JP2002003620A - Acrylic resin film, laminated sheet, laminated injection molded product - Google Patents

Abstract

(57) [Abstract] (with correction) [PROBLEMS] An acrylic resin film suitable for surface decoration of a laminated injection molded product, a laminated sheet obtained by laminating the film, and the film or the laminated sheet formed on the injection molded product The present invention provides a laminated injection-molded product which is laminated on a substrate. A copolymer obtained by graft-polymerizing an alkyl methacrylate in the presence of a random copolymer of an alkyl methacrylate as a main component with an alkyl acrylate and an elastic polymer of the alkyl acrylate. A composition having a slit width of 1 mm or less
10 obtained by melt extrusion from a die
10% heat shrinkage after heat treatment in 0 ° C atmosphere for 10 minutes
An acrylic resin film having a thickness of 10 μm or more and 500 μm or less, a laminated sheet using the film, and a laminated injection molded product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylic resin film suitable for decorating the surface of a laminated injection molded article, and
The present invention relates to a laminated sheet obtained by laminating such an acrylic resin film.

[0002]

2. Description of the Related Art In recent years, as a method of decorating the surface of a resin molded product instead of painting, a decorative film such as printing is inserted into an injection molding die, injection molded, and then only the decorative layer is molded. A transfer method in which the film is peeled off after being transferred to the surface, a method of decorating simultaneously with injection molding such as an insert molding method and an in-mold molding method in which the decorative film is left on the molded product as the outermost surface of the molded product; A method of laminating on the surface of a molded article is widely used.

[0003] In particular, as an acrylic resin film suitable for in-mold molding, Japanese Patent Application Laid-Open No. 8-323934 discloses that a rubber-containing polymer (II) having a specific particle size is used in a smaller amount than in the past, so that the surface hardness and heat resistance can be improved. It describes that an acrylic resin film having excellent properties and moldability can be obtained.

Japanese Patent Application Laid-Open No. 11-147237 discloses an acrylic resin film having a glass transition temperature of about 105.degree.
An acrylic resin film having excellent surface hardness containing a rubber-containing polymer having a hard core structure is disclosed.

Japanese Patent No. 2965973 and Japanese Patent No. 3003032 disclose a sheet for in-mold molding using a laminated film from a transparent acrylic film layer, a picture layer and a base film layer, and an insert molding method. .

[0006]

Generally, an acrylic resin film or a laminated sheet having an acrylic resin layer formed of an acrylic resin film is formed into a three-dimensional shape by vacuum or air pressure molding or the like in an injection mold. In the in-mold molding method of performing injection molding after performing the above, a step of preheating and softening the acrylic resin film or the laminated sheet before vacuum or pressure forming is required.

In such a process, when a conventionally known acrylic resin film is used, wrinkles may occur in the acrylic resin film during preheating, or the acrylic resin film may be broken during vacuum forming. Was. In addition, wrinkles or tears may occur during lamination.

Further, when a conventionally known laminated sheet is used, the interface between the acrylic resin film and the base sheet may peel off.

In addition, in both the case of the acrylic resin film and the laminated sheet, a long preheating is required in order to suppress wrinkles, peeling and tearing and to produce a laminated injection molded product having a good appearance. And the productivity was sometimes insufficient.

[0010] Particularly, when manufacturing a laminated injection molded product having a large area shape or a deep drawing shape, it is sometimes necessary to carry out preheating for a particularly long time, and the productivity may be low.

However, JP-A-8-323934, JP-A-11-147237, and Japanese Patent No. 296
In Japanese Patent No. 5973 and Japanese Patent No. 3003032, for example, with respect to a surface decoration acrylic resin film or a laminated sheet that can be adapted to a large area shape or a deep drawn shape by short-time preheating, specifically, It is not described, and also in the examples in the publication, the obtained acrylic resin film or laminated sheet is used for a molded article having a large area shape or a deep drawing shape, and the preheating time is shortened, which is excellent. It does not specifically show how to achieve improved productivity.

That is, in the simultaneous decoration of a large-area or deep-drawn molded article by injection molding, even when an acrylic resin film or a laminated sheet is molded in a short pre-heating time, wrinkles, tears, and the interface of the laminated sheet may occur. An acrylic resin film and a laminated sheet capable of realizing good moldability without causing problems such as peeling have not been found, and there has been a strong demand for the development of a technique satisfying these.

In view of the above situation, the present invention provides an acrylic resin film and a laminated sheet which can shorten the preheating time without producing problems such as wrinkles, peeling and tearing in the production of a laminated injection molded product. It is another object of the present invention to produce a large-area or deep-drawn laminated injection molded product with good productivity.

[0014]

According to the present invention for achieving the above object, the heat shrinkage after heat treatment in a 100 ° C. atmosphere for 10 minutes is 10% or less, and 10 μm or more and 50 μm or more.
An acrylic resin film having a thickness of 0 μm or less is provided.

[0015]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below.

In the acrylic resin film of the present invention, the heat shrinkage after heat treatment in a 100 ° C. atmosphere for 10 minutes is 10% or less. By manufacturing laminated injection molded products using such acrylic resin film,
The preheating time can be reduced without causing problems such as wrinkles, peeling, and tearing, and a large-area or deep-drawn laminated injection molded product can be manufactured with good productivity.

That is, if the heat shrinkage after heat treatment in a 100 ° C. atmosphere for 10 minutes is 10% or less, this is used for in-mold molding or insert molding, and even when the pre-heating time is short, wrinkles, Peeling and tearing can be suppressed. In addition, even when used for lamination molding and the heating time is short, wrinkles, peeling and tearing can be suppressed.
As a result, good moldability and productivity can be realized.

Further, using a laminated sheet obtained from an acrylic resin film having a heat shrinkage of 10% or less and a base sheet such as an ABS resin sheet, a polypropylene sheet, a PVC sheet or an acrylic resin film having a thickness of more than 500 μm, When performing in-mold molding under a large area shape or a deep drawing shape condition, even when the preheating time is short, occurrence of peeling at the interface between the base material sheet and the acrylic resin film is suppressed. As a result, good moldability and productivity can be realized.

From the viewpoint of moldability and productivity during in-mold molding, the heat shrinkage after the heat treatment of the acrylic resin film in a 100 ° C. atmosphere for 10 minutes is preferably 8% or less, more preferably 5% or less. preferable.

