Microparticle-containing resin composition and resin film

Abstract

To provide a microparticle-containing resin composition by which a resin film excellent in matte appearance, surface quality, solvent resistance, and flex resistance can be produced, and a resin film obtained using the composition.SOLUTION: The microparticle-containing resin composition of the present disclosure contains a thermoplastic resin (R) and microparticles (P), wherein the microparticles (P) satisfy 2≤D50≤4.5 and 1.1≤(Log(D50 / D10)) / (Log(D90 / D50))≤2.0, where D10 [μm], D50 [μm], and D90 [μm] represent, respectively, a cumulative 10% particle diameter, a cumulative 50% particle diameter, and a cumulative 90% particle diameter in a volume-based cumulative particle size distribution measured by a laser diffraction / scattering method, the surface fluorine element content measured by fluorescent X-ray analysis being 1 to 20 mass%, the thermoplastic resin (R) content being 50 to 99.5 mass%, and the microparticle (P) content being 0.5 to 25 mass%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a fine particle-containing resin composition and a resin film using the same. [Background technology]

[0002] Resin films (matte resin films) having a matte (frosted) appearance with an uneven surface are sometimes used for applications such as interior and exterior parts of automobiles, exterior parts of household electrical appliances, exterior parts of furniture, and wall materials. Furthermore, depending on the application, printing may be applied to at least one film surface of the matte resin film to impart design or decorative properties such as a sense of luxury and depth. BACKGROUND ART Conventionally, matte resin films made of a microparticle-containing resin composition containing a thermoplastic resin and microparticles (matting agent) have been known (Patent Documents 1 to 4). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 06-073199 (Patent No. 3307989) [Patent Document 2] Japanese Patent Application Publication No. 10-237261 [Patent Document 3] JP 2002-361712 A (Patent No. 3964234 A) [Patent Document 4] JP 2009-143174 A (Patent No. 5108487 A) Summary of the Invention [Problem to be solved by the invention]

[0004] In applications where a matte resin film is used as the outermost layer, such as a decorative film, the matte resin film preferably has a good matte appearance, good appearance quality, and solvent resistance. In this specification, "good appearance quality" means that there is no foreign matter defect or the number of foreign matter defects is sufficiently small. Although the matte resin films made from the conventional microparticle-containing resin compositions have good matting properties and printability, it tends to be difficult to produce films with good appearance quality for the following reasons. In the conventional matte resin films, aggregates of microparticles (matting agents) may be visually recognized as foreign matter defects. In addition, in general, when producing resin films, molten resins that have been melt-filtered using a filter are used to produce films that are free of or have sufficiently few foreign matter defects caused by resin degradation products and gelled products. However, when producing films from conventional microparticle-containing resin compositions, the filter may become clogged with the microparticles (matting agents), making it impossible to remove foreign matter such as resin degradation products and gelled products from the molten resin, which may remain as foreign matter defects. The above-mentioned matte resin films made of conventional fine particle-containing resin compositions may also have insufficient mechanical properties such as solvent resistance and / or bending resistance.

[0005] The present disclosure has been made in consideration of the above circumstances, and aims to provide a microparticle-containing resin composition that can be used to produce a resin film that has a matte appearance, good appearance quality, solvent resistance, and bending resistance, and a resin film using the same. [Means for solving the problem]

[0006] The present disclosure provides the following fine particle-containing resin composition and resin film. [1] A microparticle-containing resin composition comprising a thermoplastic resin (R) and microparticles (P), The microparticles (P) have a cumulative 10% particle diameter D10 [μm], a cumulative 50% particle diameter D50 [μm], and a cumulative 90% particle diameter D90 [μm] in a volume-based cumulative particle diameter distribution measured by a laser diffraction / scattering method that satisfy 2≦D50≦4.5 and 1.1≦(Log(D50 / D10)) / (Log(D90 / D50))≦2.0, and a surface fluorine content measured by X-ray fluorescence analysis of 1 to 20 mass%; A microparticle-containing resin composition having a thermoplastic resin (R) content of 50 to 99.5 mass % and a microparticle (P) content of 0.5 to 25 mass %.

[0007] [2] The microparticle-containing resin composition according to [1], wherein the microparticles (P) have a volume-based particle size distribution measured by a laser diffraction / scattering method, which has a first peak with a maximum particle size of 0.1 to 1 μm and a second peak with a maximum particle size of 2 to 8 μm.

[0008] [3] The microparticle-containing resin composition according to [1] or [2], wherein the microparticles (P) are inorganic particles. [4] The microparticle-containing resin composition according to [3], wherein the microparticles (P) are one or more types of inorganic particles selected from the group consisting of mica and talc. [5] The fine particle-containing resin composition according to any one of [1] to [4], wherein the thermoplastic resin (R) comprises a combination of a methacrylic resin and a rubber-like polymer, a polycarbonate resin, or a polypropylene resin.

[0009] [6] A resin film comprising a microparticle-containing resin layer made of the microparticle-containing resin composition according to any one of [1] to [5]. [7] The resin film according to [6], wherein the thickness of the fine particle-containing resin layer is 10 to 500 μm. [8] The resin film according to [6] or [7], comprising the fine particle-containing resin layer and a printed layer. [Effects of the Invention]

[0010] According to the present disclosure, it is possible to provide a microparticle-containing resin composition that can be used to produce a resin film that has a matte appearance, good appearance quality, solvent resistance, and flex resistance, and a resin film using the same. [Brief explanation of the drawings]

[0011] [Figure 1] 1 is a graph showing an example of measurement of the volume-based particle size distribution and the volume-based cumulative particle size distribution of fine particles (P). DETAILED DESCRIPTION OF THE INVENTION

[0012] Generally, terms such as "film" and "sheet" are used for thin film molded bodies depending on the thickness, but there is no clear distinction between them. In this specification, "film" includes "sheet".

[0013] [Resin composition containing fine particles] The microparticle-containing resin composition of the present disclosure contains one or more thermoplastic resins (R) and one or more microparticles (P), and may contain one or more optional components as needed. The microparticle-containing resin composition of the present disclosure can be used to provide a resin film having a single layer structure or a laminate structure, which includes a microparticle-containing resin layer made of the microparticle-containing resin composition of the present disclosure. This resin film can be used as a matte resin film.

[0014] As the fine particles (P), fine particles generally called matting agents or light diffusing agents can be used. The fine particles (P) can impart a matte appearance to the resin film by their light diffusing effect and / or surface roughness imparting effect. At least one side of the resin film of the present disclosure may be a smooth surface without surface irregularities at the time of film formation. In this case, after film formation, the resin film of the present disclosure may be softened by heating at an appropriate temperature to cause the fine particles (P) to protrude from the film surface, thereby converting the smooth surface without surface irregularities into an irregular surface.

[0015] The content of the fine particles (P) (total amount when there are multiple types unless otherwise specified) is 0.5 to 25% by mass. The lower limit is preferably 1% by mass, more preferably 2% by mass, even more preferably 3% by mass, particularly preferably 4% by mass, and most preferably 5% by mass. The upper limit is preferably 22% by mass, more preferably 20% by mass, even more preferably 18% by mass, even more preferably 15% by mass, even more preferably 12% by mass, particularly preferably 10% by mass, and most preferably 8% by mass. When the content of the fine particles (P) is equal to or greater than the lower limit, the light diffusion effect and / or the effect of providing surface irregularities due to the fine particles (P), and the matting effect due to these can be effectively obtained. If the content of the fine particles (P) is too high, the flexibility of the resin film of the present disclosure may decrease, and mechanical properties such as flex resistance may also decrease. If the content of the fine particles (P) is equal to or less than the upper limit, the resin film of the present disclosure can have good flexibility and good mechanical properties such as flex resistance.

