JPH10237261A - Matte acrylic film and matte molded product laminated with acrylic film - Google Patents

Abstract

(57) [Abstract] [Problem] A matte appearance with excellent luxury and depth.
Obtaining an acrylic film without gloss and a molded article using the same. SOLUTION: The thermoplastic polymer (I) 0 to 10 parts by weight,
Consisting of 5.5 to 25 parts by weight of a rubber-containing polymer (II) and 65 to 94.5 parts by weight of a thermoplastic polymer (III),
The total of (I), (II) and (III) is 100 parts by weight, and the proportion of the elastic (co) polymer in the rubber-containing polymer (II) is (I), (II) and (III). 5 to 18% by weight of the total, and the surface gloss is 10% to 100%,
A matte acrylic film for an acrylic laminated molded product having a thickness of 300 μm or less and a matted molded product obtained by laminating the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylic laminated molded product obtained by laminating and bonding a specific acrylic film, and an acrylic film used for producing such a molded product.

[0002]

2. Description of the Related Art There are an in-mold molding method and a press molding method as a method for imparting a design property to a molded product at low cost.
The in-mold molding method inserts a printed sheet or film of polyester resin, polycarbonate resin, acrylic resin, etc. into a three-dimensional shape by vacuum molding or the like before or without molding, into an injection mold. Then, a resin serving as a base material is injection-molded, and there are a case where a resin sheet or a film is integrated with a base resin and a case where only printing is transferred.

In the press molding method, a printed sheet or film of a polyester resin, a polycarbonate resin, an acrylic resin, or the like is placed on the surface of a base resin plate or a molded product in the presence or absence of an adhesive, It is a method of integrating with a heating press.

On the other hand, acrylic films are used for protecting surfaces of polycarbonate, vinyl chloride, etc. due to their excellent transparency and weather resistance. However, since the thickness is 300 μm or less, it is difficult to form a film without flexibility, and there is a problem that the surface hardness is low.

For example, an acrylic resin composition having excellent transparency, weather resistance and film moldability is disclosed in Japanese Patent Application Laid-Open No. 63-779.
No. 63 is disclosed. However, there is no mention of the particle size of the rubber-containing polymer, and the particle size of the rubber-containing polymer obtained in the examples is 0.15 μm or less. Further, since the amount of the rubber-containing polymer added was substantially 28% by weight or more, the surface hardness was inferior.

As a means for matting the surface of a molded article, there is a method of transferring the surface by using a mat or press mold having a matte surface.

[0007]

A molded article obtained by laminating an acrylic film by in-mold molding is excellent in a sense of depth and luxury like a molded article subjected to coating treatment. However, in general, an acrylic film has a surface hardness and heat resistance. However, there are drawbacks such as insufficient insufficiency, easy formation of a molded article, and poor surface appearance when exposed to high temperatures.

In addition, in in-mold molding using a mat having a matte surface and press molding using a mold having a matte surface, a good mat state is obtained immediately after molding. However, there is a problem that the surface gloss increases when exposed to high temperatures.

An object of the present invention is to provide an acrylic film having excellent surface hardness and matting properties and a molded article using the acrylic film.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the particle size of the rubber-containing polymer which has been conventionally used for acrylic films has been increased. By using a smaller amount of a rubber-containing polymer having a specific particle size than before, it has been found that an acrylic film having excellent surface hardness can be obtained. It has been found that a molded article free from defects can be obtained, and the present invention has been achieved.

That is, the gist of the present invention is as follows.
0 to 10 parts by weight of the thermoplastic polymer (I), 5.5 to 25 parts by weight of the rubber-containing polymer (II) and the thermoplastic polymer (II)
I) 65 to 94.5 parts by weight, wherein the total of (I), (II) and (III) is 100 parts by weight, and the proportion of the elastic (co) polymer in the rubber-containing polymer (II) is (I), (I
A matte acrylic film for an acrylic laminated molded product having a thickness of 300 μm or less, which is 5 to 18% by weight of the total of I) and (III) and a surface gloss of 10% to 100%, and a matte molding obtained by laminating the same In the goods.

The thermoplastic polymer (I) is obtained by polymerizing 50 to 100% by weight of methyl methacrylate and 0 to 50% by weight of at least one other vinyl monomer copolymerizable therewith. Viscosity (0.1 g of polymer
Dissolved in 100 mL of chloroform and measured at 25 ° C.) exceeds 0.2 L / g.