The shape of the in-mold molded product in which the effects of the present invention can be confirmed, that is, a large-area shape or a deep-drawn shape, has a projected area of 500 cm ² or more, such as used for a center console panel of a vehicle inner layer part. Having a shape with a drawing depth of 10 mm or more, such as moldings for vehicle exterior parts, having a long dimension of 1 m or more, helmets and plastic containers having a shape with a drawing depth of 150 mm or more, etc. Can be mentioned.

When simultaneously molding and injection molding a molded article having a large area shape or a deep drawn shape as described above, it is assumed that an acrylic resin film or a laminated sheet having a heat shrinkage of more than 10% is used. However, if a sufficient preheating time is secured at an appropriate temperature, it is possible to suppress problems such as wrinkles, tears, and interfacial peeling of the laminated sheet. However,
When molding by shortening the preheating time, the heat shrinkage rate is 1
If it is larger than 0%, the acrylic resin film or the laminated sheet will be three-dimensionally processed in a state where the stress due to shrinkage remains in the acrylic resin film.
Wrinkles, tears, interface peeling of the laminated sheet, and the like may occur.

Even when the preheating time is shortened and molding is performed with high productivity, if an acrylic resin film having a heat shrinkage of 10% or less after heat treatment in a 100 ° C. atmosphere for 10 minutes is used, Problems such as wrinkles, tears, and interfacial peeling of the laminated sheet are suppressed, and a good molded product can be obtained.

For example, an acrylic resin film or a laminated sheet is formed with a non-contact heating plate by using a vacuum moldable injection mold having a box-shaped cavity having a projected area of 500 cm ² and a drawing depth of 10 mm. Even when the time for heating to 130 ° C. (preliminary heating time) is as short as 30 seconds, wrinkling and tearing of the acrylic resin film can be suppressed during vacuum molding or injection molding to be performed subsequently. In the case of a laminated sheet, peeling at the interface between the base sheet and the acrylic resin film can be suppressed. More preferably, even when the preheating time is set to 10 seconds, wrinkling and tearing of the acrylic resin film and interfacial peeling of the laminated sheet can be suppressed.

In particular, even when the preheating time is as short as 10 seconds, an acrylic resin film and a laminated sheet exhibiting good in-mold moldability can shorten the molding cycle when producing a laminated injection molded product. High industrial value.

The thickness of the acrylic resin film of the present invention is
It is 500 μm or less. When the film thickness is 500 μm or less, good film-forming properties can be realized, stable production can be performed, and the rigidity of the obtained acrylic resin film is reduced, so that good secondary workability such as laminating properties can be realized. In addition, since the mass per unit area can be reduced,
Economically favorable. From the above viewpoints, the thickness is more preferably 300 μm or less.

The thickness of the acrylic resin film of the present invention is at least 10 μm. If the film thickness is 10 μm or more, a film strength applicable to secondary processing can be realized. Further, in order to improve the film-forming properties and the deep and transparent feeling of the injection molded product obtained by laminating the acrylic resin film, the thickness is more preferably 50 μm or more, and still more preferably 100 μm or more.

The pencil hardness (measured according to JIS K 5400) of the acrylic resin film of the present invention is preferably H or more. If the pencil hardness is H or more, it can be used as the outermost surface of a vehicle interior or exterior part or the like that requires particularly high surface hardness or scratch resistance.

The acrylic resin composition for producing the acrylic resin film of the present invention is not particularly limited, but those having excellent film-forming properties are preferred.

The thermal deformation temperature (measured according to ASTM D648) of the acrylic resin composition is preferably 80 ° C. or higher. If the heat distortion temperature is 80 ° C or higher,
At the time of heating the laminated injection-molded article, occurrence of surface roughness due to residual stress is suppressed. Furthermore, when used for vehicle applications,
If the heat deformation temperature is 100 ° C. or more, for example, it can be used near the handle portion, and if it is 110 ° C. or more,
For example, it can be used in the vicinity of a meter panel, and thus has high industrial utility value.

Examples of the acrylic resin composition used in the present invention include 75 to 94.5 parts by mass of a thermoplastic polymer (I) and 5.5 to 25 parts by mass of a rubber. Containing polymer (II), and the thermoplastic polymer (I) contains 50% by mass of an alkyl methacrylate ester.
The above, a simple composition comprising 50% by mass or less of an alkyl acrylate and 49% by mass or less of at least one vinyl monomer copolymerizable with at least one of an alkyl methacrylate and an alkyl acrylate. It is obtained by polymerizing the monomer mixture (I), and the rubber-containing polymer (II) has a multilayer structure of two or more layers including an elastic inner layer and a hard outer layer. Has at least one layer of an elastic (co) polymer obtained by polymerizing an alkyl acrylate, and the hard outer layer is mainly graft-polymerized with an alkyl (meth) acrylate in the presence of the elastic (co) polymer. Having at least one layer made of a hard polymer obtained by the above method.

The alkyl methacrylate and the alkyl acrylate used in the thermoplastic polymer (I) are not particularly limited, but preferably have 1 to 4 carbon atoms as the alkyl group.

Examples of such alkyl methacrylates include methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like, with methyl methacrylate being preferred. As alkyl acrylate,
Examples thereof include methyl acrylate, ethyl acrylate, butyl acrylate, and the like. The content of the alkyl acrylate is 50% by mass or less, but preferably 0.1% by mass or more and 40% by mass or less.

As the copolymerizable vinyl monomer used in the thermoplastic polymer (I), known monomers can be used.

The reduced viscosity of the thermoplastic polymer (I) (0.1 g of the polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) is such that a suitable elongation of the acrylic resin composition at the time of melting is obtained.
0.1 L / g or less is preferable in order to realize good film forming properties. Further, in order to realize sufficient flexibility of the acrylic resin film and to suppress cutting of the film during film formation and printing, it is preferably 0.05 L / g or more.

The method of polymerizing the thermoplastic polymer (I) is not particularly limited, but it can be carried out by a conventional method such as suspension polymerization, emulsion polymerization, or bulk polymerization. It should be noted that a chain transfer agent may be required to adjust the viscosity to a preferable range. Known chain transfer agents can be used, but mercaptans are preferred. The amount of the chain transfer agent can be appropriately determined depending on the type and composition of the monomer.