[0016] The content of the thermoplastic resin (R) in the microparticle-containing resin composition of the present disclosure (total amount if multiple types are used unless otherwise specified) is 50 to 99.5% by mass. The lower limit is preferably 60% by mass, more preferably 70% by mass, even more preferably 75% by mass, even more preferably 78% by mass, even more preferably 80% by mass, even more preferably 82% by mass, even more preferably 85% by mass, even more preferably 88% by mass, particularly preferably 90% by mass, and most preferably 92% by mass. The upper limit is preferably 99% by mass, more preferably 98% by mass, even more preferably 97% by mass, particularly preferably 96% by mass, and most preferably 95% by mass. When the content of the thermoplastic resin (R) is within the above range, the resin film of the present disclosure can have a good matte appearance and good mechanical properties such as flex resistance.

[0017] (Thermoplastic resin (R)) The thermoplastic resin (R) is not particularly limited, and may be a general-purpose resin or a so-called engineering plastic, or may be a non-rubber polymer or a rubber polymer.

[0018] <Non-rubber polymer> Examples of non-rubber polymers include olefin-based resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; methacrylic resins such as polymethyl methacrylate (PMMA) and methyl methacrylate-styrene (MS) resin; polycarbonate-based resins; styrene-based resins such as polystyrene, styrene-maleic anhydride copolymer, high-impact polystyrene, acrylonitrile-styrene (AS) resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-ethylene-propylene-diene-styrene (AES) resin, acrylic-acrylonitrile-styrene (AAS) resin, acrylonitrile-chlorinated ethylene-styrene (ACS) resin, and methacrylic butadiene styrene (MBS) resin; poly ester-based resins such as polyethylene terephthalate (PET) and polybutylene terephthalate; amide-based resins such as nylon 6 and nylon 66; polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyvinyl alcohol, ethylene-vinyl acetate-based resins, cellulose acetate-based resins, acrylic-chlorinated ethylene-based resins, acetal-based resins, fluorine-based resins, sulfone-based resins, ether sulfone-based resins, methylpentene-based resins, arylate-based resins, resins containing alicyclic structure-containing ethylenically unsaturated monomer units, phenylene sulfide-based resins, phenylene oxide-based resins, ether ether ketone-based resins, ethylene-ethyl acrylate-based resins, chlorinated ethylene-based resins, urethane-based resins, modified polyphenylene ethers, and silicone-modified resins. Among these, methacrylic resins (PM), polycarbonate resins (PC), polypropylene resins (PP), and combinations thereof are particularly preferred.

[0019] Examples of the methacrylic resin (PM) include homopolymers or copolymers containing methacrylic acid units and / or methacrylic acid ester units; modified products thereof, and the like. The methacrylic resin (PM) is preferably a homopolymer or copolymer containing structural units derived from one or more methacrylic acid esters, including methyl methacrylate (MMA). The hydrocarbon group in the methacrylic acid ester may be an acyclic aliphatic hydrocarbon group such as a methyl group, an ethyl group, or a propyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group such as a phenyl group. From the viewpoint of transparency, the content of the methacrylic acid ester monomer unit in the methacrylic resin (PM) (total amount in the case of multiple types, unless otherwise specified) is preferably 90 to 100% by mass. The lower limit is more preferably 95% by mass, and particularly preferably 98% by mass.

[0020] The methacrylic resin (PM) may contain structural units derived from one or more other monomers besides methacrylic acid esters. Examples of such other monomers include acrylic acid esters such as methyl acrylate (MA), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate (BA), isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, and 3-dimethylaminoethyl acrylate. Among them, from the viewpoint of availability, MA, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and tert-butyl acrylate are preferred, MA and ethyl acrylate are more preferred, and MA is particularly preferred. The content of structural units derived from other monomers in the methacrylic resin (PM) (total amount in the case of multiple types unless otherwise specified) is preferably 0 to 10% by mass. The upper limit is more preferably 5% by mass, and particularly preferably 2% by mass.

[0021] The methacrylic resin (PM) is preferably obtained by polymerizing one or more methacrylic acid esters, including MMA, and, if necessary, other monomers. When using multiple types of monomers, the multiple types of monomers are usually mixed to prepare a monomer mixture, and then polymerization is carried out. The polymerization method is not particularly limited, and from the viewpoint of productivity, radical polymerization methods such as bulk polymerization, suspension polymerization, solution polymerization, and emulsion polymerization are preferred. The methacrylic resin (PM) may be a modified methacrylic resin obtained by further modifying the methacrylic resin obtained by the above polymerization method by a known method.

[0022] Polycarbonate resins (PC) are resins with excellent impact resistance and other properties. Examples of production methods include interfacial polymerization, in which an aqueous solution of a dihydric phenol and an organic solvent solution of a carbonate precursor are reacted at the interface, and transesterification, in which a dihydric phenol and a carbonate precursor are reacted at high temperature, under reduced pressure, and in the absence of a solvent. Commercially available products such as "Calibur (registered trademark)" and "SD Polyca (registered trademark)" manufactured by Sumika Styron Polycarbonate Co., Ltd., "Iupilon / Novarex (registered trademark)" manufactured by Mitsubishi Engineering Plastics Corporation, "Toughlon (registered trademark)" manufactured by Idemitsu Kosan Co., Ltd., and "Panlite (registered trademark)" manufactured by Teijin Chemicals Co., Ltd. may also be used.

[0023] Polypropylene resins (PP) are homopolymers or copolymers containing propylene units, such as homopolypropylene, propylene-ethylene random copolymers, propylene-ethylene block copolymers, propylene-butene random copolymers, propylene-ethylene-butene random copolymers, propylene-pentene random copolymers, propylene-hexene random copolymers, propylene-octene random copolymers, propylene-ethylene-pentene random copolymers, propylene-ethylene-hexene random copolymers, and modified products thereof.

[0024] <Rubber-like polymer> The thermoplastic resin (R) preferably contains one or more rubber-like polymers, since such a resin film has sufficient bending strength, can be easily wound onto a roll in continuous production by a roll-to-roll process, and has good impact resistance. Examples of rubber-like polymers include styrene-based thermoplastic elastomers such as SEPS, SEBS, and SIS; olefin-based rubbers such as IR, EPR, and EPDM; acrylic-based thermoplastic elastomers; vinyl chloride-based thermoplastic elastomers; urethane-based thermoplastic elastomers; ester-based thermoplastic elastomers; amide-based thermoplastic elastomers; ionomer-based resins; styrene-butadiene block copolymers; ethylene-propylene rubber; butadiene-based resins; acrylic rubber; silicone rubber; and acrylic multilayer polymers. Among these, multilayer structure particles containing one or more rubber layers (so-called core / shell structure rubber particles) and block copolymers are preferred. From the viewpoint of impact resistance, etc., acrylic multilayer structure polymers (A) are particularly preferred.

[0025] The acrylic multilayer structure polymer (A) is preferably an acrylic multilayer structure polymer particle in which at least one inner layer (the layer inside the outermost layer) is a crosslinked elastic polymer layer whose main component monomer unit is an acrylic acid alkyl ester monomer unit having an alkyl group of 1 to 8 carbon atoms and / or a conjugated diene monomer unit, and the outermost layer is a thermoplastic polymer layer whose main component monomer unit is a methacrylic acid alkyl ester monomer unit having an alkyl group of 1 to 8 carbon atoms. In this specification, unless otherwise specified, the "major component monomer unit" is defined as 50 to 100 mass % of the monomer unit.

[0026] The acrylic multilayered polymer particles (A) are so-called core / shell structured rubber particles in which one or more inner layers, including a crosslinked elastic polymer layer, are covered with an outermost thermoplastic polymer layer. The acrylic multilayered polymer particles (A) are preferably graft copolymer fine particles in which the molecular chains of a crosslinked elastic polymer layer constituting at least one inner layer excluding the outermost layer are covalently bonded to the molecular chains in the adjacent layer.