Rubber-containing polymer (II) 50 to 99.9% by weight of alkyl acrylate, 0 to 49.9% by weight of other copolymerizable vinyl monomer, and 0 of copolymerizable crosslinkable monomer 100 to 100 parts by weight of an elastic (co) polymer obtained by polymerizing 0.1 to 10% by weight, and 50 to 100% by weight of a methacrylate ester, and a vinyl monomer 0 to 50 copolymerizable therewith. A polymer in which 10 to 400 parts by weight of a monomer or a mixture thereof is bound,
And a rubber-containing copolymer having a particle size of 0.2 μm to 0.4 μm.

Thermoplastic polymer (III) 50 to 100% by weight of a methacrylate having an alkyl group having 1 to 4 carbon atoms, and 0 to 50% of an acrylate
% Of at least one vinyl monomer copolymerizable therewith is obtained by polymerization of 0 to 49% by weight, and its reduced viscosity (0.1 g of a polymer dissolved in 100 mL of chloroform, Is 0.1 L / g or less.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The acrylic film according to the present invention can be obtained as a roll having a thickness of 300 μm or less, and has not been subjected to an operation such as crosslinking as a means for increasing the surface hardness. It is excellent in secondary workability such as bending and the like, and is most suitable for production of an acrylic laminated molded product.

The thermoplastic polymer (I) used in the present invention
Is 50 to 100% by weight of methyl methacrylate and at least one of other vinyl monomers copolymerizable therewith.
0% by weight of the polymer, and its reduced viscosity (polymer 0.
1 g is dissolved in 100 mL of chloroform and measured at 25 ° C.) is a thermoplastic polymer exceeding 0.2 L / g, and is a component that improves the film-forming property. Film formation is possible without using the thermoplastic polymer (I),
Since the melt tension decreases, it is impossible to form the film without lowering the discharge amount during film formation and lowering the resin temperature, and the productivity becomes worse and the thickness unevenness of the film increases. preferable.

The reduced viscosity of the thermoplastic polymer (I) is important. If the reduced viscosity is 0.2 L / g or less, a film having good thickness accuracy cannot be obtained. The reduced viscosity of the thermoplastic polymer (I) used is usually more than 0.2 L / g and 2
L / g or less, preferably 1.2 L / g or less.

The thermoplastic polymer (I) used in the present invention
In the above, as a vinyl monomer copolymerizable with methyl methacrylate, an alkyl acrylate, an alkyl methacrylate, an aromatic vinyl compound, a vinyl cyanide compound and the like can be used. The polymerization is preferably performed by an emulsion polymerization method, and the polymer can be recovered in a powder form by a usual emulsion polymerization method and a post-treatment method.

The rubber-containing polymer (II) used in the present invention
Is a graft copolymer having an effect of imparting excellent impact resistance and elongation to a resin composition and having a multilayer structure containing an alkyl acrylate as a main component of rubber.

The rubber-containing polymer (II) used in the present invention
Consists of 50 to 99.9% by weight of an alkyl acrylate, 0 to 49.9% by weight of another copolymerizable vinyl monomer and 0.1 to 10% by weight of a copolymerizable crosslinkable monomer. An elastic body is obtained by polymerizing the monomer mixture, and in the presence of 100 parts by weight of the obtained elastic (co) polymer, 50 to 100% by weight of a methacrylate ester and a vinyl monomer copolymerizable therewith It is obtained by polymerizing 10 to 400 parts by weight of a monomer comprising 0 to 50% by weight or a mixture thereof in at least one stage.

As the alkyl acrylate used here, those having 1 to 8 carbon atoms in the alkyl group can be used, and among them, butyl acrylate, 2-ethylhexyl acrylate and the like are preferable. In obtaining an elastic (co) polymer, 49.9% by weight or less of another copolymerizable vinyl monomer can be copolymerized. As the vinyl monomer used herein, methyl methacrylate, butyl methacrylate, alkyl methacrylate such as cyclohexyl methacrylate, styrene,
Acrylonitrile and the like are preferred. Further, in the present invention, a copolymerizable crosslinkable monomer is used. 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.