As the rubber-containing polymer (II), 50% by mass or more to 99.9% by mass of an alkyl acrylate is used.
49.9% by mass of the following and another copolymerizable vinyl monomer
0.1% by mass or more and 10% by mass or less of the copolymerizable crosslinkable monomer
% By mass or less to obtain an elastic (co) polymer, and then the resulting elastic (co) polymer 1
In the presence of 00 parts by mass, a mixture of a monomer containing 50% by mass or more of a methacrylic acid ester and 50% by mass or less of a vinyl monomer copolymerizable therewith is used in an amount of 10 parts by mass to 400 parts by mass. It is preferable to produce by polymerizing the following in at least one stage.

In order to suppress the resulting acrylic resin film from becoming brittle, the rubber-containing polymer (I
The proportion of the elastic (co) polymer in I) is preferably at least 5% by mass, more preferably at least 8% by mass of the total of the thermoplastic polymer (I) and the rubber-containing polymer (II). On the other hand, in order to improve the transparency of the obtained acrylic resin film, the content is preferably 18% by mass or less, more preferably 12% by mass or less.

In particular, a rubber-containing polymer (II) having the following semi-hard core structure can be used. That is, the rubber-containing polymer (II) having a semi-hard core structure comprises a polymer (II-A) in the innermost layer and a rubber polymer (II-B) in the intermediate layer.
(II-A) + (II-
B)) and a hard polymer (II-C) as the outermost layer, wherein the innermost layer is a polymer (II-A) containing alkyl methacrylate and alkyl acrylate as main components, and the intermediate layer is an alkyl acrylate Rubber polymer having a glass transition temperature of less than 0 ° C. containing an ester as a main component (II-
B), the outermost layer has a three-layer structure composed of a hard polymer (II-C) containing alkyl methacrylate as a main component.

From the viewpoint of moldability, the content of the polymer (II-A) in the elastic (co) polymer is preferably 20% by mass or more, more preferably 30% by mass or more, and preferably 60% by mass or less. For the same reason, in the elastic (co) polymer, the content of the rubber polymer (II-B) is preferably 40% by mass or more.
It is more preferably at least 80% by mass, more preferably at most 80% by mass.

The glass transition temperature of the innermost layer polymer (II-A) is preferably 0 ° C. or higher, more preferably 15 ° C. or higher, and preferably less than 25 ° C. When the glass transition temperature is 0 ° C or higher, the plasticizer whitening resistance of the obtained acrylic resin film is improved, and when the glass transition temperature is lower than 25 ° C, the moldability of the obtained acrylic resin film during vacuum forming is improved. is there.

As the alkyl acrylate used in the production of the above-mentioned elastic (co) polymer, those having an alkyl group having 1 to 8 carbon atoms are preferable. Among them, butyl acrylate and acrylic acid-2 -Ethylhexyl and the like are preferred. As the copolymerizable vinyl monomer used for obtaining the elastic (co) polymer, alkyl methacrylates such as methyl methacrylate, butyl methacrylate and cyclohexyl methacrylate, and styrene and acrylonitrile are preferable.

In the production of the elastic (co) polymer, it is preferable to use a copolymerizable crosslinkable monomer. The crosslinkable monomer used is not particularly limited, but is preferably ethylene glycol dimethacrylate, butanediol dimethacrylate, allyl acrylate, allyl methacrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene,
Examples thereof include diallyl maleate, trimethylol triacrylate, and allyl cinnamate, which can be used alone or in combination of two or more.

Examples of the methacrylate ester to be grafted on the elastic (co) polymer include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-methacrylic acid.
Ethylhexyl, cyclohexyl methacrylate and the like are used.

As the vinyl monomer to be grafted to the elastic (co) polymer, alkyl acrylates such as methyl acrylate, butyl acrylate and cyclohexyl acrylate, styrene, acrylonitrile and the like are used. The mixture of the monomers to be grafted is preferably at least 10 parts by mass with respect to 100 parts by mass of the elastic (co) polymer in order to suppress aggregation of the elastic (co) polymer.
It is more preferably at least 20 parts by mass, preferably at most 400 parts by mass, more preferably at most 200 parts by mass.

The average particle size of the rubber-containing polymer (II) described above is preferably 0.2 μm or more in order to realize a sufficient film-forming property of the obtained acrylic resin film.
0.25 μm or more is more preferable. In addition, in order to realize sufficient transparency of the acrylic resin film, 0.4 μm
Or less, more preferably 0.35 μm or less.

The rubber-containing polymer (I) used in the present invention
I) can be produced by a known emulsion polymerization method. The polymerization temperature varies depending on the type and amount of the polymerization initiator used, but is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, preferably 95 ° C. or lower, and more preferably 120 ° C. or lower.

As the polymerization initiator, known ones can be used, and as a method for adding the polymerization initiator, a method of adding the polymerization initiator to one or both of the aqueous phase and the monomer phase can be used.

As the emulsifier, anionic, cationic and nonionic surfactants can be used, and anionic surfactants are particularly preferred. As anionic surfactants, potassium oleate, sodium stearate, sodium myristate, sodium N-lauroyl sarcosinate, carboxylate salts such as dipotassium alkenyl succinate, sulfate salts such as sodium lauryl sulfate, and octyl sulfo succinate And sulfonic acid salts such as sodium dodecylbenzenesulfonate and sodium alkyldiphenylether disulfonate, and phosphoric acid ester salts such as sodium polyoxyethylene alkylphenyl ether phosphate.

The latex obtained by the emulsion polymerization method is coagulated by a known coagulation method such as an acid coagulation method, a salt coagulation method, a freeze coagulation method and a spray drying method. 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. As the salt coagulation method, inorganic salts such as sodium sulfate, magnesium sulfate, aluminum sulfate, and calcium chloride can be used. And organic salts such as calcium acetate and magnesium acetate. The coagulated polymer is further washed, dehydrated and dried.

In the present invention, in order to improve the film forming property of the acrylic resin film and to control the thickness and the film forming speed of the acrylic resin film with high precision, the acrylic resin composition contains 50% by mass of methyl methacrylate. And at least one vinyl monomer copolymerizable with methyl methacrylate
It is preferable to add a thermoplastic polymer (III) obtained by polymerizing a monomer mixture (III) containing 0% by mass or less.

The amount of the thermoplastic polymer (III) to be added to 100 parts by mass of the acrylic resin composition is preferably from 0.1 part by mass to 10 parts by mass in order to sufficiently improve the film forming property.

