JP7207034B2 - matte film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a matte film having good transparency, fine texture and excellent mattness, and a molded product containing the same.

Acrylic films are widely used as protective films laminated on the surfaces of various substrates such as plastics, glass, slates, rubbers, metal plates, and wooden plates because of their excellent weather resistance and transparency. In addition, substrates whose surfaces are protected with acrylic films are used in many applications such as interior and exterior materials for buildings and furniture. However, in recent years, there has been a demand for a more sophisticated image for base materials such as wallpaper and leather furniture that are used indoors, and the use of matte film-laminated base materials is increasing.

The production method of this matte film mainly includes (1) a method of applying fine unevenness to the film surface by means of a metal or rubber mat roll having a roughened surface, followed by thermoforming, and (2) fine particles such as sand or metal. is sprayed onto the surface of the film to be treated to give fine unevenness (sandblasting method), and (3) a method of adding a fine organic or inorganic filler (matting agent) to the resin for constituting the film. ing.

In method (1) for matting a film using a matte roll, there is the problem that the matte roll is easily clogged by additives such as ultraviolet absorbers added to the resin, and that unevenness in the thickness of a thin film becomes uneven gloss as it is, resulting in uniformity. There is a problem that it is difficult to obtain a matte film.
The sandblasting method (2) has a problem that a thin and soft film may stretch or break during sandblasting.

In method (3), in which a matting agent is added to the film-constituting resin, when an organic or inorganic matting agent is used, an acrylic resin film having a surface matte appearance with an excellent sense of luxury and depth is provided. It is possible (for example, Patent Document 1). However, an acrylic resin film using particles having a large particle size as a matting agent has problems such as rough texture or high haze. If the texture is rough, the design of the product laminated with this matte film may be impaired. It is not preferable because there is a problem that beauty is spoiled. There is also a method of reducing the particle size of the matting agent in order to reduce the haze and provide a fine appearance (for example, Patent Document 2). However, if the particle size is too small, a large amount of delustering agent must be blended in order to obtain the desired matte finish, which is not economical and also makes the film brittle and easily cracked. Further, when the particle size is 3 μm or less, there is a problem that the glossiness is strongly felt and the appearance is deteriorated as compared with a film using particles having a particle size of 4 μm or more as a matting agent.

JP-A-10-237261 JP 2010-284804 A

An object of the present invention is to provide a matte film or sheet with good transparency, fine texture, and good appearance without excessive shine even at low gloss, and a laminated sheet or laminated molded product using the same. .

The above problems are solved by any one of the present inventions [1] to [10] below.
[1] A polymer (b-1) containing 75 to 99% by mass of a thermoplastic resin (A) and at least one polyfunctional monomer having two or more non-conjugated double bonds per monomer A resin composition (i) obtained by graft polymerization of a monomer (b-2) to and containing 1 to 25% by mass of a polymer (B) having a volume average particle diameter of 1 to 3.8 μm, A thermoplastic film comprising a resin composition (i) in which the polymer (B) is dispersed in the resin composition (i) and has a major axis/minor axis of 2.8 or more.
[2] The thermoplastic film of [1], wherein the thermoplastic resin (A) is an acrylic resin.
[3] The polymer (b-1) contains 50 to 100% by mass of an alkyl acrylate, 0 to 50% by mass of an alkyl methacrylate, or other copolymerizable with the alkyl acrylate and alkyl methacrylate. The thermoplastic film according to any one of [1] or [2], containing 0 to 10% by mass of one or more vinyl monomers.
[4] Any one of [1] to [3] containing 0.01 to 0.4% by mass of the polyfunctional monomer with respect to 100% by mass of the polymer (b-1) thermoplastic film.
[5] The thermoplastic film according to any one of [1] to [4], wherein the polyfunctional monomer has a molecular weight of 200 g/mol or more.
[6] The monomer (b-2) is copolymerizable with 0 to 40% by mass of alkyl acrylate, 60 to 100% by mass of alkyl methacrylate, and the alkyl acrylate and alkyl methacrylate. The thermoplastic film according to any one of [1] to [5], containing 0 to 10% by mass of one or more other vinyl monomers.
[7] When the polymer (B) is a total of 100% by mass of the polymer (b-1) and the monomer (b-2), the polymer (b-1) is 50 to 90% by mass, The thermoplastic film according to any one of [1] to [6], wherein the monomer (b-2) is 10 to 50% by mass.
[8] The thermoplastic film according to any one of [1] to [7], wherein the thermoplastic film has an MI value of 0.1 to 2.8 g/10 min.
[9] The relationship between the arithmetic mean roughness Ra and the 60 degree gloss value of the thermoplastic film satisfies the relationship of Ra ≤ (10 × (60 degree gloss value)) ^-1 and Ra < 1 [1] to [8] The thermoplastic film according to any one of.
[10] The thermoplastic film according to any one of [1] to [9], wherein the thermoplastic film has a 60° gloss value of 5 to 90.
Further, in this specification, (meth)acryl means acrylic or methacrylic, and (meth)acrylic acid alkyl ester means acrylic acid alkyl ester or methacrylic acid alkyl ester.