As the monomer to be grafted onto the elastic (co) polymer, at least 50% by weight of methacrylate is used. Specifically, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate are used. And cyclohexyl methacrylate.
Further, 50% by weight or less of a copolymerizable vinyl monomer is used, and these are not particularly limited, but specifically, methyl acrylate, butyl acrylate,
Examples include alkyl acrylates such as cyclohexyl acrylate, styrene and acrylonitrile.
The monomer mixture to be grafted is an elastic (co) polymer 10
10 to 400 parts by weight, preferably 20 parts by weight, per 0 parts by weight
２００200 parts by weight are used, and the polymerization can be performed in at least one stage. If the amount of the monomer mixture to be grafted is less than 10 parts by weight with respect to 100 parts by weight of the elastic (co) polymer, transparency is deteriorated due to aggregation of the elastic (co) polymer, which is not preferable.

The rubber-containing polymer (II) used in the present invention
Has a particle diameter of 0.2 to 0.4 μm, preferably 0.25 to 0.35 μm. The rubber-containing polymer (II) can be obtained by ordinary emulsion polymerization. Particle size 0.2
If it is less than μm, the film obtained becomes brittle with the use amount of the rubber-containing polymer (II) of the present invention, and film formation becomes impossible. When the particle diameter exceeds 0.4 μm, the elongation of the film decreases.

The thermoplastic polymer (II) used in the present invention
I) includes 50 to 100% by weight of a methacrylate having an alkyl group having 1 to 4 carbon atoms, 0 to 50% by weight of an acrylate, and at least one other vinyl monomer copolymerizable therewith. Obtained by polymerizing 0 to 49% by weight;
The reduced viscosity (0.1 g of polymer was added to 100 m of chloroform)
Dissolved in L and measured at 25 ° C.) is 0.1 L / g or less. If the reduced viscosity of the thermoplastic polymer (III) exceeds 0.1 L / g, the melt viscosity of the film raw material resin becomes too high, resulting in poor film-forming properties. Further, the reduced viscosity of the thermoplastic polymer (III) is preferably at least 0.05 L / g. When it is lower than 0.05 L / g, the film becomes too brittle, and the film tends to break during film formation and printing.

As the methacrylate used in the thermoplastic polymer (III), methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like can be used, but methyl methacrylate is most preferred. As the acrylate, methyl acrylate, ethyl acrylate, butyl acrylate and the like can be used. The acrylate is in the range of 0 to 50% by weight, preferably 0.1 to 40% by weight.
Used in the range of weight percent. Known monomers can be used as other copolymerizable vinyl monomers.

The method for polymerizing the thermoplastic polymer (III) is not particularly limited, but it can be carried out by a usual method such as suspension polymerization, emulsion polymerization, or bulk polymerization. It is necessary to use a chain transfer agent in order to limit the viscosity in the present invention. Known chain transfer agents can be used,
Preferred are mercaptans. The amount of chain transfer agent is
It is necessary to appropriately determine the type and composition of the monomer.

The acrylic film of the present invention is a film comprising the thermoplastic polymer (I), the rubber-containing polymer (II) and the thermoplastic polymer (III) thus obtained.

In the present invention, the thermoplastic polymer (I) is used in an amount of 0 to 10 parts by weight. Film formation is possible without using the thermoplastic polymer (I),
In order to obtain sufficient film formability, it is preferable to use the compound in an amount of 0.1 part by weight or more. If the amount exceeds 10 parts by weight, the viscosity of the resin composition comprising the thermoplastic polymer (I), the rubber-containing polymer (II) and the thermoplastic polymer (III) becomes too high, and the film-forming property deteriorates.

The rubber-containing polymer (II) is used in an amount of 5.5 to 25 parts by weight. In particular, the proportion of the elastic (co) polymer in the rubber-containing polymer (II) is determined by the ratio of the polymer (I) or (II). ) And (II
It must be from 5 to 18% by weight of the total of I). When the proportion of the elastic (co) polymer is less than 5% by weight, the film becomes brittle and the film cannot be formed. When the proportion of the elastic (co) polymer exceeds 18% by weight, the surface hardness decreases.

The acrylic film of the present invention contains inorganic particles and / or organic cross-linked particles having an average particle size of 0.5 to 20 μm, or a linear polymer (IV) having a hydroxyl group.
It is preferable to add 0 parts by weight to obtain a matte film. The gloss of the film can be appropriately selected depending on its design effect, but a film having a surface gloss of 10% to 100% is preferable. As the inorganic particles to be used, mica, talc and the like are preferable from the viewpoint of matting effect. Examples of the organic cross-linked particles include cross-linked polystyrene particles, cross-linked polymethyl methacrylate particles, cross-linked polyurethane particles, cross-linked silicone particles, and the like. Cross-linked polymethyl methacrylate particles are preferable because they do not impair transparency.

