JP2003340986A - Laminated film or sheet for substitution for coating, method for manufacturing it, and laminated body having laminated film or sheet for substitution for coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated film or sheet for substitution for coating having a matte acrylic resin film with a good matte appearance on the outermost layer, feelings of high quality, depth and calmness, a decorative layer in which the occurrence of dropout of printing is suppressed, and good appearance characteristics, and a laminated body laminated with this on a base material. <P>SOLUTION: A method for manufacturing the laminated film or sheet for substitution for coating having an acrylic resin film (I), a decorative layer (II) and a thermoplastic resin film or sheet (III) comprises forming the decorative layer (II) with appearance defects of ≤10 per 1 m<SP>2</SP>on the thermoplastic resin film or sheet (III) and laminating the acrylic resin film (I) with a 60° surface gloss of ≤50% on the decorative layer (II). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating substitute laminated film or sheet, a method for producing the same, and a laminate having the coating substitute laminated film or sheet.

[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 comprises forming a decorative layer such as printing on the surface of a film or sheet of polyester resin, polycarbonate resin, acrylic resin or the like, and molding this into a desired shape by a vacuum molding method or the like. Instead, it is placed in the injection molding die and the resin that serves as the base material is injection molded. By this method, the resin film or sheet having the decorative layer formed thereon and the substrate can be integrated with high productivity, or only printing can be transferred.

An acrylic resin film which can be suitably used in such an in-mold molding method is disclosed in JP-A-9-2.
It is disclosed in Japanese Patent No. 63614. This acrylic resin film is excellent in printability when the foreign matter having a diameter of 80 μm or more is 1 / m ² or less and the thickness is 300 μm or less,
For example, it is produced using an acrylic composition containing a thermoplastic polymer obtained by polymerizing a predetermined monomer mixture by a predetermined method and a rubber-containing polymer in a predetermined amount.
When printing is performed on this acrylic resin film, printing omission caused by convex portions (hereinafter referred to as fish eyes) on the surface due to foreign matter is suppressed, and excellent printability can be realized. Further, Japanese Patent Laid-Open No. 8-323934 discloses an acrylic resin film which can be used in place of coating having excellent surface hardness.

On the other hand, in recent years, it has been demanded that the surface of an acrylic resin film on which a decorative layer for printing or the like is formed has a matte state to add design characteristics such as a high-grade feeling and a deep feeling. Such a requirement can be realized by using a matte acrylic resin film.

For example, JP-A-10-237261 discloses a thermoplastic polymer obtained by polymerizing a predetermined monomer mixture by a predetermined method, and a rubber-containing polymer controlled to have a predetermined particle size. Contains a specified amount and has a surface gloss of 1
Disclosed is a matte acrylic film having a thickness of 0 to 100% and a thickness of 300 μm or less for an acrylic laminated molded article, and further, as a matte agent, a matte acrylic film to which inorganic particles, organic crosslinked particles, and a hydroxyl group-containing linear polymer are added. Has been done.
This matte acrylic film is excellent in surface hardness, has a high-grade appearance and is excellent in depth and has a matte appearance. Further, it has a suppressed matt finish and can be suitably used as a substitute for coating.

Furthermore, on the other hand, a metallic tone,
Many decorated films have been studied, and for example, JP-A No. 11-207887 discloses a pearl pigment and a vinylidene fluoride resin, or a pearl pigment and a vinylidene fluoride resin and a methacrylic acid ester resin. A vinylidene fluoride-based resin film having a metallic tone and having a surface layer contained therein is disclosed. JP 2
000-33675 discloses a decorative sheet in which a colorless transparent acrylic resin sheet is laminated on a colored acrylic resin sheet having a decorative layer such as a metal thin film layer. Japanese Unexamined Patent Publication No. 2000-86853 discloses a laminated film including an uncolored acrylic resin film and a colored acrylic resin film to which metal powder is added, or a colored olefin resin film. .

Further, Japanese Patent Application Laid-Open No. 2000-84772 discloses that at least a base sheet and a metal color layer are formed,
Under an ambient temperature of 150 ° C., a test piece of a simultaneously formed sheet having a width of 10 mm is sandwiched between a pair of chucks and fixed at a distance of 10 mm between the opposite edges of the chucks, and one end of the test piece is 10 mm.
60 in Japanese Industrial Standard (JIS) Z8741 with a load applied at a constant speed per minute and extended to 20 mm.
A molded simultaneous painting sheet having a reflection surface gloss of 75% or more is disclosed. In addition, JP-A-11-24526
No. 1 discloses an acrylic film insert molded article having a printed acrylic resin film as a surface layer by injection molding using an acrylic printing insert film in which a printed layer having at least a pattern layer is formed on the acrylic film, for example, metal. A method of manufacturing a tonal wheel cap and bumper is disclosed.

[0008]

However, although the film disclosed in Japanese Patent Laid-Open No. 10-237261 is excellent in matting property, printing when the matting acrylic resin film is printed. No details are given regarding omission. Therefore, the inventors of the present invention produced a matte acrylic resin film described in Japanese Patent Application Laid-Open No. 10-237261 and conducted a printing test. As a result, it was found that an extremely large number of print defects could occur. . That is, this matte acrylic resin film may have good matteness but insufficient printability.

As described above, when a conventional matte acrylic resin film is printed, appearance defects such as print omissions caused by fish eyes and the like may become extremely large. When wood-grain printing is applied to such a film, it is not likely to cause a noticeable deterioration in appearance because the print omission looks as if it is a worm-eating hole, but it is obvious especially when metal-like printing is applied. However, the appearance and appearance may be impaired due to the deterioration of design and decoration. The matte acrylic resin film having a large number of such print defects has low industrial utility value. Also,
There is also a problem in that the yield may decrease because the part where printing is missing cannot be used as a product.

Further, Japanese Patent Laid-Open No. 2000-86853,
JP-A-2000-84972, JP-A-11-245
No. 261, JP-A No. 11-245261, and the like, a metal-tone film or sheet having a layer made of an acrylic resin or a layer containing an acrylic resin on the surface has a sufficient matte property of the acrylic resin layer. In some cases, the resulting metal-tone film or sheet does not have high glossiness and has a glossy appearance and lacks a high-grade appearance. Therefore, it is strongly desired to develop a metal-like decorating film or sheet having a high-class appearance and a calming appearance, which can be used as a substitute for coating, and a laminate obtained by laminating the film or sheet on a base material.

The present invention provides a laminated film or sheet as a paint substitute, which has a good matte appearance, suppresses the occurrence of print omission, and has excellent appearance characteristics such as a high-grade feeling, a deep feeling, and a calm feeling, and its production. It is an object of the present invention to provide a method and a laminate in which a laminated film or sheet as a paint substitute is laminated on a substrate.

[0012]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors formed a decorative layer on a thermoplastic resin film or sheet, and specified on it. It was found that a laminated film or sheet exhibiting good appearance and designability and suitable for use as an alternative to coating can be produced by laminating an acrylic resin film having a surface glossiness of 1.

That is, the method for producing a laminated film or sheet for coating alternative of the present invention is the acrylic resin film (I).
And a decorative layer (II) and a thermoplastic resin film or sheet (III), which is a method for producing a laminated film or sheet for coating substitution, wherein the thermoplastic resin film or sheet (III) has an external appearance. A decorative layer (II) having 10 or less defects per 1 m ² is formed, and 60 is formed on the decorative layer (II).
A feature of laminating an acrylic resin film (I) having a surface gloss of 50% or less. Also, the decorative layer (II)
It is preferable that the acrylic resin film (I) is laminated after the colored layer (IV) is formed thereon. Further, on the thermoplastic resin film or sheet (III), a colored layer (I
The decorative layer (II) can be formed after forming V). Further, the acrylic resin film (I) is 0.1 to 100 parts by mass of the following acrylic resin component (A).
It is preferably formed from an acrylic resin composition containing 40 parts by mass of a matting agent. Acrylic resin component (A) 5.5 to 99.9% by mass of the rubber-containing polymer (A-1),
Consisting of a thermoplastic polymer (A-2) having 0.1 to 94.5 mass% of a methacrylic acid alkyl ester as a main component,
The rubber-containing polymer (A-1) is a monomeric compound containing an methacrylic acid alkyl ester as a main component in an elastic copolymer (a-1) obtained by polymerizing a monomer composition containing an acrylic acid alkyl ester. It is obtained by graft-polymerizing a body composition. In addition, the acrylic resin film (I),
It is preferably formed from an acrylic resin composition containing 0.1 to 40 parts by mass of a matting agent with respect to 100 parts by mass of the following acrylic resin component (B). Acrylic resin component (B) A multilayer structure polymer having an innermost polymer (B-1), a crosslinked elastic polymer (B-2) layer, and an outermost polymer (B-3) layer in this order from the inside. , The innermost polymer (B-1) is 80 to 1
0% by mass of an acrylic acid alkyl ester having a C1-8 alkyl group and / or a methacrylic acid alkyl ester having a C1-4 alkyl group;
Graft of 0.1 to 5 parts by weight based on 100 parts by weight of another monomer having 20% by weight of a copolymerizable double bond and 0 to 10% by weight of a polyfunctional monomer. Obtained by polymerizing a monomer composition containing a crossing agent, a crosslinked elastic polymer (B-
2) The layer is composed of 80 to 100% by mass of an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms and 0 to 20.
With another monomer having a mass% copolymerizable double bond,
The outermost polymer obtained by polymerizing a monomer composition containing 0.1 to 5 parts by mass of a graft crossing agent based on 100 parts by mass of a total of 0 to 10% by mass of a polyfunctional monomer. The (B-3) layer comprises 51 to 100% by mass of a methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms, and 0 to 49% by mass of another monomer having a copolymerizable double bond. It is obtained by polymerizing a monomer composition containing: and further between the crosslinked elastic polymer (B-2) layer and the outermost polymer (B-3) layer.
To 90% by mass of an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms, 90 to 10% by mass of an methacrylic acid alkyl ester having an alkyl group of 1 to 4 carbon atoms, and 0 to 20% by mass. A monomer containing 0.1 to 5 parts by mass of a graft crossing agent based on 100 parts by mass of a total of 100 parts by mass of a monomer having a polymerizable double bond and a polyfunctional monomer of 0 to 10% by mass. The composition has at least one intermediate polymer (B-4) layer obtained by polymerizing the composition, and the content (% by mass) of the alkyl acrylate is equal to that of the crosslinked elastic polymer (B
-2) It decreases from the layer toward the outermost polymer (B-3) layer. The thermoplastic resin film or sheet (III) is preferably melt-extruded through a screen mesh of 200 mesh or more. Further, the decorative layer (II) is preferably a metallic print layer or a metallic layer. The laminated film or sheet for coating alternative of the present invention is characterized by being obtained by the above-mentioned manufacturing method. The laminated body of the present invention is characterized in that the coating substitute laminated film or sheet is laminated on the base material such that the acrylic resin film (I) is the outermost layer.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
FIG. 1 shows one form of a film or sheet as a paint substitute, which is obtained by the production method of the present invention, in which an appearance defect is 10 per 1 m ² on a thermoplastic resin film or sheet (III).
A decorative layer (II) having no more than individual pieces is formed, and the decorative layer (I
An acrylic resin film (I) having a 60 ° surface gloss of 50% or less is laminated on the I). Hereinafter, the acrylic resin film (I), the decorative layer (II), and the thermoplastic resin film or sheet (III), which are the constituent elements of the coating substitute laminated film or sheet, will be sequentially described.