[0027] Examples of alkyl acrylate esters having an alkyl group having 1 to 8 carbon atoms used in the crosslinked elastic polymer layer include methyl acrylate (MA), ethyl acrylate, n-butyl acrylate (BA), 2-ethylhexyl acrylate, propyl acrylate, and combinations thereof. From the viewpoint of impact resistance, n-butyl acrylate (BA) is preferred. Examples of conjugated diene monomers used in the crosslinked elastic polymer layer include 1,3-butadiene, isoprene, and combinations thereof.

[0028] The crosslinked elastic polymer layer may contain an acrylic acid alkyl ester and / or a conjugated diene monomer having an alkyl group having 1 to 8 carbon atoms, as well as a vinyl monomer copolymerizable therewith. Examples of copolymerizable vinyl monomers include methacrylic acid esters such as methyl methacrylate (MMA), ethyl methacrylate, n-butyl methacrylate, and cyclohexyl methacrylate; aromatic vinyl compounds such as styrene (St), p-methylstyrene, and α-methylstyrene (αMSt); maleimide compounds such as N-propylmaleimide, N-cyclohexylmaleimide, and No-chlorophenylmaleimide; and polyfunctional monomers such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, triethylene glycol dimethacrylate, hexanediol dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, triethylene glycol diacrylate, allyl methacrylate, and triallyl isocyanurate. In this specification, a "polyfunctional monomer" is a monomer having a plurality of polymerizable functional groups.

[0029] From the viewpoint of impact resistance of the resin film, the content of acrylic acid alkyl ester units having an alkyl group of 1 to 8 carbon atoms and / or conjugated diene monomer units in the crosslinked elastic polymer layer (total amount in the case of multiple types unless otherwise specified) is preferably 60 to 100% by mass, with the lower limit being more preferably 70% by mass, particularly preferably 80% by mass, and most preferably 90% by mass.

[0030] In the acrylic multilayered polymer particles (A), examples of methacrylic acid alkyl esters having an alkyl group of 1 to 8 carbon atoms used in the outermost thermoplastic polymer layer include methyl methacrylate (MMA), ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, and cyclohexyl methacrylate. The content of methacrylic acid alkyl ester monomer units in the thermoplastic polymer layer (total amount if multiple types are used unless otherwise specified) is preferably 70 to 100% by mass in terms of dispersibility of the acrylic multilayered polymer particles (A). The lower limit is more preferably 80% by mass.

[0031] The number of layers of the acrylic multi-structured polymer particles (A) is not particularly limited, and from the viewpoints of thermal stability and productivity, it is preferably 2 to 4 layers, more preferably 3 layers. The acrylic multilayered polymer particles (A) are preferably three-layered polymer particles (AX) comprising, from the center, a first layer consisting of a crosslinked polymer layer containing 30 to 98.99 mass% of methyl methacrylate (MMA) units, 1 to 70 mass% of acrylate alkyl ester units having an alkyl group of 1 to 8 carbon atoms, and 0.01 to 2 mass% of polyfunctional monomer units; a second layer consisting of a crosslinked elastic polymer layer containing 70 to 99.9 mass% of acrylate alkyl ester units having an alkyl group of 1 to 8 carbon atoms, 0 to 30 mass% of methyl methacrylate (MMA) units (optional component), and 0.1 to 5 mass% of polyfunctional monomer units; and a third layer (outermost layer) consisting of a rigid thermoplastic polymer layer containing 80 to 99 mass% of methyl methacrylate (MMA) units and 1 to 20 mass% of acrylate alkyl ester units having an alkyl group of 1 to 8 carbon atoms. In the three-layer structure polymer particles (AX), the proportion of each layer is not particularly limited, but it is preferable that the first layer is 5 to 40 mass %, the second layer is 20 to 55 mass %, and the third layer (outermost layer) is 40 to 75 mass %.

[0032] The average particle size of the acrylic multilayered polymer particles (A) is not particularly limited and is preferably 0.05 to 0.30 μm. The lower limit is more preferably 0.07 μm, particularly preferably 0.08 μm. The upper limit is more preferably 0.25 μm, particularly preferably 0.20 μm. If the average particle size is less than the lower limit, the handleability of the acrylic multilayer structure polymer particles (A) tends to decrease. If the average particle size is more than the upper limit, the resin film of the present disclosure tends to whiten when stress is applied, and the transmittance tends to decrease (stress whitening resistance deteriorates).

[0033] The "average particle size of the acrylic multilayer structure polymer particles (A)" can be the particle size at which the cumulative frequency is 50% (also referred to as the 50% cumulative particle size, median size, or volume-average particle size) in the volume-based cumulative particle size distribution measured by a laser diffraction / scattering method using a latex or aqueous dispersion containing the acrylic multilayer structure polymer particles (A) as a sample, or the average particle size of multiple particles measured from an electron microscope image of a sample containing the acrylic multilayer structure polymer particles (A).

[0034] The polymerization method for the acrylic multilayered polymer particles (A) is not particularly limited, but emulsion polymerization is preferred. First, one or more raw material monomers are emulsion-polymerized to obtain core particles, and then one or more other monomers are emulsion-polymerized in the presence of the core particles to form shells around the core particles. If necessary, one or more additional monomers are emulsion-polymerized in the presence of particles consisting of the core and shell to form another shell. By repeating this polymerization reaction, an emulsion latex containing the desired number of layers of acrylic multilayered polymer particles (A) can be produced. The resulting latex typically contains, in addition to the acrylic multilayered polymer particles (A), a linear methacrylic resin having methyl methacrylate (MMA) units.

[0035] The emulsifier used in emulsion polymerization is not particularly limited, and examples thereof include anionic emulsifiers, nonionic emulsifiers, and nonionic-anionic emulsifiers. Examples of anionic emulsifiers include dialkyl sulfosuccinates such as sodium dioctyl sulfosuccinate and sodium dilauryl sulfosuccinate; alkyl benzene sulfonates such as sodium dodecyl benzene sulfonate; and alkyl sulfates such as sodium dodecyl sulfate. Examples of nonionic emulsifiers include polyoxyethylene alkyl ethers and polyoxyethylene nonylphenyl ethers. Examples of nonionic and anionic emulsifiers include polyoxyethylene nonylphenyl ether sulfates such as sodium polyoxyethylene nonylphenyl ether sulfate; polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene alkyl ether sulfate; and alkyl ether carboxylates such as sodium polyoxyethylene tridecyl ether acetate. The number of moles of oxyethylene units added in the exemplified compounds of nonionic emulsifiers or nonionic-anionic emulsifiers is generally 30 moles or less, preferably 20 moles or less, and particularly preferably 10 moles or less, in order to prevent the foaming properties of the emulsifier from becoming extremely high.

[0036] Examples of polymerization initiators used in emulsion polymerization include persulfate initiators such as potassium persulfate and ammonium persulfate; and redox initiators such as persulfoxylate / organic peroxide and persulfate / sulfite. In the emulsion polymerization, a chain transfer agent can be used as needed, such as alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, n-lauryl mercaptan, tert-dodecyl mercaptan, and sec-butyl mercaptan.

[0037] In emulsion polymerization for each layer, raw materials such as one or more monomers, one or more emulsifiers, one or more polymerization initiators, and, if necessary, one or more chain transfer agents can be added to the polymerization reaction system by any known method, such as a batch addition method, a divided addition method, or a continuous addition method.

[0038] The polymerization reaction temperature for each layer is preferably 30 to 120°C, more preferably 50 to 100°C. The polymerization reaction time for each layer varies depending on the type and amount of polymerization initiator and emulsifier used, and the polymerization temperature, but is usually 0.5 to 7 hours for each layer. The mass ratio of monomer to water (monomer / water mass ratio) is preferably 1 / 20 to 1 / 1.