The reduced viscosity of the thermoplastic polymer (III) (0.1 g of the polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) is set at 0.1 to obtain an acrylic resin film having good thickness accuracy. This is preferably higher than 2 L / g, preferably 2 L / g or less, and more preferably 1.2 L / g or less.

Further, in order to suppress the resulting acrylic resin film from becoming brittle, a rubber-containing polymer (I
The proportion of the elastic (co) polymer in I) is preferably at least 5% by mass of the total of the thermoplastic polymer (I), the rubber-containing polymer (II) and the thermoplastic polymer (III). In order to improve the transparency of the resin film, 18
% By mass or less is preferred.

The vinyl monomers copolymerizable with methyl methacrylate used in the production of the thermoplastic polymer (III) include alkyl acrylates, alkyl methacrylates, aromatic vinyl compounds and vinyl cyanide. Compounds and the like can be used. The polymerization is preferably carried out by an emulsion polymerization method. The polymer latex is produced by separating and collecting a polymer latex produced by a known emulsion polymerization method using various coagulants or by separating and collecting a solid content by spray drying to obtain a polymer powder.

The heat distortion temperature of the acrylic resin composition used in the present invention varies depending on the amount of the rubber-containing polymer (II) used, but mainly the heat distortion temperature of the thermoplastic polymer (I) is dominant. It is. The heat distortion temperature of the thermoplastic polymer (I) can be controlled by adjusting the monomer composition of the thermoplastic polymer (I) by a known method. Although it depends on various conditions, for example, when methyl acrylate is used as a copolymer component, when the heat distortion temperature is 80 ° C. or more, the methyl methacrylate content in the thermoplastic polymer (I) is 88% by mass or more. When the heat distortion temperature is set to 100 ° C. or higher, it can be adjusted by setting the methyl methacrylate content in the thermoplastic polymer (I) to 95% by mass or higher. When the heat deformation temperature is 110 ° C. or higher, the thermoplastic polymer (I) contains
Maleimides such as maleic anhydride and phenylmaleimide may be copolymerized. Even when the heat distortion temperature is 80 ° C. or more and 100 ° C. or more, maleimides such as maleic anhydride and phenylmaleimide can be copolymerized. In this case, the content of methyl methacrylate may be reduced. .

The acrylic resin film of the present invention may contain, if necessary, general compounding agents such as stabilizers, lubricants, processing aids, plasticizers, impact-resistant aids, foaming agents, fillers, coloring agents,
Matting agents, ultraviolet absorbers and the like can be added. In particular, in terms of protection of the substrate, in order to impart weather resistance, 0.1%
It is preferable to add the ultraviolet absorber in the range of not less than 5% by mass and not more than 5% by mass. The molecular weight of the ultraviolet absorber used is preferably 300 or more, particularly preferably 40 or more.
0 or more. By using an ultraviolet absorber having a molecular weight of 300 or more, it is possible to prevent the ultraviolet absorber from volatilizing and contaminating the mold when performing vacuum molding or pressure molding in the injection mold.

The type of the ultraviolet absorbent is not particularly limited, but a benzotriazole-based compound having a molecular weight of 400 or more or a triazine-based compound having a molecular weight of 400 or more can be particularly preferably used. Specific examples of the former include Tinuvin 234 of Ciba-Geigy. Asahi Denka Kogyo's ADK STAB LA-31,
A specific example of the latter is Ciba Geigy's Tinuvin 15
77 and the like. As a hindered amine light stabilizer (HALS), ADK STAB L from Asahi Denka Kogyo Co., Ltd.
A-57 or the like can also be used.

Using the acrylic resin composition obtained as described above, an acrylic resin film can be produced by a melt extrusion method such as a melt casting method, a T-die method, an inflation method or the like; Although it is possible, from the viewpoint of economical efficiency, it is preferable to manufacture using an extrusion film forming machine equipped with a T die, a cooling roll, and a winding machine.

The T-die used is not particularly limited.
From the viewpoint of stabilizing the flowability of the molten resin in the T-die, a hanger coat type T-die is preferable.

The slit width of the T-die used is preferably 1 mm or less. Slit width is 1
mm or less, when forming an acrylic resin film having a thickness of 500 μm or less, the draw ratio becomes small,
An acrylic resin film having a heat shrinkage of 10% or less after heat treatment for 10 minutes in an atmosphere at a temperature of 10 ° C. can be easily produced.

Even when the film is formed by using a T-die having a slit width of more than 1 mm and increasing the draw ratio, the film is annealed after the film is formed.
An acrylic resin film having a heat shrinkage of 10% or less after a heat treatment for 10 minutes in an atmosphere of ° C. can be produced. However, since the annealing treatment is disadvantageous from the viewpoint of productivity, a method of forming a film by melt extrusion using a T die having a slit width of 1 mm or less is preferable.

The acrylic resin composition melt-extruded from the T-die is formed into a film by a take-off machine equipped with a cooling roll. The method of cooling the molten resin is not particularly limited, but a method of forming a film by contacting with one metal roll;
A method of forming a film by sandwiching it between a plurality of metal rolls, non-metal rolls and / or metal belts can be exemplified.

In the method in which a molten acrylic resin composition is cast into contact with a single metal roll to form a film, the above-mentioned T-die having a slit width of 1 mm or less is used. It is preferable from the viewpoint of easily manufacturing a resin film.

On the other hand, if a method of forming a film by sandwiching it between a plurality of metal rolls, non-metal rolls and / or metal belts is used, the surface smoothness of the obtained acrylic resin film is improved, and the acrylic resin film is subjected to printing treatment. The printing omission at the time of performing can be suppressed.

As the metal roll, a metal mirror-finished touch roll; Japanese Patent No. 2808251 or WO
A roll or the like used in a sleeve touch system including a metal sleeve (metal thin-film pipe) and a forming roll described in JP-A-97 / 28950 can be exemplified. Further, as the non-metallic roll, a touch roll of silicon rubber or the like can be exemplified. Further, examples of the metal belt include a metal endless belt. It should be noted that a plurality of these metal rolls, non-metal rolls, and metal belts can be used in combination.

In the above-described method of forming a film by sandwiching a plurality of metal rolls, non-metal rolls and / or metal belts, the acrylic resin composition after the melt extrusion is substantially banked (resin pool). It is preferable that the film is formed by holding the film in a state where there is no surface and transferring the surface without being substantially rolled.