As the acrylic resin film (I), 6
If the 0 ° surface glossiness is 50% or less, sufficient matting property is exhibited and there is no particular limitation. However, the acrylic resin component (A) or the acrylic resin component (B) 10 which will be described later is used.
It is preferably formed from an acrylic resin composition containing 0.1 to 40 parts by weight of a matting agent with respect to 0 parts by weight.

Here, the 60 ° surface glossiness means an incident angle of 60.
Reflected light at an equal angle (reflection angle 60 °) with respect to the incident light of 90 °, that is, the reference surface of the specular reflected light (refractive index 1.567).
(The plane of the glass) in the same condition under the same conditions.

(Acrylic resin component (A)) The acrylic resin component (A) is obtained by grafting a specific elastic copolymer (a-1) with a monomer composition constituting a hard polymer (a-2). A rubber-containing polymer (A-1) containing a polymerized rubber-containing polymer (A-1) and a thermoplastic polymer (A-2) obtained by polymerizing a monomer composition containing an alkyl methacrylic acid as a main component. The content of the polymer (A-1) is 5.5 to 99.9% by mass, and the content of the thermoplastic polymer (A-2) is 0.1 to 94.5% by mass. When the rubber-containing polymer (A-1) and the thermoplastic polymer (A-2) are contained in such a proportion, an acrylic resin film (I) having good film-forming property can be obtained.

The elastic copolymer (a-1) which is the inner layer of the rubber-containing polymer (A-1) is obtained by polymerizing a monomer composition containing an alkyl acrylate ester.
It has a layer or a multilayer structure of two or more layers. The alkyl acrylate is not particularly limited, and known ones can be used, but butyl acrylate, 2-ethylhexyl acrylate and the like are particularly preferably used. You may use these individually or in combination of 2 or more types. Moreover, since the acrylic resin film (I) has good moldability, the content (use amount) of the alkyl acrylate ester constituting the elastic copolymer (a-1) is excellent. ), 35 mass% to 99.9 mass% is preferable, and 50 mass% to 99.9 mass% is more preferable.

As the monomer constituting the elastic copolymer (a-1), a crosslinkable monomer can be used in addition to the acrylic acid alkyl ester. The crosslinkable monomer is not particularly limited, but ethylene glycol dimethacrylate,
It is preferable to use butanediol dimethacrylate, allyl acrylate, allyl methacrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, diallyl maleate, trimethylolpropane triacrylate, allyl cinnamate, etc. . You may use these individually or in combination of 2 or more types. The content (use amount) of the crosslinkable monomer is 0.1% by mass to 1 in the elastic copolymer (a-1).
It is preferably 0% by mass.

As the monomer constituting the elastic copolymer (a-1), other copolymerizable vinyl monomers can be used in addition to the above-mentioned monomers. As the other copolymerizable vinyl monomer, methyl methacrylate, butyl methacrylate, alkyl methacrylate such as cyclohexyl methacrylate, styrene, acrylonitrile and the like are preferable, and these are used alone or in combination of two or more kinds. May be. The content (use amount) of such a vinyl monomer is preferably 64.9% by mass or less.

The elastic copolymer (a-1) may have a structure of one layer or two or more layers as described above. When the structure has two or more layers, the content of the acrylic acid alkyl ester and the content of the crosslinkable monomer as the whole of the elastic copolymer (a-1) may be within the ranges described above. Also,
When a hard core structure is used, the content of the alkyl acrylate in the first layer (innermost layer) is preferably 35% by mass or less.

The hard polymer (a-2) is a rubber-containing polymer ((a-1) obtained by graft-polymerizing a monomer composition containing alkyl methacrylate as a main component to the elastic copolymer (a-1). It is the outer layer of A-1). The methacrylic acid alkyl ester is not particularly limited, but includes methyl methacrylate, ethyl methacrylate, butyl methacrylate,
It is preferable to use 2-ethylhexyl methacrylate, cyclohexyl methacrylate, or the like. The methacrylic acid alkyl ester may be used alone or in combination of two or more kinds. The content (usage) of the methacrylic acid alkyl ester is 50% by mass in the hard polymer (a-2).
The above is preferable.

As the monomer constituting the hard polymer (a-2), other copolymerizable vinyl monomers can be used in addition to the methacrylic acid alkyl ester. Other copolymerizable vinyl monomers are not particularly limited,
It is preferable to use alkyl acrylates such as methyl acrylate, butyl acrylate, cyclohexyl acrylate, styrene, acrylonitrile and the like. You may use these individually or in combination of 2 or more types. The content (use amount) of such a vinyl monomer is preferably 50% by mass or less in the hard polymer (a-2).

The hard polymer (a-2) may have a structure of one layer or two or more layers, like the elastic copolymer (a-1). When the structure has two or more layers, the content of the methacrylic acid alkyl ester as the whole hard polymer (a-2) may be 50% by mass or more.

In the rubber-containing polymer (A-1), the content of the hard polymer (a-2) is the elastic copolymer (a-1).
The amount is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more, relative to 100 parts by mass. Further, it is preferably 400 parts by mass or less, and more preferably 200 parts by mass or less with respect to 100 parts by mass of the elastic copolymer (a-1).

The particle size of the rubber-containing polymer (A-1) comprising the elastic copolymer (a-1) and the hard polymer (a-2) is preferably 0.01 μm or more, and particularly the film-forming property. From the viewpoint, it is preferably 0.08 μm or more. The upper limit is preferably 0.5 μm or less,
In particular, it is preferably 0.3 μm or less.

The thermoplastic polymer (A-2) contained in the acrylic resin component (A) is obtained by polymerizing a monomer composition containing alkyl methacrylate as a main component and is a known substance. Can be used. The methacrylic acid alkyl ester is not particularly limited, and known ones can be used, but methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like are preferable, and methyl methacrylate is particularly preferable. The methacrylic acid alkyl ester may be used alone or in combination of two or more kinds. The content (use amount) of the methacrylic acid alkyl ester is 50% by mass in the thermoplastic polymer (A-2).
It is preferably ˜99.9% by mass.

In addition to the methacrylic acid alkyl ester, an acrylic acid alkyl ester can be used as the monomer constituting the thermoplastic polymer (A-2). The alkyl acrylate is not particularly limited, but methyl acrylate, ethyl acrylate, butyl acrylate, etc. are preferably used. The acrylic acid alkyl ester may be used alone or in combination of two or more kinds. Further, the content (use amount) of the acrylic acid alkyl ester is preferably 0.1% by mass to 50% by mass in the thermoplastic polymer (A-2).

In addition to the above-mentioned monomers, other copolymerizable vinyl monomers can be used as the monomer constituting the thermoplastic polymer (A-2). Such other copolymerizable vinyl monomers include aromatic vinyl compounds such as styrene, vinyl cyanide monomers such as acrylonitrile, and unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride. , N-phenylmaleimide, N-cyclohexylmaleimide and the like are preferable, and these may be used alone or in combination of two or more kinds. The content (use amount) of such a vinyl monomer is the thermoplastic polymer (A
In 2), it is preferably 49.9 mass% or less.

The reduced viscosity of the thermoplastic polymer (A-2) is
It is preferable that the content of the film raw material resin is 0.1 L / g or less because the film raw material resin is appropriately stretched and the film forming property is improved. As it is hard to wake up,
It is preferably 0.05 L / g or more.

An example of the method for producing the acrylic resin component (A) is shown below. As the method for producing the rubber-containing polymer (A-1), first, the elastic copolymer (a-1) is prepared. Examples of the method for preparing the elastic copolymer (a-1) include known emulsion polymerization methods. As described above, the elastic copolymer (a
-1) may have a multilayer structure of two or more layers. In that case, the monomer composition to be the inner layer is sequentially added and polymerized, and after the polymerization is completed, a single amount to be the next layer is formed. A latex containing the elastic copolymer (a-1) can be obtained by adding and polymerizing the body composition. Then, in the presence of the elastic copolymer (a-1), the monomer composition constituting the hard polymer (a-2) is graft-polymerized. Emulsion polymerization is mentioned as a polymerization method. In this case as well, polymerization can be carried out in multiple stages to obtain a hard polymer (a-2) having a multilayer structure.

The polymerization temperature varies depending on the kind and amount of the polymerization initiator, but is preferably 40 ° C. or higher, particularly preferably 60 ° C. or higher. The upper limit is preferably 120 ° C. or lower, and particularly 9
It is preferably 5 ° C or lower.

As the polymerization initiator, known ones can be used, and the addition method thereof may be addition to either or both of the aqueous phase and the monomer phase.