[0039] The acrylic multilayer structure polymer particles (A) contained in the polymer latex obtained by emulsion polymerization are granular. The average particle diameter thereof is preferably 0.05 to 0.3 μm. The latex containing the acrylic multilayer structure polymer particles (A) can be used to produce the microparticle-containing resin composition of the present disclosure. The acrylic multilayer structure polymer particles (A) can be recovered as a powder or other polymer by subjecting the polymer latex produced by emulsion polymerization to coagulation, dehydration, drying, or the like using known methods, as needed. Examples of methods for separating and recovering the powder or other acrylic multilayer structure polymer particles (A) include salting-out coagulation, freeze-coagulation, and spray-drying. Among these, the salting-out coagulation and freeze-coagulation methods are preferred because impurities can be easily removed by washing with water. It is preferable to perform a filtration step using a wire mesh or the like with a mesh size of 50 μm or less before the coagulation step in order to remove foreign matter mixed in the latex.

[0040] (Fine particles (P)) The fine particles (P) may be those generally referred to as matting agents or light diffusing agents. The fine particles (P) may be inorganic particles, organic particles, organic-inorganic composite particles, or a combination thereof. Examples of inorganic particles include calcium carbonate, magnesium carbonate, barium sulfate, titanium oxide, magnesium oxide, zinc oxide, zirconium oxide, aluminum oxide, aluminum hydroxide, silica (silicon dioxide), calcined calcium silicate, calcined kaolin, hydrated calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, glass, talc, clay, mica, carbon black, and white carbon. Examples of organic particles include resin particles such as crosslinked styrene-based resin particles, high-molecular-weight styrene-based resin particles, and crosslinked siloxane-based resin particles. The fine particles (P) may be particles obtained by surface-treating the above-mentioned particles with a fatty acid or the like.

[0041] The fine particles (P) are preferably inorganic particles, and are preferably one or more inorganic particles selected from the group consisting of mica and talc, with mica being more preferred. Mica may be either synthetic or natural. Mica is a type of mineral known as "mica," and has a structure in which crystal faces grown in a planar direction are stacked in multiple layers, giving it a large aspect ratio. Mica is generally added to resin compositions for the purposes of improving rigidity, heat resistance, and imparting barrier properties.

[0042] The aspect ratio (major axis / thickness) of the fine particles (P) having a layer structure such as mica is preferably 10 to 100, from the viewpoint of the formability and mechanical properties of the resin film. The lower limit is more preferably 20, and particularly preferably 30. The upper limit is more preferably 90, even more preferably 80, still more preferably 70, particularly preferably 60, and most preferably 50.

[0043] Generally, multilayer particles containing one or more rubber layers (e.g., acrylic multilayer polymers) are not included in the fine particles (P) because they have a small difference in refractive index from other thermoplastic resins (R) and do not act as matting agents or light diffusing agents.

[0044] As explained in the section [Problems to be Solved by the Invention], in conventional matte resin films, aggregates of fine particles (matting agents) may be visually recognized as foreign matter defects. Furthermore, in general, in the production of resin films, a film is produced using a molten resin that has been melt-filtered using a filter, thereby producing a film that is free of or has a sufficiently small amount of foreign matter defects caused by resin deterioration products, gelled products, etc. However, in the production of films from conventional microparticle-containing resin compositions, the filter is clogged with the microparticles (matting agent), making it impossible to remove foreign matter such as resin deterioration products and gelled products from the molten resin, which may remain as foreign matter defects.

[0045] In order to solve the above problems, in the present disclosure, the microparticles (P) have a cumulative 10% particle diameter D10 [μm], cumulative 50% particle diameter D50 [μm], and cumulative 90% particle diameter D90 [μm] in a volume-based cumulative particle diameter distribution measured by a laser diffraction / scattering method, which satisfy the following relations: 2≦D50≦4.5, and 1.1≦(Log(D50 / D10)) / (Log(D90 / D50))≦2.0. D50 is also referred to as the volume average particle diameter.

[0046] If D50 (volume average particle diameter) is less than the lower limit, the light diffusion effect and / or surface roughening effect of the fine particles (P), and the resulting matting effect, may not be effectively obtained. If D50 (volume average particle diameter) is more than the upper limit, aggregates of the fine particles (P) may be visually recognized as foreign matter defects, and the fine particles (P) may clog the filter used for melt filtration during film production, reducing the continuous productivity of the resin film. If D50 (volume average particle diameter) is within the above range, the light diffusion effect and / or surface roughening effect of the fine particles (P), and the resulting matting effect, are effectively obtained, and the aggregates of the fine particles (P) are prevented from being visually recognized as foreign matter defects, and the filter used for melt filtration during film production is prevented from being clogged by the fine particles (P), reducing the continuous productivity of the resin film. The lower limit of D50 is more preferably 2.2, particularly preferably 2.5, and most preferably 2.8. The upper limit is preferably 4.2, more preferably 4.0, even more preferably 3.8, particularly preferably 3.5, and most preferably 3.2.

[0047] When (Log(D50 / D10)) / (Log(D90 / D50)) is within the above range, the particle size distribution of the fine particles (P) is suitable, and the fine particles (P) contain a good balance of fine particles with relatively small particle sizes and fine particles with relatively large particle sizes. In this case, the fine particles with relatively large particle sizes can effectively achieve a light diffusion effect and / or an effect of imparting surface irregularities, a matting effect due to these, and an effect of improving mechanical properties such as mechanical strength. In addition, the fine particles with relatively small particle sizes can effectively prevent aggregates of the fine particles (P) from being visually recognized as foreign matter defects, and can effectively prevent a decrease in continuous productivity of the resin film due to clogging of the filters used for melt filtration during film production by the fine particles (P). The lower limit of (Log(D50 / D10)) / (Log(D90 / D50)) is more preferably 1.2, even more preferably 1.3, still more preferably 1.4, particularly preferably 1.5, and most preferably 1.6. The upper limit is more preferably 1.9, particularly preferably 1.8, and most preferably 1.7.

[0048] D10 and D90 are not particularly limited as long as they satisfy the above-mentioned requirements. D10 is preferably 0.5 to 1.6. The lower limit is more preferably 0.7, even more preferably 0.8, particularly preferably 0.9, and most preferably 1.0. The upper limit is more preferably 1.5, even more preferably 1.4, particularly preferably 1.3, and most preferably 1.2. D90 is preferably 4.5 to 6.5. The lower limit is more preferably 4.6, even more preferably 4.8, particularly preferably 5.0, and most preferably 5.2. The upper limit is more preferably 6.2, even more preferably 6.0, particularly preferably 5.9, and most preferably 5.8.

[0049] The fine particles (P) preferably have a volume-based particle size distribution measured by a laser diffraction / scattering method that has a first peak with a maximum particle size of 0.1 to 1 μm and a second peak with a maximum particle size of 2 to 8 μm. The peak top of the first peak or the second peak is the inflection point where the slope of the tangent changes from positive to negative in the volume-based particle size distribution curve, and the particle size at this inflection point is the maximum value of the particle size of the first peak or the second peak. The volume-based particle size distribution curve of the fine particles (P) can be bimodal, having the first peak and the second peak (in other words, having two maximum values).

[0050] The fine particles (PS) having a relatively small particle size included in the first peak can effectively prevent aggregates of the fine particles (P) from being visually recognized as foreign matter defects, and can easily pass through the filter used for melt filtration during film production, effectively preventing the filter used for melt filtration during film production from being clogged with the fine particles (P), which would reduce continuous film productivity. The fine particles (PL) having a relatively large particle size included in the second peak can effectively achieve the light diffusion effect and / or the effect of imparting surface irregularities, and the resulting matting effect. These effects can be effectively achieved by the fine particles (P) containing fine particles (PS) having a relatively small particle size and fine particles (PL) having a relatively large particle size.