A film, a sheet and a laminated molded product having a very fine grained appearance and a good matt state with a low shine can be obtained. The resulting film can be suitably used in various applications such as interior and exterior applications for automobiles and buildings, and exterior applications where direct sunlight is severe.

[Thermoplastic resin (A)]
Examples of the thermoplastic resin (A) include acrylic resins, polycarbonate resins, polystyrene resins, vinyl chloride resins, ASA resins, and the like. Mixtures of these various thermoplastics may also be used. Acrylic resins are particularly preferred from the viewpoint of transparency and weather resistance.

The acrylic resin used herein refers to a resin containing at least 80% by mass of (meth)acrylic acid ester. From the viewpoint of film-forming properties, the acrylic resin is preferably an acrylic resin composition described below.

The acrylic resin composition will be described. The acrylic resin composition comprises 5.5 to 100% by mass of a rubber-containing polymer (a-1) and 0 to 94.5% by mass of a thermoplastic polymer (a-2) obtained mainly from a methacrylic acid alkyl ester. Preferably, the resin composition contains 100% by mass of component (a-1) and component (a-2) in total.

The rubber-containing polymer (a-1) used in the acrylic resin composition is an elastic copolymer (a-1-1) having a one-stage or two-stage structure obtained mainly from an acrylic acid alkyl ester. 2 or more stages, wherein a hard polymer (a-1-2) having a 1-stage or 2-stage or more structure is formed by graft-polymerizing a monomer containing a methacrylic acid alkyl ester as a main component in the presence of is preferably a rubber-containing polymer having a multistage structure of

Examples of the alkyl acrylate used in the elastic copolymer (a-1-1) include various conventionally known alkyl acrylates. Particularly preferred are methyl acrylate, butyl acrylate and 2-ethylhexyl acrylate. The amount of acrylic acid alkyl ester used is preferably 35 to 99.9% by mass based on the total monomers used in the elastic copolymer (a-1-1). If the amount used is 35% by mass or more, the formability of the film will be good. A more preferable usage amount is 50% by mass or more. When the elastic copolymer (a-1-1) has a structure of two or more stages, each range of these usage amounts is the amount of alkyl acrylate of the elastic copolymer (a-1-1) as a whole. It indicates the amount used. For example, when the elastic copolymer (a-1-1) has a hard core structure, the amount of alkyl acrylate used in the first stage (core) can be less than 35% by mass.

As monomers constituting the elastic copolymer (a-1-1), alkyl acrylate and other vinyl monomers copolymerizable therewith can also be used. When other vinyl monomers are used, the amount used is preferably 64.9% by mass or less in the total monomers. Preferred examples of other vinyl monomers include alkyl methacrylates such as methyl methacrylate, butyl methacrylate and cyclohexyl methacrylate, styrene, and acrylonitrile. These can be used individually by 1 type or in combination of 2 or more types.

A polyfunctional monomer is preferably used as part of the monomers constituting the elastic copolymer (a-1-1). Examples of polyfunctional monomers include ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, allyl (meth)acrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, diallyl maleate, trimethylolpropane triacrylate, allyl cinnamate and the like. These can be used individually by 1 type or in combination of 2 or more types. The amount of polyfunctional monomer used is preferably 0.1 to 10% by mass based on all monomers.

The rubber-containing polymer (a-1) is obtained by graft-polymerizing a monomer containing alkyl methacrylate as a main component in the presence of the elastic copolymer (a-1-1) described above to obtain a hard polymer. It is a rubber-containing polymer having a multistage structure of two or more stages formed by forming (a-1-2).

A methacrylic acid alkyl ester is used as a main component in the graft polymerization for obtaining the hard polymer (a-1-2). Specifically, the amount of methacrylic acid alkyl ester used is preferably 50% by mass or more based on the total monomers used for graft polymerization. Examples of methacrylic acid alkyl esters include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and the like.

As monomers used for graft polymerization to obtain the hard polymer (a-1-2), alkyl methacrylate and other vinyl monomers copolymerizable therewith can also be used. When other vinyl monomers are used, the amount used is preferably 50% by mass or less in the total monomers. As other vinyl monomers, for example, alkyl acrylates such as methyl acrylate, butyl acrylate and cyclohexyl acrylate, styrene, acrylonitrile and the like are preferable. These can be used individually by 1 type or in combination of 2 or more types.

Each of these monomers is graft-polymerized in one or more stages in the presence of the elastic copolymer (a-1-1) to form a hard polymer (a-1-2) and a rubber-containing polymer. (a-1) is obtained. The amount of the hard polymer (a-1-2) in the rubber-containing polymer (a-1) is preferably 10% by mass or more with respect to 100% by mass of the elastic copolymer (a-1-1), 20 mass % or more is more preferable, while 400 mass % or less is preferable, and 200 mass % or less is more preferable.

