having 1 to 13 carbon atoms 10-99
A total of 100 parts by mass, and 0 to 79 parts by mass of an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms
A hydroxyl-containing polymer obtained by polymerizing a monomer composition consisting of parts by mass. 7. The acrylic resin film according to claim 6, wherein the glass transition temperature of the hydroxyl group-containing polymer (D) is 80 ° C. or higher. 8. The acrylic resin film according to claim 5, wherein the matting agent is a hydroxyl group-containing polymer (E) shown below. Hydroxy group-containing polymer (E) 5-80 parts by mass of hydroxyalkyl acrylate or hydroxyalkyl methacrylate having an alkyl group having 1-8 carbon atoms, alkyl methacrylate having an alkyl group having 1-13 carbon atoms 10-94
A hydroxyl group-containing polymer obtained by polymerizing a monomer composition comprising 100 parts by mass of 1 part by mass and 1 to 80 parts by mass of an aromatic vinyl monomer. 9. The acrylic resin film according to claim 8, wherein the glass transition temperature of the hydroxyl group-containing polymer (E) is 80 ° C. or higher. 10. The acrylic resin film according to claim 5, wherein when heated at 120 ° C. for 48 hours, one of the film surfaces has a 60 ° surface glossiness of 50% or less. 11. The acrylic resin film according to claim 1, wherein a pattern is printed on the surface having a higher surface glossiness of 60 °. 12. The acrylic resin film according to claim 11, wherein the number of missing prints on the printed surface is 10 / m ² or less. 13. A method for producing an acrylic resin film according to claim 1, wherein the acrylic resin composition is melt-extruded and then sandwiched between a mirror roll and a rubber roll to form a film. Film production method. 14. A method for producing an acrylic resin film according to claim 1, wherein the acrylic resin composition is melt-extruded, and then sandwiched between a mirror-finished roll and a roll with embossments to form a film. A method for producing an acrylic resin film. 15. The acrylic resin film according to claim 1, wherein the surface having a higher surface glossiness of 60 ° is in contact with the acrylic resin film,
A laminate formed by laminating the acrylic resin film on a substrate. 16. A laminate for a vehicle interior having the acrylic resin film according to claim 7 as a surface layer.