As the emulsifier, anionic, cationic or nonionic surfactants can be used, but anionic surfactants are particularly preferable. Examples of the anionic surfactant include potassium oleate, sodium stearate, sodium myristate, sodium N-lauroyl sarcosinate, dipotassium alkenyl succinate and the like, sulfate ester salts such as sodium lauryl sulfate and dioctyl sulfosuccinate. Examples thereof include sulfonates such as sodium acid salt, sodium dodecylbenzenesulfonate, sodium alkyldiphenyl ether disulfonate, and phosphate ester salts such as sodium polyoxyethylene alkylphenyl ether phosphate. The addition amount of the emulsifier may be appropriately determined according to the polymerization conditions.

The polymer latex obtained by the emulsion polymerization method is preferably filtered through a filter having an opening of 100 μm or less, and then acid coagulation method, salt coagulation method, freeze coagulation method,
It is solidified by a known solidification method such as a spray drying method. As 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, and as the salt coagulation method, inorganic salts such as sodium sulfate, magnesium sulfate, aluminum sulfate and calcium chloride. Organic salts such as calcium acetate and magnesium acetate can be used. The coagulated polymer is further washed, dehydrated and dried to obtain a powdery rubber-containing polymer (A-1).

The method for producing the thermoplastic polymer (A-2) is not particularly limited, and the usual methods such as suspension polymerization, emulsion polymerization and bulk polymerization can be used for polymerization. In addition, a chain transfer agent or other polymerization aid may be used during the polymerization. Although various kinds of chain transfer agents can be used, mercaptans are particularly preferable. The rubber-containing polymer (A-1) thus obtained
And the thermoplastic polymer (A-2) can be mixed to obtain the acrylic resin component (A).

(Acrylic resin component (B)) The acrylic resin component (B) is the innermost polymer (B-) in order from the inside.
1), a crosslinked elastic polymer (B-2) layer, and an outermost polymer (B-3) layer, and further a crosslinked elastic polymer (B-2).
Between the layer and the outermost polymer (B-3) layer, the intermediate polymer (B
-4) A multi-layered polymer having four or more layers, which has at least one layer.

The innermost polymer (B-1) is an acrylic acid alkyl ester having 80 to 100% by mass of an alkyl group having 1 to 8 carbon atoms and / or an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms. 0 to 20% by mass of an ester and a monomer having a copolymerizable double bond, and 0 to 1
It can be obtained by polymerizing a monomer composition containing 0.1 to 5 parts by mass of a graft crossing agent, based on 100 parts by mass of a total of 0% by mass of a polyfunctional monomer.

1 carbon atom constituting the innermost polymer (B-1)
The alkyl acrylate having an alkyl group of ~ 8 is not particularly limited, but methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, etc. may be used. It is preferable to use one having a low glass transition temperature (Tg). Also,
The methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is not particularly limited, but methyl methacrylate, ethyl methacrylate, propyl methacrylate,
It is preferable to use butyl methacrylate or the like. These acrylic acid alkyl esters and methacrylic acid alkyl esters may be used alone or in combination of two or more kinds.

These (meth) acrylic acid alkyl esters include innermost polymer (B-1), crosslinked elastic polymer (B-2), outermost polymer (B-3) and intermediate polymer ( B-
It is preferable to use the same layer 4), but it is possible to mix two or more kinds of monomers or to use another kind of (meth) acrylic acid alkyl ester depending on the final purpose.

The monomer having a double bond capable of copolymerization is not particularly limited, but higher alkyl esters of acrylic acid, lower alkoxy esters of acrylic acid, cyanoethyl esters of acrylic acid, acrylamide, acrylic acid,
It is preferable to use an acrylic monomer such as methacrylic acid. In addition, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile and the like can be used.
These monomers having a copolymerizable double bond may be used alone or in combination of two or more kinds.

The polyfunctional monomer is not particularly limited, but ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, dimethacrylate 1,4.
-It is preferable to use an alkylene glycol ester of dimethacrylic acid such as butylene glycol or propylene glycol dimethacrylate, and polyvinylbenzene such as divinylbenzene or trivinylbenzene or an alkylene glycol ester of diacrylic acid can also be used. These polyfunctional monomers may be used alone or in combination of two or more kinds. These polyfunctional monomers work effectively for bridging the layer in which they are contained and do not act for bonding between other layers. Even if the polyfunctional monomer is not used at all, as long as the graft crossing agent is present, a very stable multi-layer structure can be formed, but if the hot strength is strictly required, its addition purpose It is arbitrarily used depending on the situation.

As the graft crossing agent, a copolymerizable α,
Examples include allyl, methallyl or crotyl esters of β-unsaturated carboxylic acids or dicarboxylic acids. Among these, allyl esters of acrylic acid, methacrylic acid, maleic acid or fumaric acid, especially allyl methacrylate, have excellent effects. preferable. In addition, triallyl cyanurate and triallyl isocyanurate are also effective.
In such a graft crossing agent, mainly the conjugated unsaturated bond of the ester reacts much faster than the allyl group, the methallyl group or the crotyl group, and chemically bonds. On the other hand, most of the allyl group, methallyl group, or crotyl group substantially works effectively during the polymerization of the polymer for the next layer and gives a graft bond between the adjacent two layers.

The amount of the graft crossing agent used is extremely important and a sufficient amount of the graft bond can be obtained. Therefore, the total amount of the monomers constituting the innermost polymer (B-1) is 100 parts by mass. The amount is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more. The amount of the graft crossing agent used is the crosslinked elastic polymer (B-
2) in that the amount of reaction with the polymer does not become too large, and the elasticity of the polymer formed from the innermost polymer (B-1) and the crosslinked elastic polymer (B-2) layer is sufficiently obtained. Innermost polymer (B
It is preferably 5 parts by mass or less, more preferably 2 parts by mass or less, based on 100 parts by mass of the total amount of the monomers constituting -1).

The content of the innermost polymer (B-1) is
It is preferably 5% by mass to 35% by mass in the acrylic resin component (B), and more preferably 15% by mass or less. Further, the content of the innermost polymer (B-1) is preferably smaller than the content of the crosslinked elastic polymer (B-2).

The crosslinked elastic polymer (B-2) layer is a main component which imparts rubber elasticity to the polymer having a multilayer structure,
The composition is 80 to 100% by mass of 1 to 8 carbon atoms.
An acrylic acid alkyl ester having an alkyl group of
Graft of 0.1 to 5 parts by mass based on 100 parts by mass of 0 to 20% by mass of a monomer having a copolymerizable double bond and 0 to 10% by mass of a polyfunctional monomer. It is obtained by polymerizing a monomer composition containing a crossing agent.

An alkyl acrylate ester having an alkyl group having 1 to 8 carbon atoms which constitutes the crosslinked elastic polymer (B-2), a monomer having a double bond capable of copolymerization, a polyfunctional monomer, As specific examples of the graft crossing agent, the same ones as those used for the innermost polymer (B-1) described above are applied.

The content of the crosslinked elastic polymer (B-2) is preferably 10% by mass to 45% by mass in the acrylic resin component (B). In addition, the innermost polymer (B-1)
Is preferably higher than the content of.

The outermost polymer (B-3) imparts film-forming property and moldability to the acrylic resin component (B), and has a constitution of 51-100% by mass and 1 to 4 carbon atoms. A methacrylic acid alkyl ester having an alkyl group of
It is obtained by polymerizing a monomer composition containing ˜49% by mass of a monomer having a copolymerizable double bond.

1 carbon atom constituting the outermost polymer (B-3)
Specific examples of the methacrylic acid alkyl ester having an alkyl group of 4 to 4 and the monomer having a copolymerizable double bond are the same as those used for the innermost polymer (B-1) described above. Is applied.

The content of the outermost polymer (B-3) is
The content in the acrylic resin component (B) is preferably 10% by mass or more, more preferably 40% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 60% by mass or less.

Intermediate polymer (B-4) provided between the crosslinked elastic polymer (B-2) layer and the outermost polymer (B-3) layer.
The layer comprises 10 to 90% by mass of an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms, 90 to 10% by mass of an methacrylic acid alkyl ester having an alkyl group of 1 to 4 carbon atoms, and 0 to 20. 0.1 to 5 parts by weight of a graft crossing agent is added to 100 parts by weight of a total of 100% by weight of a monomer having a copolymerizable double bond and 0 to 10% by weight of a polyfunctional monomer. It is obtained by polymerizing the containing monomer composition. The content of the acrylic acid alkyl ester is from the crosslinked elastic polymer (B-2) layer to the outermost polymer (B-2).
-3) It monotonically decreases toward the layer. That is, the content (% by mass) of the acrylic acid alkyl ester in the intermediate polymer (B-4) layer is the same as the content of the acrylic acid alkyl ester in the crosslinked elastic polymer (B-2) layer and the outermost weight. Coalescence (B
-3) between the content of the alkyl acrylate in the layer. The intermediate polymer (B-4) layer may be a single layer or a multi-layer. In the case of a multi-layer, all the layers constituting the intermediate polymer (B-4) layer are alkyl as a whole. The content of acid acrylic ester is controlled as described above.

An acrylic acid alkyl ester having a C1-8 alkyl group constituting the intermediate polymer (B-4) layer, a methacrylic acid alkyl ester having a C1-4 alkyl group, a copolymerizable diester Specific examples of the monomer having a heavy bond, the polyfunctional monomer, and the graft crossing agent are the same as those used for the innermost polymer (B-1) described above.

As described above, the amount of the graft crossing agent used is 0.1 to 5 parts by mass based on 100 parts by mass of the total amount of the monomer composition constituting the intermediate polymer (B-4) layer. It is preferably part. The graft crossing agent used in the intermediate polymer (B-4) layer is essential for closely bonding the polymer layers and obtaining excellent properties.

The content of the intermediate polymer (B-4) layer is 5 in the acrylic resin component (B) in that the function as the intermediate polymer layer is sufficiently obtained and the final polymer is well balanced.
It is preferably from mass% to 35 mass%.

As a method for producing the acrylic resin component (B), a sequential multistage polymerization method by emulsion polymerization is the most suitable polymerization method, but it is not particularly limited, and, for example, after emulsion polymerization, It can also be carried out by emulsion suspension polymerization or the like, in which the outer polymer (B-3) is converted into a suspension polymerization system during polymerization.