[0051] The lower limit of the maximum particle size of the first peak is more preferably 0.2 μm, even more preferably 0.3 μm, even more preferably 0.4 μm, particularly preferably 0.5 μm, and most preferably 0.6 μm. The upper limit is more preferably 0.9 μm, particularly preferably 0.8 μm. The lower limit of the maximum particle size of the second peak is more preferably 2.5 μm, particularly preferably 3 μm, and the upper limit is more preferably 7 μm, even more preferably 6 μm, particularly preferably 5 μm, and most preferably 4 μm.

[0052] The difference in refractive index between the thermoplastic resin (R) and the fine particles (P) is not particularly limited, and is preferably 0.02 or more. The lower limit is more preferably 0.03, and particularly preferably 0.04. By using fine particles (P) whose refractive index difference with the thermoplastic resin (R) is 0.03 or more, the light diffusion effect of the fine particles (P) can be satisfactorily obtained, and a good matte appearance can be obtained.

[0053] In the present disclosure, the fine particles (P) have a surface fluorine content of 1 to 20 mass% as measured by X-ray fluorescence analysis. The lower limit is preferably 3 mass%, more preferably 5 mass%, even more preferably 8 mass%, particularly preferably 10 mass%, and most preferably 12 mass%. The upper limit is preferably 18 mass%, more preferably 15 mass%, and particularly preferably 14 mass%. When the surfaces of the fine particles (P) contain an appropriate amount of elemental fluorine, the resin film of the present disclosure can have good solvent resistance to various solvents.

[0054] As the fine particles (P), commercially available products can be used as they are or after being subjected to an appropriate treatment. If necessary, the fine particles (P) can be subjected to a known pulverization treatment before being mixed with the thermoplastic resin (R). Examples of pulverization devices include jet mill pulverizers, ball mill pulverizers, cutting mill pulverizers, and impact pulverizers. Among these, jet mill pulverizers that pulverize particles by impact with high-speed compressed air or gas jets are preferred, and fluidized-bed jet mill pulverizers are particularly preferred. In fluidized-bed jet mill pulverizers, the fine particles (P) can be pulverized by causing them to collide with each other through the collision of opposing jets of air. This method can obtain fine particles having a desired particle size distribution while preventing contamination by impurities. If necessary, the fine particles (P) may be subjected to a separation treatment such as sieving using a filter with appropriate openings before being mixed with the thermoplastic resin (R), instead of or in addition to the pulverization treatment.

[0055] (optional ingredient) The microparticle-containing resin composition of the present disclosure may contain one or more optional components as needed, provided that the effects of the present invention are not impaired. Examples of optional components include various additives such as antioxidants, heat deterioration inhibitors, UV absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, colorants (dyes, pigments, organic dyes, etc.), impact modifiers, foaming agents, fillers, and fluorescent materials. The timing of adding the additives is optional, such as during or after polymerization of the thermoplastic resin (R), during or after kneading the thermoplastic resin (R) and the fine particles (P). The content of the additives can be appropriately set within a range that does not impair the effects of the present invention. For example, the content of the antioxidant is preferably 0.01 to 1 part by mass, the content of the ultraviolet absorber is preferably 0.01 to 3 parts by mass, the content of the light stabilizer is preferably 0.01 to 3 parts by mass, and the content of the lubricant is preferably 0.01 to 3 parts by mass, per 100 parts by mass of the thermoplastic resin (R) (100 parts by mass in total if multiple types are used).

[0056] [Method of manufacturing fine particle-containing resin composition] The microparticle-containing resin composition of the present disclosure can be produced by melt-kneading multiple materials, including one or more thermoplastic resins (R), one or more microparticles (P), and, if necessary, one or more optional components, so that each component is uniformly dispersed. The melt-kneading may be carried out multiple times. The melt-kneading can be carried out using a melt-kneading device such as an extruder, a kneader-ruder, a mixing roll, or a Banbury mixer. From the viewpoint of melt-kneading properties, extruders such as single-screw extruders, twin-screw extruders, and multi-screw extruders are preferred, with twin-screw extruders being more preferred. The melt-kneading temperature is adjusted appropriately depending on the melting temperature of the resin components and is preferably 140 to 300°C. The lower limit is more preferably 160°C, even more preferably 180°C, even more preferably 200°C, even more preferably 220°C, particularly preferably 240°C, and most preferably 250°C. The upper limit is more preferably 280°C, particularly preferably 270°C, and most preferably 260°C. The shear rate applied to the fine particle-containing resin composition during melt-kneading is preferably 100 sec -1 More than 200 seconds, preferably -1 That's all. The resulting melt-kneaded product may be molded directly into a film, or may be processed into any desired form such as pellets, granules, or powder to improve convenience during storage, transportation, or molding.

[0057] [Resin film] The resin film of the present disclosure is a film having a single layer structure or a laminate structure including a microparticle-containing resin layer made of the microparticle-containing resin composition of the present disclosure. The resin film of the present disclosure can be used as a matte resin film. The resin film of the present disclosure having a laminated structure may be a laminated film including two or more microparticle-containing resin layers made of the microparticle-containing resin composition of the present disclosure, or a laminated film including one or more microparticle-containing resin layers made of the microparticle-containing resin composition of the present disclosure and one or more other layers. The resin film of the present disclosure may be an unstretched film or a stretched film. Unless otherwise specified, the term "film" refers to an unstretched film. The thickness of the microparticle-containing resin layer made of the microparticle-containing resin composition of the present disclosure is not particularly limited, but is preferably 10 to 500 μm. The lower limit is more preferably 30 μm, even more preferably 40 μm, particularly preferably 50 μm, and most preferably 80 μm. The upper limit is more preferably 400 μm, even more preferably 300 μm, particularly preferably 200 μm, and most preferably 150 μm.

[0058] The other layer may be a resin layer having a composition other than that of the microparticle-containing resin composition of the present disclosure. The resin constituting the other resin layer is not particularly limited, and examples thereof include polycarbonate resins, vinyl chloride resins, vinylidene fluoride resins, (meth)acrylic resins, styrene resins such as ABS resins, AES resins, and AS resins, and combinations thereof. Other layers include various functional layers such as a printing layer, a hard coat layer, an antiglare layer, an antireflection layer, an antisticking layer, a diffusion layer, an antistatic layer, an antifouling layer, and an easy-slip layer containing fine particles, etc.

[0059] [Manufacturing method of resin film] The resin film of the present disclosure having a single layer structure can be produced by a known film forming method such as extrusion molding, solution casting, compression molding (press molding), inflation molding, blow molding, calendar molding, melt casting, etc. Among these, extrusion molding is preferred from the viewpoint of productivity, etc.

[0060] A method for producing the resin film of the present disclosure having a laminated structure includes the following steps: (1) A method of producing a laminated film by melt-co-extruding a plurality of types of the microparticle-containing resin compositions of the present disclosure having different compositions (co-extrusion molding method); (2) A method of producing a laminated film by melt-co-extruding one or more of the microparticle-containing resin compositions of the present disclosure and one or more other thermoplastic resins (compositions) (co-extrusion molding method); (3) A method of producing a laminated film by first obtaining a film from either the microparticle-containing resin composition of the present disclosure or another thermoplastic resin (composition), and then melt-extrusion coating the obtained film with the other resin. (4) A method in which films are prepared in advance from both the microparticle-containing resin composition of the present disclosure and another thermoplastic resin (composition), and then these films are press-bonded by thermocompression; (5) A method of producing a laminated film by first obtaining a film from the microparticle-containing resin composition of the present disclosure and then polymerizing the polymerizable composition on the obtained film can be exemplified. Among these, co-extrusion molding is preferred.