The particle size of the rubber-containing polymer (a-1) is preferably 0.01 μm or more, more preferably 0.08 μm or more, and is preferably 0.5 μm or less, more preferably 0.3 μm or less. In particular, from the viewpoint of film-forming properties, the particle diameter is preferably 0.08 μm or more. The volume average particle size of the polymer (a-1) is measured with a light scattering photometer. Commercially available particle size distribution analyzers include, for example, the light scattering photometer DLS-700 (trade name) manufactured by Otsuka Electronics Co., Ltd.

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

Various conventionally known polymerization initiators can be used as the polymerization initiator. The polymerization initiator may be added to either one of the aqueous phase and the monomer phase, or both.

Emulsifiers used in emulsion polymerization include anionic, cationic and nonionic surfactants, with anionic surfactants being particularly preferred. Examples of anionic surfactants include carboxylate surfactants such as potassium oleate, sodium stearate, sodium myristate, sodium N-lauroyl sarcosinate and dipotassium alkenyl succinate, and sulfuric acid such as sodium lauryl sulfate. Ester salt-based surfactants, sulfonate-based surfactants such as sodium dioctylsulfosuccinate, sodium dodecylbenzenesulfonate, and sodium alkyldiphenyl ether disulfonate, and phosphate-based surfactants such as sodium polyoxyethylene alkylphenyl ether phosphate activator and the like.

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

The thermoplastic polymer (a-2) used in the acrylic resin composition is a polymer obtained mainly from a methacrylic acid alkyl ester, and various conventionally known polymers can be used.

As the thermoplastic polymer (a-2), 50 to 99.9% by mass of alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms, 0.1 to 50% by mass of alkyl acrylate, and these It is obtained by polymerizing a total of 100% by mass of 49.9% by mass or less of other vinyl monomers copolymerizable with if necessary, and has a reduced viscosity (0.1 g of polymer in 100 mL of chloroform From the viewpoint of film-forming properties, it is preferable to use a polymer having a dissolution (measured at 25° C.) of 0.1 L/g or less.

More specifically, it is preferable that the reduced viscosity is 0.1 L/g or less, since moderate elongation occurs when the film material resin is melted, and the film formability is improved. Moreover, it is preferable that the reduced viscosity is 0.05 L/g or more because the film does not become brittle and the film is less likely to break during film formation and printing.

As the methacrylic acid alkyl ester used for obtaining the thermoplastic polymer (a-2), for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like are preferable, and methyl methacrylate is particularly preferable.

Moreover, as the alkyl acrylate ester, for example, methyl acrylate, ethyl acrylate, butyl acrylate, etc. are preferable, and methyl acrylate is particularly preferable.

Further, other vinyl monomers include aromatic vinyl compounds such as styrene, vinyl cyanide monomers such as acrylonitrile, unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride, and N-phenylmaleimide. , N-cyclohexylmaleimide and the like.

The method for producing the thermoplastic polymer (a-2) is not particularly limited, and various polymerization methods such as suspension polymerization, emulsion polymerization and bulk polymerization can be used. A chain transfer agent, other polymerization aids, and the like may be used during the polymerization. Although various chain transfer agents can be used, mercaptans are particularly preferred.

[Polymer B]
The polymer (B) is a polymer (b-1) containing one or more polyfunctional monomers having two or more non-conjugated double bonds per monomer, and a monomer (b-2 ) and having a volume average particle diameter of 1 to 3.8 μm.

Polymer (B) is preferably composed of an acrylic resin. In addition, the polymer (B) is added to the thermoplastic resin (A) described above, and it is possible to obtain a resin composition having a matte appearance and a molded article thereof, and therefore it is preferably used as a matting agent. be able to.

The polymer (b-1) is a polymer containing 100% by mass in total of an alkyl acrylate, an alkyl methacrylate, and at least one other vinyl monomer copolymerizable therewith. is preferred.

The alkyl acrylate used in the polymer (b-1) is, for example, an alkyl acrylate typified by methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, i-butyl acrylate, and the like. , lower alkoxy acrylates, cyanoethyl acrylate, acrylic acid amide, acrylic acid ester monomers such as acrylic acid, and vinyl cyanide monomers such as acrylonitrile. These can be used alone or in combination of two or more. The use range of the acrylic acid alkyl ester is 50 to 100% by mass, preferably 60 to 95% by mass, more preferably 70 to 90% by mass. If the alkyl acrylate content is less than 50% by mass, the flexibility of the film will be reduced and the film will not be deformed, resulting in poor appearance.

Alkyl methacrylates used in the polymer (b-1) are alkyl methacrylates represented by, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, and the like. Examples include methacrylic acid ester monomers such as esters, lower alkoxy methacrylates, cyanoethyl methacrylate, methacrylic acid amides and methacrylic acid, and vinyl cyanide monomers such as methacrylonitrile. These can be used alone or in combination of two or more. The use range of the methacrylic acid alkyl ester is 0 to 50% by mass, preferably 5 to 40% by mass, more preferably 10 to 30% by mass. When the methacrylic acid alkyl ester is 50% by mass or more, the flexibility decreases and the film does not deform, resulting in poor appearance.