When the film is formed without forming a bank (resin pool), the acrylic resin composition in the cooling process is transferred onto the surface without being rolled, so that the acrylic resin film formed by this method is heated. The shrinkage can be reduced, and an acrylic resin film having a specific heat shrinkage can be easily produced.

When a film is formed using a plurality of metal rolls, non-metal rolls, and / or metal belts, the surface of at least one metal roll, non-metal roll, or metal belt to be used is embossed, matted. By performing shape processing such as processing, the shape can be transferred to one or both surfaces of the acrylic resin film.

The acrylic resin film of the present invention can be used as a print film by printing a picture on one side, if necessary, in order to impart design properties. As a printing method for printing such a pattern, a gravure printing method,
Known printing methods such as a flexographic printing method and a silk screen printing method can be exemplified.

By laminating the above-mentioned printing film on the surface of an injection-molded article made of a thermoplastic resin, it is possible to easily form a picture layer or the like. In this case, the acrylic resin film has a deep transparent film. A feeling can be given, and the design property can be improved.

As a method of manufacturing a laminated injection molded product by laminating an acrylic resin film or a printed film on the surface of the injection molded product, a method of laminating the acrylic resin film or the printed film on the surface of the injection molded product (lamination molding method); Acrylic resin film or printed film is processed in advance into the shape of an injection molded product by vacuum or air pressure molding, and after arranging this in an injection molding die, injection molding is performed to form a laminated injection molded product simultaneously with injection molding. Method (insert molding method): A method in which an acrylic resin film or a printed film is vacuum- or pressure-molded in an injection molding mold cavity, and then injection-molded to form a laminated injection-molded product at the same time as injection molding (in-mold molding). Method) and the like.

The thermoplastic resin constituting the injection-molded article is not particularly limited as long as it has excellent adhesiveness. For example, ABS resin, AS resin, polystyrene resin, polycarbonate resin, vinyl chloride resin, acrylic resin , A polyester-based resin, or a resin containing these as a main component can be used. However, even in the case of a non-heat-fusible base resin such as a polyolefin resin, it is possible to adhere at the time of molding by using an adhesive layer.

Further, in the present invention, a laminated sheet obtained by laminating an acrylic resin film or a printed film and a thermoplastic resin sheet or a base sheet made of a thermoplastic resin film is laminated by the lamination method, the insert method or the imprint method described above. It is also possible to produce a laminated injection-molded product by laminating it on the surface of an injection-molded product by a molding method.

Examples of the thermoplastic resin constituting the base sheet include polypropylene, ABS resin, polyester resin, polyvinyl chloride, and acrylic resin containing a matting agent and / or a coloring agent. Lamination of these substrate sheets and an acrylic resin film or a printing film can be performed by lamination by heating, lamination using an adhesive, or the like.

When a laminated sheet is used, a pattern can be printed on a substrate sheet by a gravure printing method, a flexographic printing method, a silk screen printing method, or the like.

As described above, the acrylic resin film of the present invention has a heat shrinkage of 10% or less after heat treatment in a 100 ° C. atmosphere for 10 minutes. Even when a thermal lamination method with a short heating time, an insert molding method with a short preheating time, an in-mold molding method with a short preheating time, or the like is employed, wrinkles and tears may occur in the acrylic resin film. This suppresses the occurrence of interfacial peeling of the laminated sheet.

As a result, the obtained laminated injection-molded article can impart excellent design properties, weather resistance and surface scratch resistance of the acrylic resin film to the surface of the injection-molded article with high productivity, and can be used for various industrial applications. Can be used.

Industrial application examples of the laminated injection molded article containing the acrylic resin film of the present invention include: vehicle parts such as vehicle exteriors and vehicle interiors; building materials parts such as wall materials and window frames; daily use such as tableware and toys. Household goods such as vacuum cleaner housing, television housing and air conditioner housing; interior members; ship members; electronic communication devices such as personal computer housings and mobile phone housings.

[0079]

The present invention will be described in more detail with reference to the following examples, which do not limit the present invention in any way. Unless otherwise specified below, “parts” and “%”
Means "part by mass" and "% by mass", respectively, and a commercially available high-purity product was used as the reagent and the like.

The following abbreviations may be used: methyl methacrylate MMA, methyl acrylate MA, butyl acrylate BA, styrene St, allyl methacrylate AMA, 1.3-butylene glycol dimethacrylate 1.3BD, t-butylhydro Peroxide tBH, t-hexyl hydroperoxide tHH, n-octyl mercaptan nOM.

(Evaluation method) The obtained thermoplastic polymer (I), rubber-containing polymer (II), and thermoplastic polymer (I)
Each property of II) and the acrylic resin film was measured as follows.

(A) Thermoplastic polymers (I) and (II)
I) Reduced viscosity (L / g): At 25 ° C., 0.1 g of a sample was dissolved in 100 mL of chloroform, and measured using an AVL-2C automatic viscometer manufactured by Sun Electronics Industry.

(A) Average particle size (μm) of rubber-containing polymer (II): Rubber-containing polymer (I) obtained by emulsion polymerization
The final average particle diameter of the polymer latex of I) was measured by a dynamic light scattering method using a light scattering photometer DLS-700 manufactured by Otsuka Electronics Co., Ltd.

(C) Total light transmittance (%) of acrylic resin film: Measured according to JIS K6714.

(D) Surface gloss of acrylic resin film (%): The surface gloss of the film was measured using a gloss meter (Model GM-26D manufactured by Murakami Color Research Laboratory).
Was used to measure the surface gloss at 60 °.

(E) Pencil hardness of acrylic resin film:
It measured according to JISK5400.

(F) Film forming property of acrylic resin film: T
A film having a thickness of 100 μm was formed by a die method.
A film was cut several times in a time, and a film was cut off due to frequent cutting of the film.

(G) Thermal deformation temperature (° C.) of acrylic resin composition: The acrylic resin composition was pelletized, and a test piece for measuring thermal deformation temperature based on ASTM D648 was molded by injection molding. After the obtained test piece was annealed at 80 ° C. for 24 hours, ASTM D6 was applied under a low load (0.45 MPa).
According to 48, the heat distortion temperature was measured.