The linear polymer having a hydroxyl group (IV) used in the present invention is a hydroxyalkyl acrylate having 1 to 8 carbon atoms and / or a hydroxyalkyl methacrylate of 1 to 80% by weight, 10 to 99% by weight of an alkyl methacrylate having 1 to 13 carbon atoms of an alkyl group, 0 to 79% by weight of an alkyl acrylate having 1 to 8 carbon atoms of an alkyl group, and other copolymerizable vinyl monomers. It is obtained by polymerizing at least one kind of 0 to 50% by weight, and the reduced viscosity of the polymer (0.1 g of the polymer is dissolved in 100 mL of chloroform,
(Measured at 25 ° C.) in the range of 0.05 to 0.3 L / g.

The hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate used for the linear polymer (IV) having a hydroxyl group include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and methacrylic acid. 2,3-dihydroxypropyl acid, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate and the like. Among these, 2-hydroxyethyl methacrylate is particularly preferred. Hydroxyalkyl acrylate, or /
And the amount of the hydroxyalkyl methacrylate used is in the range of 1 to 80% by weight. If it is less than 1% by weight, the matting effect is insufficient. On the other hand, if it exceeds 80% by weight, the elongation may be lowered or the surface state may be poor. The preferable use range for the development of the matting property is 5 to 5
0% by weight. More preferably, it is used in the range of 20 to 50% by weight.

Examples of the alkyl methacrylate include:
Lower alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate are preferred, and methyl methacrylate is particularly preferred. It is necessary that the amount of the alkyl methacrylate used is in the range of 10 to 99% by weight. Preferably, it is used in the range of 30 to 85% by weight.

79% by weight of alkyl acrylate
Can be used up to, specifically, methyl acrylate,
Ethyl acrylate, butyl acrylate, acrylic acid 2-
Lower acrylate alkyl esters such as ethylhexyl are preferred. 0.5 to 4 acrylic acid alkyl esters
It is preferable to use it in the range of 0% by weight. More preferably, it is 5 to 25% by weight.

Further, in the linear polymer (IV) having a hydroxyl group used in the present invention, at least one of other vinyl monomers can be used in a range of up to 50% by weight. Specifically, known monomers can be used, for example, styrene, vinyl toluene, α-methyl styrene, vinyl aromatic monomers such as halogenated styrene, methacrylic acid, fumaric acid, maleic acid and copolymerizable carboxylic acid and Among the esters, alkyl groups having 1 to 13 carbon atoms, methacrylic acid alkyl esters, alkyl groups having 1 to 1 carbon atoms
8, excluding alkyl acrylates, vinyl halides such as vinyl chloride and vinyl bromide, vinyl esters such as vinyl acetate, and acrylonitrile.

In the present invention, the intrinsic viscosity of the hydroxyl group-containing linear polymer (IV) is adjusted to 0.05 to 0.3 L / g in order to exhibit a constant good matting property irrespective of the shaping conditions. It is necessary to adjust to the range. Specifically, a polymerization degree regulator such as mercaptan is used. As the mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and the like are used, but not particularly limited thereto, and known ones can be used. The shaping conditions referred to in the present invention are the conditions of the step of melting and kneading the acrylic resin, the linear polymer, the additives, and the like, and the conditions of the step of processing the obtained mixture into a molded product such as a film. Pointing to that.

The method for producing the linear polymer (IV) having a hydroxyl group used in the present invention is not particularly limited, but a method by suspension polymerization is preferred from the viewpoint of cost. As the initiator for suspension polymerization, those used in ordinary suspension polymerization are used, and examples thereof include organic peroxides and azo compounds.
As the suspension stabilizer, those usually used are used, and organic colloidal polymer substances, inorganic colloidal polymer substances,
Examples thereof include inorganic fine particles and combinations of these with a surfactant. The suspension polymerization is usually carried out by aqueous suspension of monomers together with a polymerization initiator in the presence of a suspension stabilizer. In addition, the polymerization can be carried out by dissolving a polymer soluble in the monomer in the monomer.