Other vinyl-based monomers copolymerizable with the alkyl acrylate and alkyl methacrylate used in the polymer (b-1) are the monomers listed for the thermoplastic polymer (a-2). can. The amount of the vinyl-based monomer used is 0 to 10% by mass, more preferably 0 to 5% by mass.

Further, the polyfunctional monomer used in the polymer (b-1) is a polyfunctional monomer having a molecular weight of 200 g/mol or more and having two or more non-conjugated double bonds per monomer. Contains one or more. The polyfunctional monomer used in the polymer (b-1) preferably has a molecular weight of 200 g/mol or more, more preferably 250 g/mol or more, even more preferably 300 g/mol or more. By adjusting the molecular weight as described above, the flexibility of the polymer B can be adjusted, and the polymer (B) can be easily deformed in the thermoplastic resin (A). Examples of polyfunctional monomers satisfying this requirement include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and pentaethylene di(meth)acrylate. Glycol di, hexaethylene glycol di(meth)acrylate, heptaethylene glycol di(meth)acrylate, octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, deca di(meth)acrylate glycol di(meth)acrylates such as ethylene glycol, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, alkylene glycol di(meth)acrylates such as propylene glycol di(meth)acrylate, Examples thereof include cyanurate monomers such as triallyl cyanurate and triallyl isocyanurate. Among them, glycol di(meth)acrylate, in which the glycol is ethylene glycol, is more preferable, and the polyfunctional monomers may include polyfunctional monomers other than those described above. Examples include α,β-unsaturated carboxylic acids such as allyl methacrylate, allyl dicarboxylic acids, methacryl or crotyl esters, and the like. The ratio of the polyfunctional monomer having a molecular weight of 200 g/mol or more and the other polyfunctional monomer is 100% by mass of the polyfunctional monomer used in the polymer (b-1), and the molecular weight is 200 g. /mol or more of the polyfunctional monomer is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more.

The proportion of the polyfunctional monomer used is 0.01 to 0.4% by mass, preferably 0.05 to 0.3% by mass, more preferably 0.05 to 0.3% by mass, relative to 100% by mass of the polymer (b-1) It is 0.1 to 0.28% by mass. If the proportion of polyfunctional monomer used is less than 0.01% by mass, the gloss value of the film does not decrease, and if it exceeds 0.4% by mass, the polymer (B) becomes hard and the appearance of the film deteriorates. .

The polymer (b-1) is not particularly defined as long as it is within the specified range of monomers whether it is a one-step or multi-step polymer. The monomer (b-2) is a polymer containing 100% by mass in total of an alkyl acrylate, an alkyl methacrylate, and at least one other vinyl-based monomer copolymerizable therewith. is preferred.

Specific examples of the alkyl acrylate used in the monomer (b-2) include the monomers used in the polymer (b-1). The amount of the acrylic acid alkyl ester used is 0 to 40% by mass, preferably 3 to 30% by mass, more preferably 5 to 25% by mass.

Specific examples of the methacrylic acid alkyl ester used for the monomer (b-2) include the monomers exemplified for the polymer (b-1). Among them, methacrylic acid alkyl esters having 1 to 4 carbon atoms in the ester are preferable because the resulting polymer (B) has good compatibility with the thermoplastic resin (A). The amount of the methacrylic acid alkyl ester used is 60 to 100% by mass, preferably 70 to 97% by mass, more preferably 75 to 95% by mass.

Other vinyl-based monomers copolymerizable with alkyl acrylates and alkyl methacrylates used in the monomer (b-2) are specific examples of the monomers listed for the polymer (b-1). mentioned. The amount of the vinyl monomer used is 0 to 10% by mass, more preferably 0 to 5% by mass.

The monomer (b-2) may contain 0 to 1% by mass of the polyfunctional monomers listed for (a-1-1) with respect to 100% by mass of the monomer (b-2).

When the polymer (B) comprises a total of 100% by mass of the polymer (b-1) and the monomer (b-2), 50 to 90% by mass of the polymer (b-1) and the monomer ( b-2) It is preferable to be 10 to 50% by mass. The proportion of polymer (b-1) is more preferably 60 to 85% by mass, more preferably 75 to 80% by mass.

The volume average particle size of the polymer (B) is preferably 1-3.8 μm, more preferably 1.2-3.5 μm, still more preferably 1.4-3.0, and 1.7-2. Most preferably 8 microns. The volume average particle size of the polymer (B) is measured by laser diffraction method according to JIS Z 8825-1. A commercially available particle size distribution analyzer is, for example, SALD-7100 (trade name) manufactured by Shimadzu Corporation.

[Resin composition (i)]
The resin composition (i) of the present invention is a resin composition containing the thermoplastic resin (A) and the polymer (B).

The resin composition (i) preferably comprises 75 to 99% by mass of the thermoplastic resin (A) and 1 to 25% by mass of the polymer (B) for a total of 100% by mass. By containing 75 to 99% by mass of the thermoplastic resin (A), it is possible to make the appearance of the film obtained by molding the resin composition into a film form matte. The content of the thermoplastic resin (A) is more preferably 77-97% by mass, more preferably 79-96% by mass.