[0061] The method for producing a monolayer film by the T-die method will be described below. The microparticle-containing resin composition of the present disclosure is melt-kneaded using an extruder and extruded in a molten state from a T-die having a wide discharge port. The melt-kneading is preferably carried out under reduced pressure using a vent or under a nitrogen gas flow. To remove foreign matter, the molten resin is preferably melt-filtered using a filter before extrusion. By forming a film using the melt-filtered molten resin, a film free of or with sufficiently few defects caused by foreign matter and gels can be obtained. The filter material for the filter is appropriately selected based on the operating temperature, viscosity, filtration accuracy, etc. Examples include nonwoven fabrics made of glass fiber, etc.; sheets made of cellulose impregnated with phenolic resin; sintered metal fiber nonwoven sheets; sintered metal powder sheets; wire mesh; and combinations thereof. Among these, from the viewpoint of heat resistance and durability, a filter formed by stacking multiple sintered metal fiber nonwoven sheets is preferred. The filtration accuracy of the filter is not particularly limited, but is preferably 200 μm or less, more preferably 100 μm or less, and particularly preferably 50 μm or less. In order to improve the accuracy of the thickness of the film, a gear pump may be installed in the extrusion molding line to carry out film production.

[0062] The molten resin extruded into a film form from a T-die is cooled using multiple cooling rolls. The number of cooling rolls is two or more, preferably three to four. In the resin film manufacturing method of the present disclosure, it is preferable that the first and second cooling rolls counting from the T-die side are both rigid metal rolls, or one is a rigid metal roll and the other is an elastic metal roll. This method provides good adhesion of the molten resin to the cooling roll and good releasability from the cooling roll, preventing the fine particles (P) from protruding from the film surface, and allows the production of a resin film in which at least one film surface has high gloss and excellent printability during manufacturing.

[0063] The rigid metal roll is a roll having no elasticity and made of a metal such as stainless steel, and examples thereof include a drilled roll and a spiral roll. The surface of the rigid metal roll is preferably a mirror finish, since this allows the production of a film with high surface smoothness. The metal elastic roll is a roll having an elastic outer cylinder made of a thin metal film on its outer periphery. The metal elastic roll is composed of, for example, a metal shaft roll made of stainless steel or the like, a metal thin film (elastic outer cylinder) made of stainless steel or the like covering the outer surface of the shaft roll, and a fluid sealed between the shaft roll and the metal thin film (elastic outer cylinder), and can exhibit elasticity in the presence of the fluid. Examples of the fluid include water and oil. The thickness of the metal thin film of the metal elastic roll is not particularly limited, but is preferably about 2 to 8 mm. The metal thin film preferably has flexibility and bendability, and preferably has a seamless structure without welded joints. A metal elastic roll equipped with such a metal thin film is excellent in durability, and if the metal thin film is mirror-finished, it can be handled in the same way as a normal mirror-finished roll, and can produce a film with high surface smoothness.

[0064] The smaller the difference between the surface temperature of the cooling roll and the glass transition temperature (Tg) of the microparticle-containing resin composition, the better the adhesion of the molten resin to the cooling roll, resulting in improved surface smoothness and gloss of the resulting film, but the releasability of the molten resin from the cooling roll tends to decrease. When the surface temperature of one of the first and second cooling rolls is T1 and the surface temperature of the other cooling roll is T2 (where T2≧T1), and the glass transition temperature (Tg) of the microparticle-containing resin composition is TgC, |TgC−T2| is preferably 10 to 40°C, more preferably 15 to 20°C. The TgC of the microparticle-containing resin composition is not particularly limited and is preferably 70 to 160° C., more preferably 90 to 150° C. The T2 is preferably 60 to 90° C., more preferably 70 to 80° C. If the T2 is within this range, a good balance is achieved between the surface smoothness and surface gloss of the film and the releasability of the molten resin from the cooling roll, which is preferred.

[0065] Since the resin film is sufficiently pressed and cooled by the first and second cooling rolls, the type and surface temperature of the third and subsequent cooling rolls, which are used as needed, are not particularly limited. The third and subsequent cooling rolls are preferably rigid metal rolls, and their surface temperatures are preferably 50 to 90°C, more preferably 60 to 80°C. The monolayer film obtained after cooling is taken up by a take-up roll. The above steps of extrusion, cooling, and taking up are carried out continuously.

[0066] The thickness of the resin film of the present disclosure produced by the above-mentioned production method is preferably 10 to 500 μm from the viewpoints of film-forming properties, secondary processability such as lamination properties, handling properties, cutting properties, and punching properties, and material costs. The lower limit is more preferably 30 μm, even more preferably 40 μm, particularly preferably 50 μm, and most preferably 80 μm. The upper limit is more preferably 400 μm, even more preferably 300 μm, particularly preferably 200 μm, and most preferably 150 μm.

[0067] The resin film of the present disclosure may be a stretched film. That is, the unstretched film obtained by the above-mentioned production method may be subjected to a stretching treatment to form a stretched film. The stretching treatment increases the mechanical strength, making it possible to obtain a film that is less susceptible to cracking. The stretching method is not particularly limited, and examples thereof include simultaneous biaxial stretching, sequential biaxial stretching, and tubular stretching. From the viewpoint of achieving uniform stretching and obtaining a high-strength film, the stretching temperature is preferably +10°C to +40°C relative to the glass transition temperature (TgC) of the microparticle-containing resin composition.

[0068] In coextrusion molding, the constituent resins (compositions) of each layer are melt-kneaded using an extruder and coextruded in the form of a film from a T-die with a wide discharge opening in the form of the desired laminate structure. Examples of lamination methods include the feedblock method, in which lamination occurs before the resins enter the T-die, and the multi-manifold method, in which lamination occurs inside the T-die. The multi-manifold method is preferred from the viewpoint of improving the interfacial smoothness between layers. The molten laminate resins coextruded from the T-die are pressurized and cooled using multiple cooling rolls. The laminated film obtained after cooling is taken up by a pair of take-up rolls. The above extrusion, cooling, and take-up processes are carried out continuously.

[0069] [Printed resin film] One embodiment of the resin film of the present disclosure is a printed resin film comprising a microparticle-containing resin layer made of the microparticle-containing resin composition of the present disclosure and a printed layer. This film can be a resin film of a single-layer structure or a laminate structure, which includes a microparticle-containing resin layer made of the microparticle-containing resin composition of the present disclosure and, if necessary, can include other resin layers, and at least one surface (usually one surface) of the resin film is printed. The printing method is not particularly limited, and examples thereof include gravure printing, flexographic printing, and silk screen printing. When the printed resin film of the present disclosure is laminated onto a substrate, it is preferable to laminate the film so that the printed surface is in contact with the substrate, from the viewpoint of protecting the printed surface and imparting a luxurious feel.

[0070] [Laminate] The laminate of the present disclosure is obtained by laminating the resin film of the present disclosure on a substrate. By laminating the resin film of the present disclosure on the substrate, the effects of improving the design of the substrate and / or protecting the substrate can be obtained. The material of the substrate is not particularly limited, and examples thereof include resin, steel, wood, glass, and combinations thereof. The resin used for the substrate is not particularly limited, and examples thereof include thermoplastic resins and thermosetting resins. Examples of thermoplastic resins used for the substrate include polycarbonate-based resins, polyethylene terephthalate (PET), amide-based resins, olefin-based resins, styrene-based resins (such as ABS resin), vinyl chloride-based resins, and (meth)acrylic-based resins. Examples of thermosetting resins used for the substrate include epoxy-based resins, phenol-based resins, and melamine-based resins.

[0071] The method for producing the laminate of the present disclosure is not particularly limited, and examples include adhesion, lamination, pressure forming, vacuum forming, three-dimensional surface decoration forming (Three Dimension Overlay Method: TOM forming), insert molding, and in-mold forming. When the substrate is made of a resin, a method of vacuum forming, pressure forming, or compression molding the resin film of the present disclosure onto the surface of the substrate under heating is preferred. Among these, a simultaneous injection molding and lamination method is particularly preferred. The simultaneous injection molding and lamination method is a method in which the resin film of the present disclosure is inserted between a pair of male and female injection molds, and then a molten thermoplastic resin is injection molded into the molds (on one side of the film). This method allows the lamination of the film to be carried out simultaneously with the production of the injection molded article.