The polymer latex obtained by the emulsion polymerization method is preferably filtered through a filter having an opening of 100 μm or less, and then acid coagulation method, salt coagulation method, freeze coagulation method,
It is solidified by a known solidification method such as a spray drying method. As 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, and as the salt coagulation method, inorganic salts such as sodium sulfate, magnesium sulfate, aluminum sulfate and calcium chloride. Organic salts such as calcium acetate and magnesium acetate can be used. The coagulated polymer is further washed, dehydrated and dried to obtain a powdery acrylic resin component (B).

(Acrylic resin composition) The acrylic resin composition is prepared by adding 0.1 to 40 parts by mass of a matting agent to 100 parts by mass of the above-mentioned acrylic resin component (A) or acrylic resin component (B). Can be obtained. By containing the matting agent in such a range, it is possible to reduce the matt finish of the acrylic resin film (I) due to heat during the secondary molding process.

As the matting agent, known ones can be used regardless of organic type or inorganic type, but from the viewpoint of matting property, film forming property and moldability, it is preferable to use a polymer having a hydroxyl group. preferable. When a polymer having a hydroxyl group is used as a matting agent, the physical properties such as the elongation of the film are hardly deteriorated, so it can be used well even in in-mold molding, which requires vacuum molding of the film in advance, without causing the film to break. it can. Further, an acrylic resin film (I) having a very low surface gloss can be formed, and as a result, a laminate having a high matte property can be obtained.

The polymer having a hydroxyl group is, for example, 1 to
80 mass% acrylic acid hydroxyalkyl ester and / or methacrylic acid hydroxyalkyl ester, 10-99 mass% methacrylic acid alkyl ester, and 0-79 mass% acrylic acid alkyl ester,
It is obtained by polymerizing a monomer composition with 0 to 50 mass% of another copolymerizable vinyl monomer.

Examples of hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, 2-hydroxyethyl acrylate, and acrylic acid. Examples thereof include 4-hydroxybutyl acid, and of these, 2-hydroxyethyl methacrylate is preferable. You may use these individually or in combination of 2 or more types. The amount of acrylic acid hydroxyalkyl ester and / or methacrylic acid hydroxyalkyl ester used is preferably 1% by mass or more in the polymer having a hydroxyl group, since a sufficient matting effect can be obtained.
It is more preferably 5% by mass or more, still more preferably 20% by mass or more. Further, when a polymer having a hydroxyl group is used as a matting agent, the dispersibility of the particles becomes good,
The amount is preferably 80% by mass or less, more preferably 50% by mass or less, since the film-forming property of the film will be good.

On the other hand, when there is a possibility that an fragrance, a hair styling agent, etc. may adhere, for example, in vehicle interior applications, the interior members are generally required to have chemical resistance. In order to develop resistance to these chemicals in the film, the amount of the (meth) acrylic acid hydroxyalkyl ester used is preferably 5 to 25% by mass. Further, from the viewpoint of achieving both matte properties and chemical resistance, 10 to 20 mass% is particularly preferable.

There is no particular limitation on the methacrylic acid alkyl ester constituting the above-mentioned polymer having a hydroxyl group, but lower methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate and butyl methacrylate are preferred, and among these, methyl methacrylate is preferred. Is preferred. You may use these individually or in combination of 2 or more types. The amount of methacrylic acid alkyl ester used is
10 mass% or more is preferable, and more preferably 30 mass%
That is all. The upper limit is preferably 99% by mass or less, more preferably 90% by mass or less.

Although the alkyl acrylate ester constituting the above-mentioned polymer having a hydroxyl group is not particularly limited,
Lower acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate are preferred. You may use these individually or in combination of 2 or more types. When an acrylic acid alkyl ester is used, its amount is preferably 0.5% by mass or more, more preferably 5% by mass or more. The upper limit is preferably 79% by mass or less, more preferably 40% by mass or less, and further preferably 25% by mass or less. On the other hand, from the viewpoint of chemical resistance, the hydroxyl group-containing polymer preferably has a glass transition temperature of 80 ° C. or higher, more preferably 90 ° C. or higher. In this case, it is necessary to use the acrylic acid alkyl ester in an amount of 5% by mass or less, preferably 2% by mass or less.

Other copolymerizable vinyl monomers constituting the polymer having a hydroxyl group are not particularly limited, but aromatic vinyl type monomers, vinyl cyanide type monomers and the like are preferable. You may use these individually or in combination of 2 or more types. The amount of the other copolymerizable vinyl monomer used is preferably 50% by mass or less.

The polymer having a hydroxyl group having the above-mentioned constitution has an intrinsic viscosity, from the viewpoint of matte expression and appearance.
It is preferably 0.05 L / g to 0.3 L / g.
More preferably, it is in the range of 0.06 to 0.15 L / g.

The method for producing the polymer having a hydroxyl group is not particularly limited, but a method by suspension polymerization or emulsion polymerization is preferable. For example, in the case of suspension polymerization, the monomer is aqueous-suspended with a polymerization initiator in the presence of a suspension stabilizer. In addition to this, it is also possible to dissolve a polymer that is soluble in the monomer.

As the suspension stabilizer, a commonly used known one is used, and examples thereof include organic colloidal polymer substances, inorganic colloidal polymer substances, inorganic fine particles, and
A combination of these and a surfactant can be mentioned. Examples of the suspension polymerization initiator include those used in ordinary suspension polymerization, for example, an organic peroxide,
Azo compounds and the like.

When preparing a polymer having a hydroxyl group, it is preferable to use a polymerization regulator such as mercaptan for controlling the molecular weight. As the mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and the like are used, but known mercaptans are not particularly limited thereto.

The amount of the matting agent blended is 0. 0 based on 100 parts by mass of the acrylic resin component (A) or the acrylic resin component (B), because a sufficient matting effect is exhibited and good matting properties are obtained. It is preferably 1 part by mass to 40 parts by mass,
It is more preferably 2 to 40 parts by mass.

When a polymer containing a hydroxyl group is used, it is preferable that the phosphorus compound is blended in a proportion of 0.01 to 3 mass% in the blending amount of the matting agent from the viewpoint of matting property. The matting property becomes good with an addition amount of 0.01% by mass or more, and an addition amount of 3% by mass or less is preferable from the economical viewpoint. More preferably, it is in the range of 0.1 to 1% by mass.

Examples of the phosphorus compounds include known phosphite compounds such as alkyl phosphite, alkylaryl phosphite, aryl phosphite, nonylphenyl phosphite, alkylnonyl phenyl phosphite, trialkyl phosphates and tripolyoxyethylene. Well-known phosphate compounds such as alkyl ether phosphates, dialkyl phosphates and metal salts thereof, dipolyoxyethylene alkyl ether phosphates and metal salts thereof, alkyl phosphates and metal salts thereof, polyoxyethylene alkyl ether phosphates and metal salts thereof, and dialkyl Alkyl phosphonate,
Examples thereof include phosphonate compounds such as alkylalkylphosphonates and metal salts thereof. Among these, phosphite compounds are preferable from the viewpoint of matte expression.
Further, among the phosphite-based compounds, those having no bulky substituents around the phosphite group are more preferable from the viewpoint of matte expression.

The acrylic resin composition containing such a matting agent preferably further contains a specific thermoplastic resin component from the viewpoint of film-forming property, particularly high level of thickness accuracy and film-forming speed, As such a thermoplastic resin component, methyl methacrylate 50 to 100% by mass and at least one vinyl monomer 0 to 5 copolymerizable therewith
Those obtained by polymerizing 0% by mass are preferable.

The vinyl monomer copolymerizable with methyl methacrylate constituting the thermoplastic resin component is not particularly limited, and examples thereof include acrylic acid acrylic ester, methacrylic acid alkyl ester, aromatic vinyl compound, vinyl cyanide compound and the like. Can be used. You may use these individually or in combination of 2 or more types. Further, the content (use amount) of methyl methacrylate in the thermoplastic resin component is preferably 50% by mass or more.

The thermoplastic resin component has a reduced viscosity (0.1 g of the thermoplastic resin component is added to 100 ml of chloroform).
And is measured at 25 ° C.) is 0.2 L / g or more. The upper limit of the reduced viscosity is preferably 2 L / g or less, more preferably 1.2 L / g.
It is the following.

The amount of the thermoplastic resin component used is 0.1 per 100 parts by mass of the acrylic resin component (A) or the acrylic resin component (B), because the effect of improving the film-forming property is sufficiently obtained.
It is preferable that the amount is at least parts by mass. Further, since the viscosity of the acrylic resin composition becomes appropriate and a good film-forming property can be obtained, it is 20 parts by mass or less relative to 100 parts by mass of the acrylic resin component (A) or the acrylic resin component (B). preferable.

As a method for preparing the thermoplastic resin component, a method by emulsion polymerization is preferable. The polymer latex produced by a known emulsion polymerization method can be separated and recovered by various coagulants, or the solid content can be separated and recovered by spray drying to obtain a powdery thermoplastic resin component.

In the acrylic resin composition used in the present invention, if necessary, general compounding agents such as stabilizers, lubricants, processing aids, plasticizers, impact resistance aids, foaming agents, fillers,
You may contain a coloring agent, a ultraviolet absorber, a light diffusing material, etc. Particularly, from the viewpoint of protecting the substrate, it is preferable to add an ultraviolet absorber in order to impart weather resistance. The molecular weight of the ultraviolet absorber is preferably 300 or more, and particularly preferably 400 or more, since it hardly volatilizes during vacuum molding or pressure molding in the injection molding die, and mold stains do not occur much. The type of the ultraviolet absorber is not particularly limited, but a benzotriazole type having a molecular weight of 400 or more or a triazine type having a molecular weight of 400 or more is preferable.
Specific examples of the benzotriazole type include Tinuvin 234 manufactured by Ciba-Geigy and ADEKA STAB LA manufactured by Asahi Denka Co., Ltd.
-31 and the like, and specific examples of the triazine-based compound include
Tinubin 1577 manufactured by Ciba Geigy and the like can be mentioned.