A method for preparing the resin composition (i) is not particularly limited, but a method of melt-kneading with various kneaders is preferable in order to transform the polymer (B) into the above-described shape. Examples include single screw extruders, twin screw extruders and roll kneaders.

The resin composition (i) may optionally contain antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, antistatic agents, flame retardants, fillers, processing aids, impact resistance aids, Various additives such as antibacterial agents, antifungal agents, foaming agents, release agents, colorants, ultraviolet absorbers, and thermoplastic polymers can be added. Antioxidants include, for example, phenol antioxidants, sulfur antioxidants and phosphorus antioxidants. Examples of heat stabilizers include hindered phenol-based heat stabilizers, sulfur-based heat stabilizers, and hydrazine-based heat stabilizers. Plasticizers include, for example, phthalates, phosphates, fatty acid esters, aliphatic dibasic acid esters, oxybenzoic acid esters, epoxy compounds and polyesters. Examples of lubricants include fatty acid esters, fatty acids, metallic soaps, fatty acid amides, higher alcohols and paraffins. Antistatic agents include, for example, cationic antistatic agents, anionic antistatic agents, nonionic antistatic agents, and amphoteric antistatic agents. Examples of flame retardants include brominated flame retardants, phosphorus flame retardants, chlorine flame retardants, nitrogen flame retardants, aluminum flame retardants, antimony flame retardants, magnesium flame retardants, boron flame retardants and zirconium flame retardants. A fire retardant is mentioned. Fillers include, for example, calcium carbonate, barium sulfate, talc, roselite and kaolin. These additives can be used alone or in combination of two or more.

[Thermoplastic film]
The thermoplastic film of the present invention is a film obtained by molding the resin composition (i) into a film. Since the thermoplastic film has fine wrinkles formed on its surface due to the deformation of the polymer (B), it is imparted with a fine matte texture. In addition, compared with a matte film using particles having a particle size of 4 μm or more and having a similar 60° gloss value, the film is less shiny and has a good appearance.

As for the dispersed shape of the polymer (A) in the thermoplastic film, it is preferable that the ratio of major axis/minor axis is 2.8 or more. By deforming the polymer (B) in the thermoplastic film so that the major axis/minor axis is 2.8 or more, fine wrinkles that cannot be formed with non-deformed crosslinked particles are formed on the film surface, resulting in a fine gloss. Gives an erased look. The length/breadth ratio is more preferably 3.0 or more, more preferably 3.5 or more.

The thermoplastic film preferably has an MI value of 0.1 to 2.8 g/10 min at 230° C. and a load of 49 N. By setting the MI value to 2.8 g/10 min or less, the polymer (B) can be deformed into the above-described shape during melt-kneading, fine wrinkles can be formed on the film surface, and the appearance can be improved. It is more preferably 2.4 g/10 min or less, still more preferably 1.9 g/10 min or less. Incidentally, the MI value of the thermoplastic film is a value measured according to JIS K7210.

The relationship between the arithmetic mean roughness Ra of at least one surface of the thermoplastic film and the 60-degree gloss value is preferably Ra≦(10×(60-degree gloss value)) ⁻¹ and Ra<1. By satisfying Ra≦(10×(60 degree gloss value)) ⁻¹ and Ra<1, fine and excellent matte appearance can be obtained. More preferably Ra ≤ (9 x (60 degree gloss value)) ^-1 and Ra < 0.75, still more preferably Ra ≤ (8 x (60 degree gloss value)) ^-1 and Ra < 0.45, most preferably is Ra≦(7×(60 degree gloss value)) ⁻¹ and Ra<0.4. The arithmetic mean roughness Ra of the film is a value measured according to JIS B 0633-2001.

The thermoplastic film preferably has a 60 degree surface gloss of 5-90. By setting the 60 degree surface glossiness within the range of 5 to 90, the appearance of the film can be recognized as a good matte appearance, which is preferable. It is more preferably in the range of 11-85, still more preferably in the range of 11-65. Incidentally, the surface glossiness of the film is a value measured according to JIS Z8741.

The haze of the matte film measured according to JIS K7136 is preferably 80% or less from the viewpoint of beautiful appearance of the matte film. Having a haze of 80% or less is preferable from the viewpoint of beauty of the decorative layer printed on the film when viewed from the matte surface. More preferably, it is 75% or less.

As for the light transmittance of the thermoplastic film, the total light transmittance measured according to JIS K7361-1 is preferably 80% or more. Having a total light transmittance of 80% or more is preferable from the viewpoint of beauty of the decorative layer when the decorative layer printed on the film is viewed from the side on which the decorative layer is not printed. It is more preferably 85% or more, still more preferably 90% or more.

The thickness of the thermoplastic film is preferably in the range of 5 to 500 μm, more preferably 15 to 300 μm, more preferably 30 μm, from the viewpoint of film handling property, laminating property, film-forming property, and processability. More preferably, it is in the range of ~300 μm.