(H) Heat shrinkage (%) of acrylic resin film: Three lines parallel to the film forming direction (flow direction) were marked on the acrylic resin film cut into A4 size. Then, it was left in a heating furnace at 100 ° C. for 10 minutes, taken out of the heating furnace, measured the length of three previously marked places, and calculated the heat shrinkage (%) at each place from the following equation. Heat shrinkage (%) = [(length before heating−length after heating) / length before heating] × 100.

(G) Evaluation of laminated injection-molded product: An acrylic resin film or a laminated sheet is placed on the surface of the female cavity of an injection mold, and is heated at 130 ° C. for 10 seconds or 30 seconds by a non-contact heating plate. And preheating. afterwards,
Vacuum forming was performed to make the film follow the cavity surface. ：: No wrinkles, tears, or peeling, Δ: Only slight wrinkles, ×: Clear wrinkles, tears, and / or peeling.

Reference Example 1 Production of Thermoplastic Polymer (I) As the thermoplastic polymer (I), an MMA / MA copolymer (MMA / MA = 90/10, reduced viscosity 0.06 L /
g) was prepared.

(Reference Example 2) Production of rubber-containing polymer (II) In a nitrogen atmosphere, deionized water 2 was placed in a reaction vessel equipped with a reflux condenser.
After adding 44 parts and raising the temperature to 80 ° C., and adding (a) shown below, while stirring, the polymer (II-
1/15 of the monomer mixture (b) of A) was charged and held for 15 minutes. Thereafter, the remainder of (b) was continuously added so that the rate of increase of the monomer mixture per hour with respect to water was 8%. Then, the mixture is kept for 1 hour, and the polymer (II-A)
Latex was obtained.

Next, 0.6 part of sodium formaldehyde sulfoxylate was added to the obtained latex, and
Hold for 5 minutes and stir at 80 ° C under nitrogen atmosphere.
The monomer mixture (c) of the polymer (II-B) shown below was continuously added so that the rate of increase of the monomer mixture per hour with respect to water was 4%. Then hold for 2 hours,
The rubber polymer (II-B) was polymerized to obtain an elastic polymer latex.

Subsequently, 0.4 parts of sodium formaldehyde sulfoxylate was added to the obtained elastic polymer latex, and the mixture was maintained for 15 minutes. The monomer mixture (d) of the outermost layer polymer (II-C) shown below was continuously added so that the rate of increase of the body mixture per hour was 10%. Thereafter, the mixture is held for 1 hour, and the outermost layer polymer (II-C)
Was carried out to obtain a latex of the rubber-containing polymer (II). The average particle diameter of the obtained rubber-containing polymer (II) was 0.28 μm.

Thereafter, the latex of the rubber-containing polymer (II) is subjected to coagulation, coagulation, and solidification reactions using calcium acetate, followed by filtration, washing with water and drying, followed by drying.
Got.

(A) Sodium formaldehyde sulfoxylate 0.6 part Ferrous sulfate 0.00012 part Disodium ethylenediaminetetraacetate 0.0003 part (b) MMA 22.0 parts BA 15.0 parts St 3.0 Part AMA 0.4 part 1.3BD 0.14 part tBH 0.18 part Sodium hydroxide of mono (polyoxyethylene nonyl phenyl ether) phosphoric acid 40% and di (polyoxyethylene nonyl phenyl ether) phosphoric acid 60% 1.0 part (C) BA 50.0 parts St 10.0 parts AMA 0.4 parts 1.3BD 0.14 parts tHH 0.2 parts Mono (polyoxyethylene nonylphenyl ether) Part of a mixture of 40% phosphoric acid and 60% di (polyoxyethylene nonylphenyl ether) phosphoric acid in sodium hydroxide 1.0 part of (d) MMA 57.0 parts MA 3.0 parts nOM 0.3 parts tBH 0.06 parts (Reference Example 3) Production of thermoplastic polymer (III) 200 parts of exchanged water were charged, 1 part of emulsifier potassium oleate and 0.3 part of potassium persulfate were charged. Next, 40 copies of MMA, BA10
Parts, NOM 0.005 part, 65 ° C under nitrogen atmosphere
For 3 hours to complete the polymerization. Subsequently, M
A monomer mixture composed of 48 parts of MA and 2 parts of BA was added dropwise over 2 hours, and after completion of the dropwise addition, the mixture was maintained for 2 hours to complete the polymerization. The obtained latex was added to a 0.25% aqueous sulfuric acid solution, and the polymer was subjected to acid coagulation, followed by dehydration, washing and drying, and the polymer was recovered in powder form. The reduced viscosity η _sp / c of the obtained copolymer was 0.38 L / g.

Reference Example 4 Production of Acrylic Resin Composition (N) 84 parts of the thermoplastic polymer (I) produced in Reference Example 1 and 16 parts of the rubber-containing polymer (II) produced in Reference Example 2 And 2 parts of the thermoplastic polymer (III) produced in Reference Example 3, and an ultraviolet absorber ADK STAB LA-31 (manufactured by Asahi Denka Co., Ltd.)
One part and 0.2 parts of a hindered amine light stabilizer (HALS) ADK STAB LA-57 (manufactured by Asahi Denka Co., Ltd.) were mixed using a Henschel mixer. Then 40mmφ
Is melt-kneaded at a cylinder temperature of 200 to 260 ° C. and a die temperature of 250 ° C. using a screw-type twin-screw extruder (L / D = 26), and pelletized to form an acrylic resin composition (N).
Got.

The heat deformation temperature of the obtained acrylic resin composition (N) was 92 ° C.

(Example 1) Acrylic resin film (N-
1), Printed film (P-1) The pellet-shaped acrylic resin composition (N) obtained in Reference Example 4 was dried at 80 ° C. for 24 hours, and a φ having a T-die was attached.
Using a film forming machine equipped with a 65 mm non-vent screw type extruder (HME-65 manufactured by Mitsubishi Heavy Industries, Ltd.), a cooling roll and a winding machine, cylinder temperature 200 to 240
The film was produced at a temperature of 250C and a T-die temperature of 250C. At the time of film formation, the acrylic resin composition in a molten state extruded from a slit having a width of 0.5 mm is cast and cooled on a single metal cooling roll, and is wound around a paper tube by a winding machine to form a film. 200 μm acrylic resin film (N-
1) was produced.

The obtained acrylic resin film (N-1)
Were evaluated for total light transmittance, surface gloss, film-forming properties, pencil hardness and heat shrinkage, and the results are shown in Table 1.