The acrylic resin composition having the above constitution is
The content of gel insoluble in chloroform is preferably 5% by mass to 75% by mass, and particularly preferably 10% by mass to 60% by mass. When the gel content is in such a range, the acrylic resin film (I) does not become brittle, an appropriate melt tension is obtained at the time of film formation, and the film formability becomes good.
Further, in order to obtain the gel content in such a range, the content of the rubber-containing polymer in the acrylic resin composition may be substantially adjusted to an appropriate range (5% by mass or more).

(Acrylic Resin Film (I)) The acrylic resin film (I) used in the present invention is important in the value of the surface glossiness, and it is necessary that the 60 ° surface glossiness is 50% or less. Is. When it is 50% or less, the laminated film or sheet as a substitute for painting sufficiently exhibits a high-class feeling and a calm feeling. The 60 ° surface gloss of the acrylic resin film (I) is particularly preferably 30% or less.

Such an acrylic resin film (I)
Can be preferably produced using the above-mentioned acrylic resin composition by various methods such as a T-die method, a melt extrusion method such as an inflation method, and a calender method. Among these, the T-die method is preferable in terms of film thickness accuracy and productivity.

As a method for producing an acrylic resin film (I) having a 60 ° surface gloss of 50% or less without using a matting agent, an acrylic resin is formed into a film by a melt extrusion method such as a T-die method. A method of sandwiching between the mirror roll and the rubber roll or the embossed roll, particularly a method of sandwiching between the mirror roll and the rubber roll when cooled by the mirror roll after forming the shape is preferable. The method of sandwiching between the mirror surface roll and the rubber roll makes it possible to manufacture a relatively thin film having a film thickness of about 50 μm, as compared with the method of sandwiching between the mirror surface roll and the textured roll. Further, in the calendering method, the film can be formed by replacing one of the two mirror-finished rolls with which the film is finally sandwiched with a rubber roll or a textured roll. As the mirror surface roll, a well-known roll can be used, but the surface roughness after chrome plating is 0.
Rolls of 5S or less are preferred. Known rubber rolls can be used as the rubber roll, but silicone rubber is preferable from the viewpoint of heat resistance. Further, in order to obtain good matting properties, sand-containing silicone rubber is preferable. Since the preferred matte appearance differs depending on the application in the acrylic resin film, the particle size and amount of sand added to the silicone rubber may be appropriately determined according to the application. For example, an average particle size of 4
50 μm of sand of 0 μm for 100 parts by mass of silicone rubber
It is possible to use a silicone rubber roll that has been added by mass. A textured roll may be used instead of the rubber roll. A known roll can be used as the embossed roll.

Generally, the acrylic resin film is
Since the surface irregularities are likely to disappear due to heat, pressure, etc., when the acrylic resin film (I) is secondarily processed into a laminated film or sheet for painting substitute, and further to a laminated body having this, glossiness occurs. Often. Therefore, in order to make it look like a real metal even after being processed into a laminated film or sheet for paint substitute or a laminated body having the same, the 60 ° surface gloss is 20% or less. Especially, it is preferable to use acrylic resin film (I) of 10% or less.

Furthermore, it is more preferable to use an acrylic resin film (I) whose 60 ° surface gloss on one film surface becomes 50% or less when heated at 120 ° C. for 48 hours, It is preferably 20% or less, more preferably 10% or less. In order to obtain such an acrylic resin film (I), it is effective to add the above-mentioned polymer containing a hydroxyl group as a matting agent.

Further, when compared among acrylic resin films having the same degree of surface gloss, the higher the heat deformation temperature of the acrylic resin film, the less the gloss-reducing property during insert molding or in-mold molding. Therefore, a higher heat distortion temperature is more advantageous from the viewpoint of glossiness upon insert molding or in-mold molding. The heat distortion temperature is preferably in the range of 85 ° C. to 105 ° C. from the viewpoints of peelability from a mirror surface roll described below, followability to a rubber roll or a textured roll (embossing roll), and luster recovery at the time of molding. It is preferably in the range of 90 to 100 ° C.

The thickness of the acrylic resin film (I) is not particularly limited, but is preferably 50 μm to 300 μm. The thickness of acrylic resin film (I) is 5
When it is 0 μm or more, a sufficient depth can be obtained as a molded product appearance. In addition, when forming into a particularly complicated shape, a sufficient thickness can be obtained by stretching. On the other hand, when the thickness of the acrylic resin film (I) is 300 μm or less, the rigidity becomes appropriate, so that the laminating property and the secondary processability are improved. Further, it is economically advantageous in terms of weight per unit area. Furthermore, the film-forming property is stable, and the film can be easily manufactured.

(Decorative layer (II)) The decorative layer (II) used in the coating substitute laminate film of the present invention is formed on a thermoplastic resin film or sheet (III) described later. As described above, by forming the decorative layer (II) on the thermoplastic resin film or sheet (III), even if the acrylic resin film (I) has a fish eye that causes printing omission, The number of appearance defects is 10
The number can be less than or equal to / m ² . The number of appearance defects is 1
It is necessary that the number is 0 pieces / m ² or less from the viewpoint of designability and decorating property, and the appearance of the obtained coating substitute laminate film or sheet, or a laminate including the same will be good.
The number of appearance defects is preferably 5 / m ² or less, particularly preferably 1 / m ² or less.

Here, in the case of the decorative layer (II) being a printed layer formed by printing, the appearance defect is a dropout that occurs because the printed layer is not transferred to the protrusions or dents on the printed surface. If the decorative layer (II) is a metal layer formed of a metal, the metal layer is not laminated in close contact with the protrusions or dents on the surface to be printed. Refers to the visible part.

As the decorative layer (II), a known layer can be used, but a printed layer or a metal layer, particularly a metallic print layer or a metal layer is preferable. The thickness of the decorative layer (II) may be appropriately determined as needed, but is usually about 0.5 to 30 μm.

When the decorative layer (II) is a metallic print layer or a metallic layer, the coating substitute laminated film or sheet looks like a carved metal surface, and has an appearance of high quality and calmness. To obtain a metal-tone film or sheet. In such a metal-like paint substitute laminate film or sheet, the 60 ° surface gloss of the acrylic resin film (I) formed on the decorative layer (II) becomes more important. The lower the surface gloss, the more the appearance of the paint substitute laminate film or sheet tends to look like a carved metal surface. Therefore, even though it is a plastic, it looks as if it were a real metal, increasing its industrial utility value.

The printing layer is formed on the thermoplastic resin film or sheet (III) by a known printing method such as a gravure printing method, a flexographic printing method and a silk screen printing method. For example, a thermoplastic resin film or sheet (II
A metallic print pattern can be formed by printing an arbitrary pattern such as wood grain on I) or using an ink prepared by mixing an aluminum paste.

The metal layer is made of aluminum, chromium, gold,
It is formed on the thermoplastic resin film or sheet (III) by a method such as a vacuum deposition method, a sputtering method or a wet plating method using a metal such as silver, copper, nickel, cobalt, zinc, brass or stainless steel. It is also possible to use a metal foil-like material via an adhesive layer or laminated by heat fusion or the like.

(Thermoplastic resin film or sheet (II
I)) Thermoplastic resin film or sheet (III) is not particularly limited, and a film or sheet using a known thermoplastic resin can be used. For example, acrylic resin, AB
S resin (acrylonitrile-butadiene-styrene resin), AS resin (acrylonitrile-styrene resin),
PVC resin (polyvinyl chloride resin), polystyrene resin, polycarbonate resin, polyester resin, polyolefin resin and the like. Among these, acrylic resin, ABS resin, PVC resin, and polyolefin resin are preferable in view of printability and secondary formability of a laminated film or sheet for coating substitute.

Further, in addition to the above-mentioned thermoplastic resin, general compounding agents such as stabilizers, lubricants, processing aids, plasticizers, impact resistance aids, colorants, and ultraviolet absorbers can be contained. .

Thermoplastic resin film or sheet (III)
Can be produced by a known method, but if the surface smoothness is good, it is possible to further reduce appearance defects such as printing defects when the decorative layer (II) is formed on the surface, so that the polishing roll should be used. A melt extrusion method and a calendar method are preferable. Further, in order to reduce fish eyes that cause appearance defects such as print omissions, it is preferable to extrude while removing foreign matters with a screen mesh of 200 mesh or more during melt extrusion. The thickness of the thermoplastic resin film or sheet (III) may be appropriately determined as needed, but is usually about 20 to 500 μm.

(Layered Film or Sheet for Coating Substitution) The laminated film or sheet for coating substitution in the example of FIG. 1 has 10 or less appearance defects per 1 m ² on the thermoplastic resin film or sheet (III). Form the decorative layer (II),
Then, an acrylic resin film (I) is laminated as a protective layer on the decorative layer (II). Thus, by forming the decorative layer (II) on the thermoplastic resin film or sheet (III), it becomes a coating substitute laminated film or sheet having a decorative layer of good appearance with few appearance defects and the like. .

An example of the method for producing the laminated film or sheet for coating alternative of the present invention will be described below. First, the decorative layer (II) formed by printing or the like is formed on the thermoplastic resin film or sheet (III) to obtain a laminated film or sheet. Then, the acrylic resin film (I) is laminated on the laminated film or sheet. Examples of the method for laminating include known methods such as thermal lamination and dry lamination. At this time, it is preferable to laminate the acrylic resin film (I) through a grained roll from the viewpoint of matt finish. Further, the acrylic resin film (I) can be directly laminated on the laminated film or sheet composed of the thermoplastic resin film or sheet (III) and the decorative layer (II) by extrusion lamination. In this case also, it is preferable to use a grained roll.