Examples of the method for producing a thermoplastic film include a melt extrusion method such as a melt casting method, a T-die method, an inflation method, and a calendering method, but the T-die method is preferable from the viewpoint of economy.

The thermoplastic film can be formed by a T-die method using an extruder or the like, and then wound around a tubular article such as a paper tube with a winder to form a roll-shaped article. In addition, uniaxial stretching (machine direction or transverse direction (direction perpendicular to the machine direction)), biaxial stretching (sequential biaxial stretching, simultaneous biaxial stretching), etc. by known stretching methods may be carried out as necessary during the film-forming process. A stretching step can be provided.

In the case of melt extrusion, it is preferable to extrude the resin composition in a molten state while filtering it through a screen mesh of 200 mesh or more in order to remove nuclei and foreign substances that cause poor appearance.

Microstructures can also be formed on the surface of the thermoplastic film, if desired. Methods for forming the fine structure include, for example, a thermal transfer method and an etching method. Among these, the thermal transfer method, in which a fine structure is formed on the surface of the film by heating a mold having a fine structure and then pressing the heated mold against the surface of the film, is advantageous in terms of productivity and economy. preferable.

Examples of the above thermal transfer method include a method in which a mold having a fine structure is hot-pressed onto an acrylic resin film cut out from a roll-shaped article to thermally transfer the fine structure in a sheet, and a heated belt-shaped fine structure. An acrylic resin film unwound from a roll-shaped article is nipped and pressurized using nip rolls in a metal mold, and a continuous shaping method is mentioned in which the fine structure is thermally transferred to the surface of the acrylic resin film. Examples of methods for producing a mold having the fine structure described above include sandblasting, etching, and electrical discharge machining.

The thermoplastic film can be laminated not only on film to film, but also on other substrates. The shape of the base material used for the production of the laminate is not particularly limited, but for example, a base material having a shape such as a film, a sheet, or a molded article having a three-dimensional shape can be used.

The present invention will now be described with reference to examples and comparative examples. In the following description, "parts" means "mass parts". Moreover, evaluation of each film was performed by the following method. Abbreviations used in the description below are as follows.
"MMA": methyl methacrylate "MA": methyl acrylate "BA": butyl acrylate "AMA": allyl methacrylate "BDMA": 1,3-butylene glycol dimethacrylate "4EG": tetraethylene dimethacrylate Glycol "9EG": nonaethylene glycol dimethacrylate "LPO": lauryl peroxide "t-BH": t-butyl hydroperoxide "n-OM": n-octyl mercaptan "MA1004": acrylic crosslinked particles (Co., Ltd. Nippon Shokubai, volume average particle size 4 μm)

(1) Film optical properties (total light transmittance and haze)
The total light transmittance and haze of the film were measured under the following conditions.
Total light transmittance was measured according to JIS K7361-1, and haze was measured according to JIS K7136 using NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd.

(2) 60° Surface Glossiness According to JIS Z8741, the 60° surface glossiness of the film was measured using a portable gloss meter (manufactured by Konica Minolta Sensing, Inc., trade name: GM-268).

(3) Surface Roughness The arithmetic mean roughness Ra of the film was measured under the following conditions. The arithmetic mean roughness Ra was measured according to JIS B 0633-2001 using Surfcom 1400D manufactured by ACCRFTECH.

(4) Dispersed particle size of the polymer (B) in the thermoplastic film The surface of the matte film that is horizontal to the extrusion direction of the film is measured with a microtome (EM-ULTRACUT UCT manufactured by Leica Microsystems) to a thickness of 80 nm or more. A section of 300 nm was cut out, placed on a grid, and observed with an electron microscope using J100S (trade name) manufactured by JEOL Ltd. Five or more polymer (B) particles with clear contrast were selected from the obtained electron microscope image, and the ratio of the major axis to the minor axis was measured and the average value was calculated. The major diameter is the longest particle diameter, and the minor diameter is the shortest particle diameter. When the polymer (A) has anisotropy, the observation surface by TEM is a plane parallel to the direction in which the polymer (A) extends. .

(5) Film appearance (shine)
Width of black and white lines through the thermoplastic film was observed, and it was evaluated whether the black and white lines could be distinguished without blurring. The distance between the thermoplastic film and the black and white line was 25 cm, and the width of the line was 1, 2, 3, 4, 7, and 9 mm. A score of 10 was given when there was no distinguishable line. The larger the numerical value, the less oily and the better the appearance.

(6) Measurement of MI value The MI value of the thermoplastic film was measured at 230°C and a load of 49N according to JIS K7210.

[Preparation Example 1]
(Creation of thermoplastic resin A-1)
250 parts of ion-exchanged water, 2 parts of ester soda salt of sulfosuccinic acid, and 0.05 part of sodium formaldehyde sulfoxylate are introduced into a polymerization vessel equipped with a cooler, and stirred under nitrogen. A mixture of 0.2 parts 1,3BD, 0.05 parts AMA and 0.025 parts cumene hydroperoxide was charged. After heating to 70° C., the reaction was continued for 60 minutes. After that, a mixture of 1.5 parts of MMA, 22.5 parts of BA, 1.0 parts of 1,3BD, 0.25 parts of AMA and 0.016 parts of cumene hydroperoxide was added for 60 minutes and polymerized to obtain a two-stage crosslinked rubber. An elastic body was obtained.