The amount of the hydroxyl group-containing linear polymer (IV) thus obtained is in the range of 1 to 20 parts by weight. In order to obtain good matting properties, it is preferable to use 2.0 parts by weight or more. When the linear polymer (IV) having a hydroxyl group is used, unlike the case where inorganic particles and / or organic crosslinked particles are used, physical properties such as elongation of the film are hardly deteriorated. Therefore, the film can be used satisfactorily even in the in-mold molding or the like that requires the vacuum forming of the film in advance without causing the film to break.

The acrylic film of the present invention may contain, if necessary, a general compounding agent such as a stabilizer, a lubricant, a processing aid,
It may contain a plasticizer, an impact aid, a foaming agent, a filler, a colorant, an ultraviolet absorber and the like. In particular, from the viewpoint of protecting the substrate, it is preferable that an ultraviolet absorber is added to impart weather resistance. The molecular weight of the ultraviolet absorber used is preferably 300 or more, and particularly preferably 400 or more. If an ultraviolet absorber having a molecular weight of less than 300 is used, it may volatilize during vacuum molding or air pressure molding in an injection mold, causing mold contamination. The type of the ultraviolet absorber is not particularly limited, but may be a benzotriazole-based compound having a molecular weight of 400 or more or a
A triazine type of at least 00 can be particularly preferably used. Specific examples of the former include Tinuvin 234 manufactured by Ciba-Geigy Corporation, Adecastab LA-31 manufactured by Asahi Denka Kogyo, and specific examples of Tinuvin 1577 manufactured by Ciba-Geigy Corporation.
And the like. The UV absorber is preferably contained in the acrylic film in a range of 0.1 to 5% by weight.

The heat distortion temperature (measured based on ASTM D648) of the acrylic film of the present invention is preferably 80 ° C. or higher. When the heat distortion temperature is less than 80 ° C,
When the acrylic laminated molded article is heated, surface roughness may occur due to residual stress. Furthermore, when used for vehicle applications, if the heat deformation temperature is 100 ° C or higher, it can be used near the handle part, and if it is 110 ° C or more, it can be used near the meter panel part. More preferred.

The heat deformation temperature of the acrylic film of the present invention depends on the amount of the rubber-containing polymer (II) used, but is mainly determined by the heat deformation temperature of the thermoplastic polymer (III) used in the present invention. . The heat distortion temperature of the thermoplastic polymer (III) can be adjusted by adjusting the monomer composition of the thermoplastic polymer (III) by a known method.
Although it depends on various conditions, for example, when methyl acrylate is used as a copolymer component, the heat distortion temperature is 8
When the temperature is 0 ° C. or higher, a thermoplastic polymer (III)
The content of methyl methacrylate in the content is 88% by weight or more,
When the heat distortion temperature is 100 ° C. or higher, the methyl methacrylate content in the thermoplastic polymer (III) is 95%.
It can be adjusted by adjusting it to not less than% by weight. When the heat distortion temperature is set to 110 ° C. or more, maleimides such as maleic anhydride and phenylmaleimide, glutarimides, glutaric anhydrides, α-methylstyrene, and the like are commonly used in the thermoplastic polymer (III). It needs to be polymerized.
Of course, even when the heat distortion temperature is 80 ° C. or more and 100 ° C. or more, it is possible to reduce the content of methyl methacrylate by copolymerizing maleimides such as maleic anhydride and phenylmaleimide.

As a method for producing the acrylic film of the present invention, any method such as a T-die method and an inflation method may be used, but the T-die method is preferred from the viewpoint of economy. In particular, when the thermoplastic resin mixture in the molten state is cooled and solidified, it is in contact with only one metal roll at the same time without being pinched by two metal rolls, thereby controlling the thickness and transferring the surface. Then, it is preferable to manufacture by cooling and solidifying.

As an acrylic film as a substitute for painting, a film printed by an appropriate printing method as necessary is usually used in order to impart a design property to a molded product. In this case, it is preferable to use an acrylic film that has been subjected to a one-sided printing process, and it is preferable to dispose the printing surface on the adhesive surface with the base resin at the time of molding from the viewpoint of protecting the printing surface and imparting a sense of quality. In addition, when utilizing as a substitute for a transparent coating utilizing the color tone of the plastic as a base material, it can be used without printing. In particular, for applications utilizing the color tone of the base material, an acrylic film is
Compared to vinyl chloride and polyester films, they are superior in depth and luxury.

Further, a colored product may be used if necessary.