Next, on one side of the acrylic resin film (N-1), a picture layer (several to several tens μm) was formed by gravure printing.
m) was printed to produce a print film (P-1).

The obtained printing film (P-1) was placed in a direction in which the printing layer was in contact with the molding material, and a cavity having a projection area of 500 cm ² and a drawing depth of 10 mm attached to an injection molding machine having a mold clamping force of 2.2 MN was used. Set on the surface of the female mold cavity of the vacuum-moldable injection mold that has
Pre-heating time is 10 seconds and 30 seconds by a non-contact heating plate.
After heating the temperature of the printing film (P-1) to 130 ° C. under the conditions, the printing film (P-1) was made to follow the cavity surface by vacuum forming. Next, after closing the mold, AB
S / PC resin (Diaalloy TC manufactured by Mitsubishi Rayon Co., Ltd.)
-7F) was injection molded at a cylinder temperature of 240 ° C. to produce a laminated injection molded product.

[0103] The obtained laminated injection-molded product showed a good molded appearance without any wrinkles, peeling or tearing at the top, side and corners, regardless of the preheating time.

Example 2 Acrylic resin film (N-
2), Printed film (P-2) The pellet-shaped acrylic resin composition (N) obtained in Reference Example 4 was dried at 80 ° C all day and night, and a φ having a T-die was attached.
Using a 65 mm non-vent screw extruder (HME-65 manufactured by Mitsubishi Heavy Industries, Ltd.), a film forming machine equipped with two cooling rolls and a winding machine, and a cylinder temperature of 200 to
A film was formed at 240 ° C. and a T-die temperature of 250 ° C. During film formation, the molten acrylic resin composition extruded from a slit having a width of 0.5 mm is passed between two metal cooling rolls, and the resin is sandwiched in a state without a bank (resin pool) and is not rolled. After the transfer, this was wound around a paper roll by a winder to produce an acrylic resin film (N-2) having a thickness of 200 μm.

The obtained acrylic resin film (N-2)
Were evaluated for total light transmittance, surface gloss, film-forming properties, pencil hardness and heat shrinkage, and the results are shown in Table 1.

Next, except that the acrylic resin film used was changed to (N-2), the printing film (P-1) was used.
Acrylic resin film (N-
A pattern was printed on 2) to produce a print film (P-2).

Using the obtained print film (P-2), a laminated injection-molded product was produced in the same manner as in the case of the print film (P-1). The obtained laminated injection molded product is
Regardless of the preheating time, a good molded appearance without wrinkling, peeling, tearing, or the like was observed on the top surface, side surfaces, and corners.

Example 3 Acrylic resin film (N-
3), Printing film (P-3) Acrylic resin film (N-2) except that the slit width of the T-die of the film forming machine used in the production of the acrylic resin film (N-2) was changed to 0.8 mm. A film was formed in the same manner as in the case of the above to produce an acrylic resin film (N-3).

The obtained acrylic resin film (N-3)
Were evaluated for total light transmittance, surface gloss, film-forming properties, pencil hardness and heat shrinkage, and the results are shown in Table 1.

Next, except that the acrylic resin film used was changed to (N-3), the printing film (P-1) was used.
Acrylic resin film (N-
A pattern was printed on 3) to produce a print film (P-3).

Using this printing film (P-3),
Laminated injection molded articles were manufactured in the same manner as in the case of the print film (P-1). The obtained laminated injection-molded product showed a good molded appearance without any wrinkles, peeling, tearing or the like on the top surface, side surfaces and corners, regardless of the preheating time.

Example 4 Acrylic resin film (N-
4) Printed film (P-4) Except for changing the slit width of the T-die of the film forming machine used to manufacture the acrylic resin film (N-1) to 1.5 mm and reducing the film take-up speed. A film was formed in the same manner as in the case of the acrylic resin film (N-1) to produce an acrylic resin film (N-4).

Acrylic resin film obtained (N-4)
Were evaluated for total light transmittance, surface gloss, film-forming properties, pencil hardness and heat shrinkage, and the results are shown in Table 1.

Next, except that the acrylic resin film used was changed to (N-4), the printing film (P-1) was used.
Acrylic resin film (N-
The pattern was printed on 4) to produce a print film (P-4).

Using this print film (P-4),
Laminated injection molded articles were manufactured in the same manner as in the case of the print film (P-1). When the pre-heating time was 30 seconds, the obtained laminated injection-molded product showed a good molded appearance without wrinkling, peeling, tearing or the like on the top surface, side surfaces and corners. , Preheating time is 10
In the case of seconds, slight wrinkles occurred on the top surface.

Example 5 Laminated Sheet (S-1) A pattern was printed on a 200 μm thick ABS resin calendar sheet manufactured by Sanbo Resin Kogyo Co., Ltd. in the same manner as in the case of the print film (P-1). Printing AB having a printing layer on the surface
An S sheet was prepared. Next, an acrylic resin film (N-2) was heat-laminated on the printed layer side of the printed ABS sheet, and a laminated sheet (S-
1) was produced.

Next, using the laminated sheet (S-1), the AB film is formed in the same manner as in the case of the print film (P-1).
The S sheet side was arranged at a position in contact with the molding resin, and a laminated injection molded product was manufactured. The obtained laminated injection-molded product shows a good molded appearance without any wrinkles, peeling or tearing at the top surface, side surfaces and corners, regardless of the preheating time. No interfacial peeling of the laminated sheet occurred in each step of the injection molding.

Comparative Example 1 Acrylic resin film (T-
1) Printed film (A-1) Acrylic resin film (N-1) except that the slit width of the T-die of the film forming machine used in the production of acrylic resin film (N-1) was changed to 2.0 mm. A film was formed in the same manner as in the above case, and an acrylic resin film (T-1) was manufactured.

The obtained acrylic resin film (T-1)
Were evaluated for total light transmittance, surface gloss, film-forming properties, pencil hardness and heat shrinkage, and the results are shown in Table 1.

Next, the printing film (P-1) was changed except that the acrylic resin film used was changed to (T-1).
Acrylic resin film (T-
A pattern was printed on 1) to produce a printed film (A-1).

Using this printing film (A-1),
Laminated injection molded articles were manufactured in the same manner as in the case of the print film (P-1). In the obtained laminated injection-molded product, wrinkles occurred on the side surface and the corner at any preheating time.