On the other hand, when heat is applied during secondary processing such as in-mold molding or insert molding, an acrylic resin film (I) having a 60 ° surface gloss of 50% or less is used as a thermoplastic resin film or sheet (III). ) And decorative layer (II)
When laminating on a laminated film or sheet consisting of (1) and (2), it is not always necessary to use a grained roll. In this case, the lamination can be carried out by a known method, but for example, it can be sandwiched between two polishing rolls under heating conditions or sandwiched between metal belts for lamination. The 60 ° surface gloss of the acrylic resin film (I) side of the laminated film or sheet for coating substitute laminated in this way may be 50% or more. The heat received during the secondary processing makes it possible to develop matte properties again. In particular, when sandwiched between two polishing rolls or sandwiched between metal belts for lamination, not only the 60 ° surface gloss of the acrylic resin film (I) is 50% or less, but also An acrylic resin film having a 60 ° surface gloss of 50% or less on one film surface when heated at 120 ° C. for 48 hours is preferable. The surface glossiness after heating is more preferably 20% or less, and most preferably 10% or less. Using such an acrylic resin film (I), sandwiching it between two polishing rolls, or sandwiching it between metal belts and laminating it for use as a coating substitute laminate film or sheet, insert molding or Molding improves the mattness after molding and increases the industrial utility value.

The laminated film or sheet as a substitute for coating produced in this manner does not have a shiny appearance, and has a high-grade feeling, a deep feeling, and a calm feeling. Further, since the number of appearance defects of the decorative layer (II) is 10 or less per 1 m ² and the occurrence of print omission is suppressed, the yield is not reduced.

Further, as a laminated film or sheet for coating substitution, as shown in FIG. 2, after the colored layer (IV) is formed on the decorative layer (II), the acrylic resin film (I) is formed.
May be laminated. Especially when a metallic print layer or metal layer is used as the decorative layer (II), the colored layer (IV)
By providing, it is possible to obtain a metallic appearance having various hues such as silver metallic, gold metallic, and blue metallic, which is preferable. In addition,
Although not shown, from the viewpoint of the decorativeness of the finally obtained coating substitute laminated film or sheet, a colored layer (I) is provided between the decorative layer (II) and the thermoplastic resin film or sheet (III).
V) can also be formed. The thickness of the colored layer (IV) may be appropriately determined as needed, but is usually about 1 to 100 μm.

The colored layer (IV) can be formed by a method similar to the method for forming the decorative layer (II), such as a gravure printing method, a flexographic printing method and a silk screen printing method. Further, a transparent colored film obtained by adding a dye or a pigment to a transparent material typified by acrylic resin can be used as the colored layer (IV). The transparent colored film can be laminated with an adhesive or heat fusion.

(Laminate Having Coating Alternative Laminated Film or Sheet) The laminate having a coating alternative laminate film or sheet is such that the acrylic resin film (I) of the coating alternative laminate film or sheet is the outermost layer. , A resin laminated on a base material, that is, the thermoplastic resin film or sheet (III) surface and the base material are bonded directly or via an adhesive, and the 60 ° surface glossiness thereof Is preferably 50% or less, more preferably 30% or less.

The base material of the laminate may be metal, wood or the like, but resin is particularly preferable. The resin is not particularly limited, and examples thereof include an acrylic resin, an ABS resin, an AS resin, a PVC resin, a polystyrene resin, a polycarbonate resin, a polyester resin, a polyolefin resin, or a resin containing these as main components. Further, the resin as the base material is a thermoplastic resin film or sheet (II
It is preferable to use the same material as I).

The base material and the thermoplastic resin film or sheet (III) are bonded by heat fusion, or in the case of a base material that is not heat fusion bonded, an adhesive is used to form a laminate film or sheet for coating substitution. The base material can be bonded at the time of molding.

An example of the method for producing a laminated body of the present invention will be described below. For example, in the case of laminating a laminate film or sheet for coating substitution on a laminate having a two-dimensional shape, a known method such as thermal lamination can be used for a base material that can be heat-sealed. In addition, the base material that is not heat-sealed may be bonded with an adhesive.

When the laminated film or sheet as a coating substitute is laminated on the three-dimensional laminated body, a known molding method such as an insert molding method or an in-mold molding method can be used. Among these, the in-mold molding method is preferable from the viewpoint of productivity.

In the in-mold molding method, after heating the laminated film or sheet for coating alternative, vacuum molding is performed in a mold having a vacuuming function. After a three-dimensional shape is formed by vacuum molding, the laminated film or sheet for coating substitute and the resin as the base material are melt-integrated by injection molding to obtain a laminate having an acrylic resin film (I) layer on the surface layer. Obtainable. This method is preferable from the viewpoints of workability and economy because molding and injection molding of the laminated film or sheet for coating substitution can be performed in one step.

Further, it is preferable that the mold with which the acrylic resin film (I) is in contact during the vacuum forming is embossed. In this case, as compared with the case where the embossing treatment is not performed, luster reduction during in-mold molding is reduced.

The heating temperature is preferably not lower than the temperature at which the coating substitute laminate film or sheet is softened, and varies depending on the thermal properties of the coating substitute laminate film or sheet and the shape of the laminate, but is 70 ° C to 190 ° C. C. is preferred.

Industrial utility value (use) of the laminate of the present invention
As for, although not particularly limited, automobile interior parts such as a console box and a shift lever box,
It can also be used for vehicle exterior parts such as door mirrors, wheel covers, and cowlings for motorcycles, as well as members that have been conventionally provided with a matte coating such as home appliances, furniture, and building materials.

The laminate having the laminated film or sheet as a substitute for coating obtained by the present invention does not have a shiny appearance, and has a high-class feeling, a deep feeling, and a calm feeling. In addition, for example, in order to form a coating film having a sufficient thickness on a molded product by coating, it may be necessary to repeat coating several dozen times. By laminating a film or sheet, the acrylic resin film (I) becomes a coating film (protective layer), so that a thick coating film can be easily formed, excellent workability and economical efficiency, and industrially advantageous Is.

[0112]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the examples. In the examples, "part" means "part by mass" and "%" means "% by mass".

[Production of Rubber-Containing Polymer (A-1)] Under a nitrogen atmosphere, deionized water 244 was placed in a reaction vessel equipped with a reflux condenser.
To 80 ° C., 0.6 part of sodium formaldehyde sulfoxylate, and 0.00012 of ferrous sulfate.
Parts, disodium ethylenediaminetetraacetate 0.0003
22 parts of methyl methacrylate, 15 parts of butyl acrylate, 3 parts of styrene, 0.4 part of allyl methacrylate, 0.14 parts of 1,3-butylene glycol dimethacrylate, and t-butyl hydroperoxide. 0.18 part, 1.0 part of a partially neutralized product of a mixture of sodium hydroxide with 40% of mono (polyoxyethylene nonylphenyl ether) phosphoric acid and 60% of di (polyoxyethylene nonylphenyl ether) phosphoric acid 1/15 of the monomer mixture was charged and held for 15 minutes. After that, the rest was continuously added at an increasing rate of the monomer mixture with respect to water of 8% / hour. After that, the elastic copolymer (a-1) was held for 1 hour to partially polymerize the elastic copolymer (a-1). Subsequently, 0.6 part of sodium formaldehyde sulfoxylate was added to the latex, which was kept for 15 minutes and then kept under nitrogen atmosphere for 8 minutes.
While stirring at 0 ° C, 50 parts of butyl acrylate,
10 parts styrene, 0.4 parts allyl methacrylate, 1,
0.14 parts of 3-butylene glycol dimethacrylate,
Partial neutralization of a mixture of sodium hydroxide with 0.2 part of t-hexyl hydroperoxide, 40% of mono (polyoxyethylene nonylphenyl ether) phosphoric acid and 60% of di (polyoxyethylene nonylphenyl ether) phosphoric acid. 1.0 part of the monomer mixture was continuously added at an increase rate of 4% / hour of the monomer mixture with respect to water. afterwards,
Polymerization was carried out by holding for 2 hours to obtain a latex of an elastic copolymer (a-1) having a two-layer structure. Next, 0.4 part of sodium formaldehyde sulfoxylate was added to the elastic copolymer (a-1) latex, which was then held for 15 minutes, while stirring at 80 ° C. under a nitrogen atmosphere, while adding 57 parts of methyl methacrylate. Methyl acrylate 3.0 parts, n
A monomer mixture of 0.3 part of octyl mercaptan and 0.06 part of t-butyl hydroperoxide was continuously added at an increase rate of 10% / hour of the monomer mixture with respect to water. Then, hold for 1 hour to polymerize the hard polymer,
A rubber-containing polymer (A-1) latex was obtained. The particle diameter of the obtained rubber-containing polymer (A-1) was 0.28 μm. Open the rubber-containing polymer (A-1) latex 5
After filtering with a 0 μm filter, coagulation, aggregation and solidification reaction were carried out using calcium acetate, filtration, washing with water and drying to obtain a powdery rubber-containing polymer (A-1).

[Production of Polymer (1) Having Hydroxyl Group] In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, etc., 10 parts of methyl acrylate, 60 parts of methyl methacrylate, 30 parts of hydroxyethyl methacrylate, n-
Octyl mercaptan 0.15 part, lauryl peroxide 0.5 part, copolymer of methyl methacrylate / methacrylate / ethyl methacrylate sulfonate 0.05
Parts, sodium sulfate 0.5 part, and ion-exchanged water 250 parts were charged, and the inside of the container was sufficiently replaced with nitrogen gas, and then the above monomer mixture was heated to 75 ° C. with stirring, and in a nitrogen gas stream. Polymerization proceeded. After 2 hours, raise the temperature to 90 ° C,
Hold for another 45 minutes to complete the polymerization and dehydrate the beads,
It was dried to obtain a polymer (1) having a hydroxyl group. The polymer (1) having a hydroxyl group had an intrinsic viscosity of 0.069 L / g and a glass transition temperature of 77 ° C.

[Production of Polymer (2) Having Hydroxyl Group] 1.0 part of methyl acrylate, 79 parts of methyl methacrylate, 20 parts of hydroxyethyl methacrylate were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, and the like. Part, n
-Octyl mercaptan 0.14 parts, lauryl peroxide 0.5 parts, copolymer of methyl methacrylate / methacrylate / ethyl methacrylate sulfonate 0.0
After charging 5 parts, 0.5 part of sodium sulfate, and 250 parts of ion-exchanged water and thoroughly replacing the inside of the container with nitrogen gas, the above monomer mixture was heated to 75 ° C. with stirring and in a nitrogen gas stream. And proceeded with the polymerization. After 2 hours, the temperature was raised to 90 ° C., and the temperature was further maintained for 45 minutes to complete the polymerization, and the beads were dehydrated and dried to obtain a polymer (2) having a hydroxyl group. Polymer (2) having a hydroxyl group has an intrinsic viscosity of 0.076 L / g
Met. The glass transition temperature was 93 ° C.