The thickness of the acrylic film is 300 μm or less, preferably 100 μm to 300 μm. 1
If the thickness is less than 00 μm, a sufficient depth cannot be obtained as a molded product appearance. Particularly when forming into a complicated shape, a sufficient thickness cannot be obtained by stretching. Further, when the thickness is more than 300 μm, the rigidity is increased, so that the laminating property, the secondary processing property, etc. are deteriorated and the film cannot be used. In addition, the weight per unit area increases, which is economically disadvantageous. Further, it is difficult to form a film, and a film cannot be stably manufactured.

In order to form a coating film having a sufficient thickness on a molded product by coating, a dozen or more recoatings are required, which is costly and extremely deteriorates productivity. In the case of an acrylic laminated molded product, since the acrylic film itself becomes a coating film, a very thick coating film can be easily formed, which is industrially advantageous.

The acrylic film of the present invention is laminated and adhered to a resin as a base material to form an acrylic laminated matte molded product. As a method of producing the acrylic laminated matte molded article, a method of subjecting an acrylic film to vacuum molding or pressure molding in an injection molding mold and then injection molding a resin as a base material, or a method of forming an acrylic film on a base resin sheet And the like, and a method of hot pressing is preferred.

The resin constituting the base material constituting the molded article of the present invention must be capable of being melt-bonded to an acrylic film, and may be made of ABS resin, AS resin, styrene resin,
Polycarbonate resin, vinyl chloride resin, acrylic resin, polyester resin or a resin containing these as a main component is exemplified. However, in terms of adhesiveness, ABS resin, AS resin, polycarbonate resin, vinyl chloride resin or a resin containing these resins as a main component is used. Is preferable, and more preferably, an ABS resin, a polycarbonate resin, or a resin containing these as a main component can be used. The use of an adhesive is not limited to this, and polyolefins such as polypropylene and polyethylene, and celluloses such as wood and paper can also be used.

The matte molded product obtained by laminating the acrylic film of the present invention is suitable for applications such as home appliances, automobile interiors / exteriors, equipment, and building materials.

[0050]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples. In the examples, "parts" means "parts by weight" as "%".
Represents "% by weight". Abbreviations in the examples are as follows.

Methyl methacrylate MMA Methyl acrylate MA Butyl acrylate BuA Allyl methacrylate AMA Styrene St Ethyl acrylate EA 2-Hydroxyethyl methacrylate HEMA Cumene piperoxide CHP n-octyl mercaptan NOM The obtained thermoplastic polymer (I) ( III), the rubber-containing polymer (II), the linear polymer (IV) and the film were measured for various physical properties by the following test methods.

1) Reduced Viscosity of Thermoplastic Polymers (I) and (III) and Linear Polymer (IV) 0.1 g of a polymer was dissolved in 100 mL of chloroform.
It was measured at 5 ° C.

2) Particle Size of Rubber-Containing Polymer (II) The final particle size of the polymer latex of the rubber-containing polymer (II) obtained by emulsification was determined by using a light scattering photometer DLS- manufactured by Otsuka Electronics Co., Ltd. The measurement was carried out by a dynamic light scattering method using No. 700.

3) Surface gloss of film and molded article after heat test The surface gloss of the film was measured using a gloss meter (Model GM-26D, manufactured by Murakami Color Research Laboratory).
The surface gloss at 0 ° was measured.

4) Heating Test of Molded Article The molded article was heated in a heating furnace at 110 ° C. for 4 hours, and after cooling, the surface gloss of the surface on which the film was laminated was measured.

(Examples 1 to 11, Comparative Examples 1 and 2) Table 1 shows the evaluation results of the films and molded products obtained by the following methods.

(A) Production of thermoplastic polymer (I) A reaction vessel was charged with 200 parts of ion-exchanged water substituted with nitrogen, and 1 part of an emulsifier, potassium oleate, and 0.3 part of potassium persulfate were charged. Then 40 parts of MMA, BuA10
Parts, NOM 0.005 parts, 65 ° C under nitrogen atmosphere
For 3 hours to complete the polymerization. Then MM
A monomer mixture comprising 48 parts of A and 2 parts of BuA was added dropwise over 2 hours, and after completion of the 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 with water, and drying.
The polymer was recovered in powder form. The reduced viscosity ηsp / c of the obtained copolymer was 0.38 L / g.

(B) Production of Rubber-Containing Polymer (II) Into a reaction vessel, the raw materials shown in the following (a) and (b) are charged in half amounts, and stirred at 80 ° C. for 90 minutes in a nitrogen atmosphere. While polymerizing. Thereafter, the other half of the raw material of (b) was continuously added over 90 minutes, and further added for 120 minutes.
Polymerization was carried out for 1 minute to obtain an elastic latex.