Subsequently, a mixture of 6 parts of MMA, 4 parts of BA, 0.075 parts of AMA and 0.013 parts of cumene hydroperoxide is reacted in the presence of this two-stage crosslinked rubber elastic body to obtain an elastic copolymer (a-1- 1), and finally, a mixture of 55.2 parts of MMA and 4.8 parts of BA is reacted to form a hard polymer (a-1-2), and a latex of the rubber-containing polymer (a-1) got

The particle size of this multistage structure polymer was 0.12 μm. The resulting polymer latex is filtered through a filter with an opening of 75 μm, salted out with 5 parts of calcium acetate per 100 parts of the polymer, washed and dried to produce a thermoplastic resin (A-1 ).

[Preparation Example 2]
(Preparation of polymer B-1)
Into a polymerization vessel equipped with a stirrer, a cooling tube, a thermocouple, and a nitrogen inlet tube, 68 parts of ion-exchanged water was added, and 3 parts of BA and 0.5 parts of AMA were added while stirring in a nitrogen atmosphere. The external temperature was fixed so that the internal temperature reached 85°C, and after the internal temperature reached 85°C, 0.05 part of potassium persulfate (KPS) was added. After confirming the temperature rise, 0.05 part of KPS was further added, and 78 parts of pre-emulsified BA, 0.05 part of AMA, 55 parts of pure water and 0.7 part of emulsifier Pelex OT-P (manufactured by Kao Corporation) were mixed for 1 hour. dripped over. After dropping, the mixture was held for 1 hour, and 17 parts of pre-emulsified MMA, 2 parts of BA, 0.05 parts of AMA, 30 parts of pure water, and 0.2 parts of Pelex OT-P were added dropwise over 1 hour. After holding for 1 hour, the polymerization was terminated. Seed particles 1 having a solid content of 39 parts, BA of 83 parts, and MMA of 17 parts were obtained.

233 parts of ion-exchanged water, 7.7 parts of seed particles 1 (solid content: 3 parts, MMA: 0.5 parts, BA: 2.5 parts) were placed in a polymerization vessel equipped with a stirrer, a cooling tube, a thermocouple, and a nitrogen inlet tube. 13.6 parts of MMA, 54.3 parts of BA, 0.1 part of 4EG, 0.15 part of AMA and 0.25 part of t-BH were added and stirred for 1 hour under a nitrogen atmosphere. After that, the internal temperature was adjusted to 50° C., and 0.0015 parts of ferrous sulfate dihydrate as an oxidizing agent, 0.045 parts of ethylenediaminetetraacetate-2-sodium and 0.24 parts of Rongalite as a reducing agent were added. After confirming the peak, the mixture was held for 1 hour, and 26.2 parts of MMA, 2.9 parts of MA and 0.5 parts of t-BH were added dropwise over 1 hour. It was held again for 1 hour to complete the polymerization. The obtained polymer was coagulated with calcium acetate, dehydrated and dried to obtain a polymer (B-1). Table 1 shows the composition of the obtained polymer.

[Preparation Example 3]
(Preparation of polymers B-2 to 4)
Polymer (B-1) was prepared in the same manner as for polymer (B-1) except that the monomers were changed so that the composition shown in Table 1 was obtained.

[Preparation Example 4]
(Preparation of polymer B-5)
Seed particles 2 were obtained in the same manner as seed particles 1 except that the amount of the cross-linking agent added was changed to 0 parts.

A polymer B-5 was obtained in the same manner as for the polymer (B-1) except that the seed particles 2 were used and the composition shown in Table 1 was changed.

[Adjustment example 5]
(Preparation of polymer B-6)
Polymer (B-1) was prepared except that seed particles 1 were used and the composition shown in Table 1 was changed.

<Example 1>
90 parts of a thermoplastic resin (A-1), 10 parts of a polymer (B-1), and 0.5 parts of a hindered phenol-based antioxidant "ADEKA STAB AO-60" (trade name) manufactured by ADEKA as an antioxidant. 1 part and 2 parts of processing aid "P-530A" manufactured by Mitsubishi Chemical Co., Ltd. are blended, hand-blended, and a cylinder is used with a twin-screw extruder (trade name: TEM35, manufactured by Toshiba Machine Co., Ltd.). It was extruded at a temperature of 100 to 240° C. and a die head temperature of 240° C. and cut to obtain pellets of the matte resin composition (i).

The pellets of resin composition (i) were dried at 80° C. for 24 hours. After drying, the pellets of the resin composition (i) were plasticized using a non-vented screw type 30 mmφ extruder set at a cylinder temperature of 230°C, and then extruded at a first temperature of 80°C with a multi-manifold die set at 230°C. A film having a predetermined thickness was obtained by transporting the film in contact with a mirror-finished cooling roll.