[Production of Polymer (3) Having Hydroxyl Group] 1.0 part of methyl acrylate, 89 parts of methyl methacrylate, 10 parts of hydroxyethyl methacrylate were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, and the like. Part, n
-Octyl mercaptan 0.11 part, lauryl peroxide 0.5 part, copolymer of methyl methacrylate / methacrylate / ethyl methacrylate sulfonate 0.0
5 parts, 0.5 part of sodium sulfate, and 250 parts of ion-exchanged water were charged, the inside of the container was sufficiently replaced with nitrogen gas, and then heated to 75 ° C. with stirring, and the polymerization was advanced in a nitrogen gas stream. After 2 hours, the temperature was raised to 90 ° C. and maintained for 45 minutes to complete the polymerization, and the beads were dehydrated and dried to obtain a polymer (3) having a hydroxyl group. The polymer (3) having this hydroxyl group had an intrinsic viscosity of 0.09 L / g and a glass transition temperature of 98 ° C.

[Production of Thermoplastic Resin Component] A reaction vessel was charged with 200 parts of ion-exchanged water bubbled with nitrogen, and 1 part of potassium oleate and 0.
I prepared three copies. Then 40 parts of methyl methacrylate,
10 parts of butyl acrylate and 0.005 part of n-octyl mercaptan were charged and stirred at 65 ° C. for 3 hours under a nitrogen atmosphere to complete the polymerization. Subsequently, a monomer mixture consisting of 48 parts of methyl methacrylate and 2 parts of butyl acrylate was added dropwise over 2 hours, and after the completion of the addition, the mixture was maintained for 2 hours to complete the polymerization. The latex obtained is 0.25
% Sulfuric acid aqueous solution, and after acid coagulation, dehydration, water washing, and drying were performed to recover a powdery thermoplastic resin component. The reduced viscosity ηsp / c of the obtained thermoplastic resin component is 0.38 L /
It was g.

Example 1 Production of Acrylic Resin Film (I) 23% by mass of the rubber-containing polymer (A-1) obtained as described above and the thermoplastic polymer (A-2). Methyl methacrylate / methyl acrylate copolymer (methyl methacrylate / methyl acrylate = 99/1, reduced viscosity 0.06 L /
g) Acrylic resin composition (1) 10 comprising 77% by mass
0 part, 10 parts of a polymer (1) having a hydroxyl group, 1 part of a thermoplastic resin component, 1 part of an ultraviolet absorber (“Tinuvin 1577”, manufactured by Ciba Geigy), a phosphite antioxidant (“P
EP8F "(manufactured by Asahi Denka Co., Ltd.) (0.6 parts) were mixed using a Henschel mixer. Then, using a 40 mmφ screw type twin-screw extruder (L / D = 26), the mixture was melt-kneaded at a cylinder temperature of 200 ° C. to 260 ° C. and a die temperature of 250 ° C. to be pelletized. The obtained pellets were dried overnight at 80 ° C. Then, a 400-mesh screen mesh provided with a 300 mm T die was provided 40
mmφ non-vent screw extruder (L / D = 2
6), using a cylinder temperature of 200 ° C to 240 ° C, T
A resin mirror melt-extruded through a T-die under a condition of a die temperature of 250 ° C., and a mirror-finished roll for cooling whose temperature was adjusted to 75 ° C. (chrome-plated roll having a surface roughness of 0.2 S).
Was used to form an acrylic resin film (I) having a thickness of 125 μm.

[Production of Laminate] As the thermoplastic resin film (III), ABS resin (“Diapet ABSS
W7 ", manufactured by Mitsubishi Rayon Co., Ltd., and equipped with a 300 mm T die and equipped with a 400 mesh screen mesh, a 40 mmφ non-vent screw extruder (L /
C = 180-220 using D = 26)
The resin melt-extruded through the T-die was formed into a film having a thickness of 200 μm through three polishing rolls whose temperature was adjusted to 75 ° C. under the conditions of the temperature of T ° C. and T-die temperature of 230 ° C. Next, this thermoplastic resin film (III) is subjected to gravure printing with a silver ink as a decorative layer (II), and finally, a matte acrylic resin film (I) is cooled with a mirror surface through an embossing roll. The matte acrylic resin film (I) was heat-laminated on the decorative layer (II) so that the surface that was in contact with the roll was in contact with the surface of the decorative layer (II) to obtain a coating substitute laminate film. The obtained coating substitute laminate film was heated at 140 ° C. for 1 minute, and then vacuum-molded with a mold having a vacuuming function. Then, in a state in which the molded laminated film for coating substitute is placed in the mold, the ABS resin as the base material (“Diapet ABS Bulksum TM2
0 ", made by Mitsubishi Rayon, a thermoplastic resin film (II
Injection molding was performed on the I) side to obtain a laminate.

Example 2 Acrylic Resin Composition (1) 1
Acrylic resin film (I), coating substitute laminate film, laminate in the same manner as in Example 1 except that 100 parts of the acrylic resin component (B) produced as described below was used instead of 00 parts. Was manufactured.

[Production of Acrylic Resin Component (B)] 250 parts of ion-exchanged water, 2 parts of ester soda salt of sulfosuccinic acid, and 0.05 part of sodium formaldehyde sulfoxylate were charged in a polymerization vessel equipped with a condenser, and nitrogen was added. After stirring under an atmosphere, 1.6 parts of methyl methacrylate, 8 parts of n-butyl acrylate, 0.4 parts of 1,3-butylene glycol dimethacrylate, 0.1 parts of allyl methacrylate and 0 cumene hydroperoxide. A mixture of .04 parts was charged. After the temperature was raised to 70 ° C., the reaction was continued for 60 minutes to complete the polymerization of the innermost polymer (B-1). Subsequently, 1.5 parts of methyl methacrylate forming a crosslinked elastic polymer (B-2) layer, 22.5 parts of butyl acrylate, 1.0 part of 1,3-butylene glycol dimethacrylate, and 0 allyl methacrylate. A mixture of .25 parts and 0.05 parts of cumene hydroperoxide was added over 60 minutes and polymerized to obtain a two-layer crosslinked rubber elastic body. Subsequently, as an intermediate polymer (B-4) layer, a mixture of 5 parts of methyl methacrylate, 5 parts of butyl acrylate and 0.1 part of allyl methacrylate was reacted. Finally, the outermost polymer (B-
3) As the layer, a mixture of 52.25 parts of methyl methacrylate and 2.75 parts of butyl acrylate was reacted to complete the polymerization, and a multilayer structure polymer was obtained. The particle diameter of the multilayer structure polymer was 0.12 μm. The obtained polymer latex was filtered with a filter having an opening of 75 μm, salted out with 5 parts by mass of calcium acetate to 100 parts by mass of the polymer, washed and dried to obtain an acrylic resin component (B). Got

(Example 3) Acrylic resin film (I)
During film formation, the resin melt-extruded through T-die is
A 125 μm thick acrylic resin film sandwiched between a mirror-finished roll (rolled with chrome plating and a surface roughness of 0.2 S) whose temperature was controlled to ℃ and a silicone rubber roll containing 50 parts of sand with an average particle size of 40 μm. An acrylic resin film (I), a laminated film, and a laminated body were produced in the same manner as in Example 1 except that (I) was used.

Example 4 Acrylic Resin Composition (1) 1
An acrylic resin film (I), a laminated film, and a laminated body were produced in the same manner as in Example 3 except that 100 parts of the acrylic resin component (B) produced in Example 2 was used instead of 00 parts.

Example 5 After forming the decorative layer (II), a blue gravure printing layer was provided as the coloring layer (IV),
An acrylic resin film (I), a laminated film, and a laminate were produced in the same manner as in Example 1 except that the acrylic resin film (I) was laminated thereon.

Example 6 Polymer Having Hydroxyl Group (1)
An acrylic resin film (I), a laminated film, and a laminated body were produced in the same manner as in Example 1 except that the polymer (2) having a hydroxyl group was used instead of.

Example 7 Polymer Having Hydroxyl Group (1)
An acrylic resin film (I), a laminated film, and a laminated body were produced in the same manner as in Example 1 except that the polymer (3) having a hydroxyl group was used instead of.

(Example 8) When obtaining the laminated film in Example 1, two metal layers were used instead of heat laminating the acrylic resin film (I) on the decorative layer (II) via an embossing roll. The same procedure as in Example 6 was carried out except that thermal lamination was performed via a belt.

(Example 9) Polymer having a hydroxyl group (1)
An acrylic resin film (I), a laminated film, and a laminated body were produced in the same manner as in Example 3 except that the acrylic resin film (I) was formed without using.

(Comparative Example 1) An acrylic resin was prepared in the same manner as in Example 1 except that the decorative layer (II) was formed on the acrylic resin film (I) instead of being formed on the thermoplastic resin film (III). A film (I), a laminated film and a laminate were produced.

(Comparative Example 2) Polymer having hydroxyl group (1)
An acrylic resin film (I), a laminated film, and a laminated body were produced in the same manner as in Example 1 except that the acrylic resin film (I) was formed without using.

(Comparative Example 3) Thermoplastic resin film (II
When the film of (I) was formed, a 400-mesh screen mesh was not used, and the film was formed through one cooling roll instead of through three polishing rolls.
An acrylic resin film (I), a laminated film and a laminated body were produced in the same manner as in Example 1.

Gel content of the acrylic resin compositions of Examples and Comparative Examples, heat distortion temperature acrylic resin film (I),
The 60 ° surface glossiness of the laminated film and the laminated body, the number of missing prints, the metallic appearance, the chemical resistance, and the gloss-reducing property were evaluated as follows.