Following the obtained elastomer latex, the following raw material (c) was added and stirred, and then the following raw material (d) was continuously added at 80 ° C. for 45 minutes, and then further added at 80 ° C. For one hour continuously,
A rubber-containing polymer (II) latex was obtained. The particle size of the obtained rubber-containing polymer (II) was 0.29 μm.

The rubber-containing polymer (II) latex is subjected to coagulation, aggregation, and solidification using calcium chloride, followed by filtration,
After washing with water and drying, a rubber-containing polymer (II) was obtained.

(A) Deionized water 300 parts N-acyl sarcosine acid 0.5 parts Boric acid 1.0 parts Sodium carbonate 0.1 parts Sodium formaldehyde sulfoxylate 0.5 parts Ferrous sulfate 0.00024 parts Ethylenediamine Disodium tetraacetate 0.00072 parts (b) BuA 80.0 parts St 19.0 parts AMA 1.0 part CHP 0.3 parts (c) Deionized water 5 parts N-acyl sarcosine acid 1.2 parts (d) 76.6 parts of MMA 3.2 parts of EA 0.28 parts of NOM 0.24 parts of CHP (c) Production of linear polymer having a hydroxyl group (IV) With stirrer, reflux condenser, nitrogen gas inlet, etc. The following mixture was charged into the reaction vessel.

MA 20 parts MMA 60 parts HEMA 20 parts NOM 0.08 parts lauroyl peroxide 1 part tribasic calcium phosphate 5 parts ion-exchanged water 250 parts After sufficiently replacing the inside of the container with nitrogen gas, the mixture of the above mixture is stirred. While heating to 75 ° C., the polymerization was advanced in a nitrogen gas stream. After 2 hours, the temperature was raised to 90 ° C. for another 4 hours.
After 5 minutes, the polymerization was completed, dehydrated and dried to obtain a linear polymer (B).

As a result of measuring the intrinsic viscosity of this linear polymer, it was 0.11 L / g.

(D) Production of acrylic film 4 parts of the thermoplastic polymer (I) obtained as described above,
18 parts of rubber-containing polymer (II), thermoplastic polymer (III)
Methyl methacrylate / methyl acrylate copolymer (methyl methacrylate / methyl acrylate = 98/2,
(Reduced viscosity 0.06 L / g) 78 parts, tinuvin 1577
(Triazine UV absorber manufactured by Ciba-Geigy) 1
Parts and various matting agents were mixed at various ratios shown in Table 1 using a Henschel mixer. Then, using a 40 mmφ screw type 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., and pelletized to obtain a film composition.

The obtained pellets were dried at 80 ° C. for 24 hours, and the cylinder temperature was 200 ° C. to 240 ° C. and the die temperature was 250 ° C. using a 40 mmφ non-vent screw type extruder (L / D = 26) equipped with a 300 mm T die. To form a film having a thickness of 200 μm.

(E) Trial production of press molded product Urethane emulsion adhesive, "VP" manufactured by Nippon Fuller
-10 "and the curing agent" HBF-70 "in a weight ratio of 100:
The mixture obtained in No. 5 was spray-coated on a wooden molded product (MDF in which a veneer was adhered to the surface), an acrylic film was mounted thereon, embossed paper was inserted, and pressure-bonded using a membrane press. The mold temperature was 120 ° C., the mold clamping pressure was 10 kgf / cm ² , and the mold clamping time was 3 minutes.

(F) Trial Production of In-Mold Molded Product An acrylic film was printed and heated at 140 ° C. for 1 minute, and then vacuum-molded using a mold having a vacuuming function.
With the molded film arranged in a mold with embossing,
ABS resin (Diapet ABS30 made by Mitsubishi Rayon)
01M) was injection-molded on the printing surface side to obtain a molded product.