The thickness of the film thus obtained was measured to be 50 μm. The surface of the obtained film not in contact with the first cooling roll was measured to have a 60 degree surface glossiness of 21, indicating good matte performance. Visually evaluated, the appearance (shine) of the film was comparable to that of the film using 4 μm crosslinked particles exhibiting the same 60° gloss value, and was good. The dispersed shape of the polymer (A) in the film had a major axis/minor axis of 4.3, and the arithmetic average roughness measured on the surface of the film not in contact with the first cooling roll was 0.25 μm. The results are summarized in Table 2.

<Examples 2-3>
The procedure of Example 1 was repeated except that the thermoplastic resin (A) and the polymer (B) were changed to those shown in Table 2 and the added amounts shown in Table 2. The 60-degree surface glossiness, fineness, and appearance (shine) also showed good results. The results are summarized in Table 2.

<Example 4>
MMA / MA copolymer (MMA / MA = 90/10, reduced viscosity 0.057 L / g) as thermoplastic resin (A-2), thermoplastic resin (A) and polymer (B), Table 2 2 and Table 2, except that the addition amount was changed to that shown in Example 1.

<Examples 5 and 6>
The procedure of Example 1 was repeated except that the thermoplastic resin (A) and the polymer (B) were changed to those shown in Table 2 and the added amounts shown in Table 2. The 60-degree surface glossiness, fineness, and appearance (shine) also showed good results. The results are summarized in Table 2.

<Comparative Examples 1 to 4>
The procedure of Example 1 was repeated except that the thermoplastic resin (A) and the polymer (B) were changed to those shown in Table 3 and the added amounts shown in Table 3.

As described above, the matte film, laminated film, decorative film, laminated sheet and laminated molded article prepared from the matte resin composition using the polymer of the present invention as a matte agent are particularly suitable for vehicle applications. , suitable for building materials. Specific examples include automotive interior applications such as instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, dashboards, weather strips, bumpers, bumper guards, side mudguards, body panels, Spoilers, front grills, strut mounts, wheel caps, center pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, windows, head lamp covers, tail lamp covers, windshield parts, etc. Automobile exterior applications, AV equipment and furniture products Applications such as front panels, buttons, emblems, surface decorative materials, etc., applications such as mobile phone housings, display windows, buttons, etc., furniture exterior materials, wall surfaces, ceilings, floors, etc. External walls such as siding, fences, roofs, gates, gable boards, and other architectural exterior materials; surface decorative materials for furniture such as window frames, doors, handrails, thresholds, and lintels; various displays, lenses, mirrors, goggles, Optical member applications such as window glass, interior and exterior applications for various vehicles other than automobiles such as trains, aircraft, and ships, various packaging containers and materials such as bottles, cosmetic containers, and accessory cases, miscellaneous goods such as prizes and small items, etc. It can be suitably used for various purposes.

Claims (7)

Acrylic resin (A) 75 to 99% by mass and polymer (b-1) containing one or more polyfunctional monomers having two or more non-conjugated double bonds per monomer (b-1) monomer A resin composition (i) obtained by graft polymerization of (b-2) and containing 1 to 25% by mass of a polymer (B) having a volume average particle diameter of 1 to 3.8 μm, wherein the polyfunctional and the polymer (b-1) contains 50 to 100% by mass of an alkyl acrylate, 0 to 50% by mass of an alkyl methacrylate, the alkyl acrylate and 0 to 10% by mass of at least one other vinyl-based monomer copolymerizable with the methacrylic acid alkyl ester, and the length/shortness of the dispersion shape of the polymer (B) in the resin composition (i) A thermoplastic film comprising a resin composition (i) having a diameter of 2.8 or more. The thermoplastic film according to claim 1 , containing 0.01 to 0.4% by mass of the polyfunctional monomer with respect to 100% by mass of the polymer (b-1). The monomer (b-2) comprises 0 to 40% by mass of alkyl acrylate, 60 to 100% by mass of alkyl methacrylate, and other vinyl copolymerizable with the alkyl acrylate and alkyl methacrylate. The thermoplastic film according to claim 1 or 2 , containing 0 to 10% by mass of one or more system monomers. When the polymer (B) is a total of 100% by mass of the polymer (b-1) and the monomer (b-2), the polymer (b-1) is 50 to 90% by mass, and the monomer The thermoplastic film according to any one of claims 1 to 3 , wherein (b-2) is 10 to 50% by mass. The thermoplastic film according to any one of claims 1 to 4 , wherein the thermoplastic film has an MI value of 0.1 to 2.8 g/10 min at a measurement temperature of 230°C and a load of 49N . Any one of claims 1 to 5 , wherein the relationship between the arithmetic mean roughness Ra of the thermoplastic film and the 60 degree gloss value satisfies the relationship of Ra ≤ (10 × (60 degree gloss value)) ^{- 1} and Ra < 1. The thermoplastic film according to . The thermoplastic film according to any one of claims 1 to 6 , wherein the thermoplastic film has a 60 degree gloss value of 5 to 90.