<Evaluation method> 1) Thermoplastic polymer (A-2), reduced viscosity of thermoplastic resin component, and intrinsic viscosity of polymers (1) to (3) having a hydroxyl group ... Intrinsic viscosity, reduction The viscosity was measured using an automatic viscometer (“AVL-2C”, manufactured by Sun Electronics Co., Ltd.) at 25 ° C. using chloroform as a solvent. The reduced viscosity was measured by dissolving 0.1 g of the sample in 100 ml of chloroform.

2) Particle size of rubber-containing polymer (A-1), acrylic resin component (B) ... Rubber-containing polymer (A-1) or acrylic resin component (B) obtained by emulsion polymerization. The final particle size of the polymer latex of the light scattering photometer ("D
LS-700 ", manufactured by Otsuka Electronics Co., Ltd., was used to measure by the dynamic light scattering method.

3) 60 ° surface glossiness The 60 ° surface glossiness was measured using a gloss meter (“GM-26D type”, manufactured by Murakami Color Research Laboratory).
The acrylic resin film (I) had a surface not in contact with a cooling mirror roll, and the coating substitute laminate film and the laminate each had a 60 ° surface gloss of the acrylic resin film (I) surface.

4) Heat distortion temperature of acrylic resin composition
-The heat distortion temperature is as follows: A pellet before molding into an acrylic resin film is molded into a heat distortion temperature measuring sample based on ASTM D648 by injection molding and annealed at 80 ° C for 24 hours, and then subjected to a low load (0.45 MPa). ) At ASTM D6
It measured according to 48.

5) Gel content of acrylic resin composition ...
・ 1 pellet before molding into acrylic resin film
After being added to a mass% chloroform solution and left standing at 25 ° C. for a whole day and night, 16000 r.p.m. p. m. Was centrifuged for 90 minutes to remove the supernatant liquid, and the mass% of the insoluble matter after drying was taken as the gel content.

6) Number of missing prints ... The obtained laminated film for coating alternative 10m ^{2 was} visually inspected to measure the number of missing prints of the decorative layer (II), and converted into 1m ² for printing. The number of missing pieces was calculated.

7) Evaluation of metallic appearance ... The appearance of the laminate was evaluated visually (compared with the machined aluminum material) and visually evaluated. The evaluation criteria are as follows. ◎: No shine, very similar to the appearance of aluminum material ○: A little shine, but similar to appearance of aluminum material △: Very glossy, but barely looks like appearance of aluminum material ×: There is a feeling of shine, it does not look like the appearance of aluminum material

8) 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 body, and was strongly adhered to the test piece with a crimping machine, and an automobile air freshener ("Gracemate Poppy citrus" was placed in the opening. System ", manufactured by Dia Chemical Co., Ltd.).
After covering the opening with a glass plate, it is placed in a constant temperature bath kept at 55 ° C. and left for 4 hours. After the test, remove the crimper,
After washing the test piece with water, it is air-dried and the whitening state of the surface of the test part is observed. The evaluation criteria are as follows. ◎: No whitening is observed ○: Very slight whitening is recognized ×: Strong whitening is observed

9) Glass transition temperature of polymer having hydroxyl group: The glass transition temperature was determined according to the formula of FOX.

10) Evaluation of glossiness during molding of acrylic resin film (I) ... Using an epoxy adhesive so that the surface which was in contact with the mirror roll during film formation by the T-die method was in contact with the polycarbonate plate. The acrylic resin film (I) obtained in each of the examples and comparative examples was laminated to obtain a laminated plate. After leaving this laminated plate in an atmosphere of 120 ° C. for 48 hours, the 60 ° surface glossiness of the laminated plate surface was measured using a gloss meter (“GM-26D type”, manufactured by Murakami Color Research Laboratory). Table 1 shows the above evaluation results.

[0143]

[Table 1]

The acrylic resin film (I), the laminated film for coating substitute and the laminated body obtained in the examples have a good matte appearance, and moreover, the occurrence of printing omission is suppressed, and a high-grade feeling, a deep feeling, The appearance characteristics with a calm feeling were good.

[0145]

According to the present invention, it is possible to produce a laminated film or sheet as a substitute for coating, which has a high appearance, a deep feeling, and a calm feeling without having a shiny appearance, and has an extremely high industrial utility value. . Further, since the number of appearance defects of the decorative layer (II) is 10 or less per 1 m ^{2 and} the occurrence of print omission is suppressed, the yield can be improved. According to the substitute laminate film or sheet obtained by the production method of the present invention, a laminate having good workability and excellent appearance can be obtained. Further, the laminate of the present invention does not have a feeling of shine, has a feeling of luxury, a feeling of depth, and a feeling of calmness, and has an extremely high industrial utility value.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of an example of a paint-replacing laminated film or sheet manufactured by the manufacturing method of the present invention.

FIG. 2 is a cross-sectional view of an example of a paint-replacing laminated film or sheet manufactured by the manufacturing method of the present invention.

[Explanation of symbols]

(I) Acrylic resin film (II) Decorative layer (III) Thermoplastic resin film or sheet (IV) Colored layer

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // (C08L 51/00 C08L 33:14 33:14) F term (reference) 4F100 AB01B AK01C AK01E AK25A AK25K AK74C AK74E AL04A AL05A AL09A AR00D BA03 BA04 BA05 BA07 BA10A BA10C BA10E BA15 CA30A EA061 EC032 EH461 EJ192 EJ422 EJ861 HB00B HB00D HB31B JB16C JL10D JN21A JN24B JN26A YY00A YY00B 4J002 BG05X BG072 BG073 BN12W BN21W BN211 GF00 4J026 AA45 AA46 AC15 BA27 DA04 DA07 DA15 DB04 DB08 DB15 FA07 GA01 GA02 GA08 GA09 GA10

Claims (9)

[Claims] 1. A method for producing a laminated film or sheet for coating substitution, comprising an acrylic resin film (I), a decorative layer (II), and a thermoplastic resin film or sheet (III), which comprises a thermoplastic resin. A decorative layer (II) having 10 or less appearance defects per 1 m ² is formed on the film or sheet (III), and the 60 ° surface gloss is 50% on the decorative layer (II). A method for producing a laminated film or sheet as a paint substitute, which comprises laminating the following acrylic resin film (I). 2. A colored layer (IV) on the decorative layer (II).
The method for producing a laminated film or sheet as a substitute for coating according to claim 1, wherein the acrylic resin film (I) is laminated after forming the film. 3. The coating according to claim 1, wherein a colored layer (IV) is formed on the thermoplastic resin film or sheet (III) and then the decorative layer (II) is formed. A method for manufacturing an alternative laminated film or sheet. 4. The acrylic resin film (I) is used in an amount of 0.1 parts by weight per 100 parts by weight of the following acrylic resin component (A).
It is formed from an acrylic resin composition containing 1 to 40 parts by mass of a matting agent, and the method for producing a laminated film or sheet for coating substitution according to any one of claims 1 to 3, characterized in that: Acrylic resin component (A) 5.5 to 99.9% by mass of the rubber-containing polymer (A-1),
A thermoplastic polymer (A-2) having 0.1 to 94.5% by mass of a methacrylic acid alkyl ester as a main component, wherein the rubber-containing polymer (A-1) is a monomer containing an acrylic acid alkyl ester. The elastomeric copolymer (a-1) obtained by polymerizing a body composition is graft-polymerized with a monomer composition containing methacrylic acid alkyl ester as a main component. 5. The acrylic resin film (I) is used in an amount of 0.1 parts by weight per 100 parts by weight of the following acrylic resin component (B).
It is formed from an acrylic resin composition containing 1 to 40 parts by mass of a matting agent, and the method for producing a laminated film or sheet for coating substitution according to any one of claims 1 to 3, characterized in that: Acrylic resin component (B) A multilayer structure polymer having an innermost polymer (B-1), a crosslinked elastic polymer (B-2) layer, and an outermost polymer (B-3) layer in this order from the inside. , The innermost polymer (B-1) is 80 to 1
0% by mass of an acrylic acid alkyl ester having a C1-8 alkyl group and / or a methacrylic acid alkyl ester having a C1-4 alkyl group;
Graft of 0.1 to 5 parts by weight based on 100 parts by weight of another monomer having 20% by weight of a copolymerizable double bond and 0 to 10% by weight of a polyfunctional monomer. The crosslinked elastic polymer (B-2) layer is obtained by polymerizing a monomer composition containing a crossing agent, and the acrylic acid alkyl ester having 80 to 100% by mass of an alkyl group having 1 to 8 carbon atoms, 0.1 to 5 parts by mass with respect to a total of 100 parts by mass of 0 to 20% by mass of another monomer having a copolymerizable double bond and 0 to 10% by mass of a multifunctional monomer. The outermost polymer (B-3) layer is obtained by polymerizing a monomer composition containing the above graft crossing agent, and the methacrylic acid alkyl ester having 51 to 100% by mass of an alkyl group having 1 to 4 carbon atoms. And 0 to 49% by weight of another monomer having a copolymerizable double bond. Is to give further crosslinked elastic polymer (B-2) layer and the outermost polymer (B-
3) A layer containing 10 to 90% by mass of an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms, and 90
10 to 10% by mass of a methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms, 0 to 20% by mass of a monomer having a copolymerizable double bond, and 0 to 10% by mass of polyfunctionality 0.1-5 with respect to 100 parts by weight in total with the monomer
It has at least one intermediate polymer (B-4) layer obtained by polymerizing a monomer composition containing parts by weight of a graft crossing agent, and the content of alkyl acrylate (% by mass).
From the crosslinked elastic polymer (B-2) layer to the outermost polymer (B-
3) It is decreasing toward the layer. 6. The coating according to claim 1, wherein the thermoplastic resin film or sheet (III) is melt-extruded through a screen mesh of 200 mesh or more. A method for manufacturing an alternative laminated film or sheet. 7. The method for producing a laminated film or sheet as a paint substitute according to claim 1, wherein the decorative layer (II) is a metallic print layer or a metallic layer. . 8. A laminated film or sheet for coating substitution, which is produced by the method for producing a laminated film or sheet for coating substitution according to any one of claims 1 to 7. 9. A laminate, wherein the coating substitute laminate film or sheet according to claim 8 is laminated on a substrate such that the acrylic resin film (I) is the outermost layer.