[0068]

[Table 1]

[0069]

According to the present invention, an acrylic film having an inexpensive, easily coated film having a sufficient thickness, an excellent matte appearance, excellent in sense of depth, and having no matte appearance, and a molded product obtained by laminating the same are provided. Obtainable.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Kazuhiko Nakagawa 4-1, Ushikawa-dori, Toyohashi-shi, Aichi Prefecture

Claims (11)

[Claims] 1. A thermoplastic polymer (I) 0 shown below
10 to 10 parts by weight, 5.5 to 25 parts by weight of the rubber-containing polymer (II) and 65 to 94.5 parts by weight of the thermoplastic polymer (III), and the total of (I), (II) and (III) Is 10
0 parts by weight, elasticity (co) in the rubber-containing polymer (II)
The proportion of the polymer is 5 to 18% by weight of the total of (I), (II) and (III), and the surface gloss is 10% to 100%.
%, A matte acrylic film for an acrylic laminated molded product having a thickness of 300 μm or less. Thermoplastic polymer (I) Obtained by polymerizing 50 to 100% by weight of methyl methacrylate and 0 to 50% by weight of at least one other vinyl monomer copolymerizable therewith, and having a reduced viscosity (weight 0.1g
Dissolved in 100 mL of chloroform and measured at 25 ° C.) exceeds 0.2 L / g. Rubber-containing polymer (II) 50 to 99.9% by weight of alkyl acrylate, 0 to 49.9% by weight of other copolymerizable vinyl monomer and 0.1 to 0.1% of copolymerizable crosslinkable monomer A monomer composed of 100 to 100 parts by weight of an elastic (co) polymer obtained by polymerizing 10% by weight, and 50 to 100% by weight of a methacrylate ester and 0 to 50 of a vinyl monomer copolymerizable therewith Or a polymer in which 10 to 400 parts by weight of the mixture is bonded,
And a rubber-containing copolymer having a particle size of 0.2 μm to 0.4 μm. Thermoplastic polymer (III) 50 to 100% by weight of a methacrylate having an alkyl group having 1 to 4 carbon atoms, and 0 to 50% of an acrylate
% Of at least one vinyl monomer copolymerizable therewith is obtained by polymerization of 0 to 49% by weight, and its reduced viscosity (0.1 g of a polymer dissolved in 100 mL of chloroform, Is 0.1 L / g or less. 2. Inorganic particles having an average particle size of 0.5 to 20 μm,
And / or the organic crosslinked particles are (I) + (II) + (II
The matte acrylic film according to claim 1, wherein 1 to 20 parts by weight is added to 100 parts by weight of I). 3. A linear polymer (IV) having a hydroxyl group as shown below is added in an amount of 1 to 20 parts by weight based on 100 parts by weight of (I) + (II) + (III). The matte acrylic film according to claim 1, wherein: Linear polymer having hydroxyl group (IV) Alkyl hydroxyalkyl acrylate having 1 to 8 carbon atoms and / or hydroxyalkyl methacrylate 1 to 80% by weight, methacryl having 1 to 13 carbon atoms of alkyl group 10 to 99% by weight of an acid alkyl ester, 0 to 79% by weight of an alkyl acrylate having 1 to 8 carbon atoms in an alkyl group, and 0 to 50% by weight of at least one other copolymerizable vinyl monomer. The reduced viscosity (0.1 g of a polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) is 0.
A linear polymer having a hydroxyl group in the range of from 0.5 to 0.3 L / g. 4. The matte acrylic film according to claim 1, which contains 0.1 to 5% by weight of an ultraviolet absorber. 5. When cooling and solidifying a thermoplastic resin mixture in a molten state, one metal roll is simultaneously held without being pinched by two metal rolls, thereby being not regulated in thickness and surface transferred. The method for producing a matte acrylic film according to claim 1, wherein the matte acrylic film is cooled and solidified by contact with the matte acrylic film. 6. An acrylic laminated matte-molded article, wherein the acrylic film according to claim 1 is laminated and adhered. 7. The laminated matte acrylic product according to claim 6, wherein the acrylic film is obtained by subjecting the acrylic film to vacuum molding or pressure molding in an injection mold, followed by injection molding of a resin as a base material. 8. The matte acrylic molded article according to claim 6, which is obtained by hot pressing an acrylic film on a base resin sheet. 9. An acrylic laminated mat-molded article according to claim 8, wherein the resin constituting the base material constituting the injection-molded article is an ABS resin, a polycarbonate resin or a resin containing these as a main component. 10. The acrylic laminated mat-molded product according to claim 6, which is obtained by printing on one side of an acrylic film and then laminating a resin serving as a base material on the printed surface side. 11. An adhesive obtained by applying an adhesive to one side of an acrylic film and laminating a substrate on the adhesive side.
An acrylic resin-laminated matte molded product according to claim 6.