[0072] The film inserted into the mold may be flat, or it may have a three-dimensional shape obtained by preforming using vacuum forming, pressure forming, or other methods. The film may be preformed in a separate molding machine, or it may be preformed in the mold of an injection molding machine used in the injection molding and lamination method. The method of injecting molten resin onto one side of a preformed film is called the insert molding method. When the substrate is made of a resin, the substrate and the film to be laminated may be co-extruded.

[0073] In the laminate of the present disclosure, the outermost layer may be the resin film of the present disclosure in order to achieve a good matte appearance. The laminate of the present disclosure can exhibit a good matte appearance by being subjected to a heat treatment without pressure after the molding. Since the resin film of the present disclosure has good solvent resistance, when used as the outermost layer of a laminate, deterioration such as whitening is suppressed even when the film is cleaned and washed using disinfectants and detergents containing various solvents. In the laminate of the present disclosure, a curable composition may be applied to the resin film of the present disclosure combined with a substrate, and then cured by irradiation with ultraviolet (UV) or electron beam (EB) to form a coating layer. In this case, the design or substrate protection can be further improved.

[0074] As described above, according to the present disclosure, it is possible to provide a microparticle-containing resin composition capable of producing a resin film having excellent mechanical properties such as a matte appearance, appearance quality, solvent resistance, and flex resistance, and a resin film using the same.

[0075] [Application] The microparticle-containing resin composition and resin film of the present disclosure can be used in any application, and are suitable for various applications requiring design, such as applications requiring a matte appearance. The resin film of the present disclosure is suitable for decorative films, building materials, etc. Suitable applications include architectural components such as doors, sashes, domes, safety window glass, partitions, staircase wainscoting, balcony wainscoting, and roofs of leisure buildings. Other applications include sign components or marking films such as advertising towers, stand signs, side signs, transom signs, and rooftop signs; display components such as showcases, partitions, and store displays; lighting components such as fluorescent light covers, mood lighting covers, lampshades, illuminated ceilings, illuminated walls, and chandeliers; transportation components such as aircraft windshields, pilot visors, motorcycle windshields, motorboat windshields, bus sunshades, automobile side visors, rear visors, head wings, headlight covers, automobile interior components, and automobile exterior components such as bumpers; and audiovisual nameplates. , stereo covers, television protective masks, vending machines, mobile phones, personal computers, and other electronic equipment parts; medical equipment parts such as incubators and X-ray parts; equipment-related parts such as machine covers, instrument covers, laboratory equipment, rulers, dials, and observation windows; solar cell parts such as solar cell back films and flexible solar cell front films; various home appliances; bathroom components such as greenhouses, large aquariums, box aquariums, clock panels, bathtubs, sanitary products, desk mats, game parts, toys, musical instruments, wallpaper, and decorative and protective films provided on the surfaces of face protection masks used during welding, etc. [Example]

[0076] Examples and comparative examples according to the present invention will be described below. In the following description, unless otherwise specified, "parts" in the units of blend amounts represent "parts by mass."

[0077] [Evaluation items and evaluation methods] The evaluation items and evaluation methods are as follows. (Volume-based particle size distribution and volume-based cumulative particle size distribution of fine particles (P)) The volumetric particle size distribution and the volumetric cumulative particle size distribution of the aqueous dispersion of the fine particles (P) were measured by a laser diffraction / scattering method using a nanoparticle size distribution measuring device (SALD-7500, manufactured by Shimadzu Corporation). The volume-based particle size distribution thus obtained was checked for the presence or absence of a first peak having a maximum particle size (particle size at the peak top) of 0.1 to 1 μm and a second peak having a maximum particle size (particle size at the peak top) of 2 to 8 μm, and if the first peak and / or the second peak were present, the maximum particle size of each peak (particle size at the peak top) was determined. The peak top is the inflection point (maximum value) where the slope of the tangent line changes from positive to negative. From the obtained volume-based cumulative particle size distribution, calculations were made starting from the smallest particle size to determine the particle size at which the cumulative frequency was 10% (cumulative 10% particle size), D10, the particle size at which the cumulative frequency was 50% (cumulative 50% particle size), D50 (median size), and the particle size at which the cumulative frequency was 90% (cumulative 90% particle size), D90. From these data, the value of (Log(D50 / D10)) / (Log(D90 / D50)) was calculated.

[0078] (Fluorine element content on the surface of fine particles (P)) Using a scanning X-ray fluorescence analyzer (Rigaku Corporation, "ZSX Primus IV"), elemental analysis of the surface of the fine particles (P) was performed by X-ray fluorescence analysis to determine the content of elemental fluorine.

[0079] (Matte film quality) The resin film obtained in each example was heated at 140°C for 1 minute and then allowed to cool naturally to room temperature (20 to 30°C). The gloss (also called 60° gloss) of the film surface was measured under 60° reflection conditions using a "VG7000" manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS Z 8741, and evaluated according to the following criteria. <Judgment criteria> Good (◯): 60° gloss is 50% or less. Poor (×): 60° gloss is greater than 50%.

[0080] (Number of foreign objects) A 100mm x 100mm test piece was cut from the resin film obtained in each example. This test piece was heated at 140°C for 1 minute, allowed to cool naturally to room temperature (20-30°C), and then placed on a matte black cloth (manufactured by Kawashima Selkon Textiles). In a room equipped with a lit three-wavelength fluorescent lamp and an illuminance of 2300-2600 lux, the film surface was visually observed using the reflected light from the fluorescent lamp perpendicular to the film surface. Foreign matter defects include aggregates of fine particles (P); foreign matter defects caused by resin deterioration and gelation, etc. The product of width and length was 0.03mm. 2 Count the number of foreign matter defects of a size greater than 100cm 2 The number of foreign matter defects (also simply referred to as the number of foreign matters) per unit was calculated and evaluated according to the following criteria. <Judgment criteria> Good (◯): The number of foreign matter particles is 10 or less. Defective (×): The number of foreign objects is more than 10.

[0081] (Solvent resistance) A 50mm x 50mm piece of gauze was placed on the resin film obtained in each example, and 0.4g of a solvent-containing sunscreen (Volkswagen test batch "VWPM3964") was evenly applied on top of it. The sample was left in an oven set to 50°C for 24 hours, then removed from the oven and left in an environment of 23±2°C and 50±5% relative humidity for 4 hours. The gauze was removed from the resin film, and the film surface was wiped dry with a dry cloth. The film surface was then visually observed and evaluated according to the following criteria. Good (◯): No change in appearance was observed. Fair (△): No gauze marks were observed, but slight whitening was observed. Poor (x): Gauze marks were observed.

[0082] (Bending resistance) A test piece 10 mm wide and 120 mm long was cut out from the widthwise center of the resin film obtained in each example so that the extrusion direction was the longitudinal direction, and the number of refractions was measured in accordance with JIS P 8115 (2001). Evaluation was based on the following criteria. <Judgment criteria> Good (◯): The number of refractions is 10 or more. Poor (x): The number of refractions is less than 10.

[0083] (Production Example 1) Polymerization of acrylic multilayer polymer particles (A-1) (1) A reactor equipped with a stirrer, thermometer, nitrogen gas inlet, monomer inlet tube, and reflux condenser was charged with 100 parts of deionized water, 0.02 parts of sodium dodecylbenzenesulfonate, and 0.1 parts of sodium carbonate. The atmosphere inside the vessel was thoroughly purged with nitrogen gas to make it substantially oxygen-free, and the internal temperature was then set to 80°C. 0.01 parts of potassium persulfate was added and stirred for 5 minutes. A monomer mixture consisting of 32.9 parts of methyl methacrylate (MMA), 2.11 parts of methyl acrylate (MA), and 0.07 parts of allyl methacrylate (ALMA) was then continuously added dropwise over 20 minutes. After the addition was completed, the polymerization reaction was continued for an additional 30 minutes until the polymerization rate reached 98% or higher.