(Comparative Example 2) Acrylic resin film (T-
2), Printing film (A-2) From the manufacturing conditions of the acrylic resin film (N-2), gradually reduce the distance between the two cooling rolls, and a bank (resin pool) is formed on the T-die side of the cooling rolls. The conditions for formation were set.

A film was formed under these conditions to produce an acrylic resin film (T-2).

Acrylic resin film obtained (T-2)
Were evaluated for total light transmittance, surface gloss, film-forming properties, pencil hardness and heat shrinkage, and the results are shown in Table 1.

Next, the printing film (P-1) was changed except that the acrylic resin film used was changed to (T-2).
Acrylic resin film (T-2) in the same manner as in
The pattern was printed on the substrate to produce a print film (A-2).

Using this printing film (A-2),
Laminated injection molded articles were manufactured in the same manner as in the case of the print film (P-1). In the obtained laminated injection-molded product, wrinkles occurred on the side surface and the corner at any preheating time.

Comparative Example 3 Laminated Sheet (V-1) The acrylic resin film used was changed from (N-2) to (T-
A laminated sheet (V-1) in which an acrylic resin film was laminated on a printed ABS sheet was manufactured in the same manner as in the case of the laminated sheet (S-1) except that the method was changed to 2).

Next, using this laminated sheet (V-1), AB AB was produced in the same manner as in the case of the laminated sheet (S-1).
The S sheet side was arranged at a position in contact with the molding resin, and a laminated injection molded product was manufactured. In the obtained laminated injection molded product, peeling occurred between the acrylic resin film and the ABS sheet layer at any preheating time.

Table 1 shows the evaluation results obtained as described above.

[0130]

[Table 1]

The following is clear from the above Examples and Comparative Examples.

First, an acrylic resin film (N-1)
To (N-4) each had a heat shrinkage of 10% or less after heat treatment in a 100 ° C. atmosphere for 10 minutes, and a laminated injection-molded product using these exhibited good molded appearance.
In particular, acrylic resin films (N-1) to (N-3)
All showed good molding appearance without wrinkling, peeling and tearing in a short preheating time.

Second, acrylic resin film (T-1)
And (T-2) each have a heat shrinkage of more than 10% after heat treatment in a 100 ° C. atmosphere for 10 minutes. Wrinkles of the acrylic resin film occur in the part,
The design was insufficient.

Third, in the laminated injection-molded article manufactured by using the laminated sheet (S-1), no delamination occurs between the acrylic resin film and the ABS sheet layer, and a good molded appearance is obtained. showed that.

Fourth, in a laminated injection-molded article manufactured by using the laminated sheet (V-1), interfacial peeling occurs between the acrylic resin film and the ABS sheet layer, resulting in insufficient design. Was.

[0136]

As is clear from the above description, 100
The heat shrinkage after the heat treatment for 10 minutes in an atmosphere at 10 ° C. is 10% or less. The preheating time can be reduced without causing any trouble.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C08L 51:00) C08L 51:00) B29K 33:00 B29K 33:00 B29L 9:00 B29L 9:00 ( 72) Inventor Hideyuki Fujii 20-1 Miyuki-cho, Otake City, Hiroshima Prefecture F-term in Otake Works, Mitsubishi Rayon Co., Ltd. (Reference) 4F071 AA33 AA33X AA76 AA77 AF25Y AF61Y AH03 AH07 AH19 BA01 BB06 BC01 BC10 BC12 BC17 4F100 AK25A AL04A AL AL09A AT00B BA02 BA07 EC18 EJ17 EJ42 GB08 GB33 JA03A JL02 YY00A 4F206 AA13 AA28 AD08 AD09 AD20 AG03 AH42 JA07 JB13 JB19 JF05 4J002 BG051 BG053 BG061 BG063 BN122 FD040 FD050

Claims (10)

[Claims] 1. A heat shrinkage rate after heat treatment for 10 minutes in a 100 ° C. atmosphere is 10% or less, and 10 μm to 500 μm.
An acrylic resin film having a thickness of not more than m. 2. The acrylic resin film according to claim 1, wherein the pencil hardness (measured according to JIS K 5400) is H or higher. 3. The acrylic resin film comprises 75 to 94.5 parts by mass of a thermoplastic polymer (I);
5.5 to 25 parts by mass of a rubber-containing polymer (I
The thermoplastic polymer (I) is produced from an acrylic resin composition containing the methacrylate and the acrylate.
A monomer mixture (I) comprising at most 49% by mass of at least one of a vinyl monomer copolymerizable with at least one of the alkyl methacrylate and the alkyl acrylate. The polymer has a reduced viscosity (0.1 g of polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) of 0.1 L / g or less, obtained by polymerization,
The rubber-containing polymer (II) has a multilayer structure of two or more layers including an elastic inner layer and a hard outer layer, and the elastic inner layer mainly has an elasticity (co-form) obtained by polymerizing an alkyl acrylate. The hard outer layer has one or more layers made of a polymer mainly obtained by graft polymerization of alkyl methacrylate in the presence of the elastic (co) polymer. 3. The acrylic resin film according to claim 1, wherein the acrylic resin film has at least two layers. 4. 100 parts by mass of the acrylic resin composition contains 0.1 to 10 parts by mass of a thermoplastic polymer (III), and the thermoplastic polymer (III)
Is a monomer mixture (III) comprising 50% by mass or more of methyl methacrylate and 50% by mass or less of one or more vinyl monomers copolymerizable with the methyl methacrylate.
Having a reduced viscosity (dissolve 0.1 g of polymer in 100 mL of chloroform and measured at 25 ° C.) of 0.2 L
/ G. 5. The acrylic resin film according to claim 1, which is melt-extruded from a T die having a slit width of 1 mm or less. 6. The acrylic resin film according to claim 5, wherein the film is formed by contacting with one metal roll after the melt extrusion. 7. After being melt-extruded from a T-die, it is substantially rolled by being pinched by a plurality of metal rolls, non-metal rolls and / or metal belts without substantially any bank (resin pool). The acrylic resin film according to any one of claims 1 to 5, wherein the film is formed by performing surface transfer without forming. 8. A laminated sheet comprising the acrylic resin film according to claim 1 and a base sheet. 9. A laminated injection-molded product obtained by laminating the acrylic resin film according to claim 1 on an injection-molded product. 10. A laminated injection molded product obtained by laminating the laminated sheet according to claim 8 on an injection molded product.