[0084] (2) Next, 0.04 parts of potassium persulfate was added to the reactor and stirred for 5 minutes, after which a monomer mixture consisting of 8.00 parts of styrene (St), 37 parts of n-butyl acrylate (BA), and 0.9 parts of allyl methacrylate (ALMA) was continuously added dropwise over 40 minutes. After the addition was completed, the polymerization reaction was continued for another 30 minutes until the polymerization rate reached 98% or higher.

[0085] (3) Next, 0.02 parts of potassium persulfate was added to the reactor and stirred for 5 minutes, after which a monomer mixture consisting of 20 parts of methyl methacrylate (MMA), 1.20 parts of methyl acrylate (MA), and 0.304 parts of n-octyl mercaptan (nOM) (chain transfer agent) was continuously added dropwise over 100 minutes. After the addition was completed, the polymerization reaction was continued for another 60 minutes until the polymerization rate reached 98% or more, thereby obtaining a latex containing acrylic multilayer structure polymer particles (A-1). The volume-based cumulative particle size distribution of the particles in the obtained latex was measured by laser diffraction / scattering method.The volume average particle size was 0.2 μm.

[0086] (4) Next, the latex containing the acrylic multilayer structure polymer particles (A-1) was frozen at -30°C for 4 hours. This frozen latex was poured into 80°C hot water in an amount twice the amount of the frozen latex, dissolved, and kept at 80°C for 20 minutes. The resulting slurry was dehydrated and dried at 70°C to obtain powdery acrylic multilayer structure polymer particles (A-1) having a three-layer structure.

[0087] (Production Example 2) Polymerization of acrylic multilayer polymer particles (A-2) (1) A reactor equipped with a stirrer, thermometer, nitrogen gas inlet, monomer inlet tube, and reflux condenser was charged with 150 parts of deionized water, 1 part of sodium dodecylbenzenesulfonate, and 0.05 parts of sodium carbonate. The atmosphere inside the vessel was thoroughly purged with nitrogen gas to make it substantially oxygen-free, and the internal temperature was then set to 80°C. 0.02 parts of potassium persulfate was added and stirred for 5 minutes. A monomer mixture consisting of 9.39 parts of methyl methacrylate (MMA), 0.61 parts of methyl acrylate (MA), and 0.02 parts of allyl methacrylate (ALMA) was then continuously added dropwise over 20 minutes. After the addition was completed, the polymerization reaction was continued for an additional 30 minutes until a polymerization rate of 98% or higher was achieved.

[0088] (2) Next, 0.05 parts of potassium persulfate was added to the reactor and stirred for 5 minutes, after which a monomer mixture consisting of 8.89 parts of styrene (St), 27.67 parts of n-butyl acrylate (BA), and 2.00 parts of allyl methacrylate (ALMA) was continuously added dropwise over 40 minutes. After the addition was completed, the polymerization reaction was continued for another 30 minutes until the polymerization rate reached 98% or higher.

[0089] (3) Next, a monomer mixture consisting of 37.61 parts of methyl methacrylate (MMA), 2.39 parts of methyl acrylate (MA), and 0.12 parts of n-octyl mercaptan (nOM) (chain transfer agent) was continuously added dropwise to the reactor over 100 minutes. After the addition was completed, the polymerization reaction was continued for another 60 minutes until the polymerization rate reached 98% or more, thereby obtaining a latex containing acrylic multilayer structure polymer particles (A-2). The volume-based cumulative particle size distribution of the particles in the obtained latex was measured by laser diffraction / scattering method.The volume average particle size was 0.09μm.

[0090] (4) Next, in the same manner as in (4) of Production Example 1, the latex containing the acrylic multilayer structure polymer particles (A-2) was frozen, slurried, dehydrated, and dried to obtain powdery acrylic multilayer structure polymer particles (A-2) having a three-layer structure.

[0091] [material] The following materials were prepared: <Methacrylic resin (PM)> (PM-1) Linear polymethyl methacrylate (PMMA), "Parapet (registered trademark) EH" manufactured by Kuraray Co., Ltd.

[0092] <Methacrylic resin composition (MR)> (MR-1) A methacrylic resin composition (MR-1) was obtained by melt-kneading 16 parts of the acrylic multilayer polymer particles (A-1), 32 parts of the acrylic multilayer polymer particles (A-2), and 52 parts of the methacrylic resin (PM-1).

[0093] <Polycarbonate resin (PC)> (PC-1) SD Polycarbonate 300 Series manufactured by Sumika Polycarbonate Co., Ltd.

[0094] <Polypropylene resin (PP)> (PP-1) "Wintec (registered trademark) WFW4" manufactured by Japan Polypropylene Corporation.

[0095] <Fine particles (P)> (P-1) Mica fine particles, "Micromica MK100" manufactured by Katakura Co-op Agri Co., Ltd., volume average particle diameter (D50) 5 μm, aspect ratio (catalog value) 30 to 50). (P-1J) Mica fine particles, jet milled product obtained by pulverizing fine particles (P-1) using a jet mill pulverizer. (P-1F) Mica fine particles, fine particles (P-1) are sieved through a filter with 20 μm openings, and the filtered product is passed through the filter. (P-2) Organic resin particles, cross-linked polymethyl methacrylate (PMMA) particles "MBX-8" manufactured by Techno Polymer Co., Ltd. Representatively, the measurement results of the volume-based particle size distribution and the volume-based cumulative particle size distribution of the fine particles (P-1J) and (P-1F) are shown in FIG. The evaluation results for each particle are shown in Table 1.

[0096] Example E1 93 parts of the methacrylic resin composition (MR-1) and 7 parts of the microparticles (P-1J) were charged into a 65 mmφ single-screw extruder equipped with a vent and a T-die. The microparticle-containing resin composition was extruded at a set temperature of 260°C and a discharge rate of 70 kg / h, and sandwiched between a mirror-finished metal rigid roll and a mirror-finished metal elastic roll both set at 90°C to obtain a 100 μm-thick resin film. The main manufacturing conditions and evaluation results are shown in Table 1. In this table, conditions not listed in the table were common conditions.

[0097] (Example E2, Comparative Example EC3) A resin film was obtained in the same manner as in Example E1, except that the mass ratio of the methacrylic resin composition (MR-1) to the fine particles (P-1J) was changed. The main production conditions and evaluation results are shown in Table 1.

[0098] (Examples E3 and E4) Resin films were obtained in the same manner as in Example E1, except that polycarbonate resin (PC-1) or polypropylene resin (PP-1) was used instead of the methacrylic resin composition (MR-1). The main production conditions and evaluation results are shown in Table 1.

[0099] (Comparative examples EC1, EC2) A resin film was obtained in the same manner as in Example E1, except that the type of fine particles (P) was changed. The main production conditions and evaluation results are shown in Table 1.

[0100] [Table 1]

[0101] (Evaluation results) In Examples E1 to E4, resin films were produced from a microparticle-containing resin composition containing a thermoplastic resin (R) and microparticles (P), wherein the microparticles (P) satisfied 2≦D50≦8 and 1.1≦(Log(D50 / D10)) / (Log(D90 / D50))≦2.0, the surface fluorine content was 1 to 20 mass%, the thermoplastic resin (R) content was 50 to 99.5 mass%, and the microparticle (P) content was 0.5 to 25 mass%. In the resin films obtained in these examples, good matte properties were obtained due to the addition of the fine particles (P). In these examples, the particle size distribution of the fine particles (P) was suitable, the dispersibility of the fine particles (P) was good in the fine particle-containing resin composition and the resin film, and aggregation of the fine particles (P) was suppressed. Furthermore, clogging of the filter used for melt filtration during film formation by the fine particles (P) was suppressed. The resin films obtained in these examples had no or sufficiently few foreign matter defects and had good appearance quality. In all of the resin films obtained in these Examples, the surfaces of the fine particles (P) contained an appropriate amount of fluorine element, and the resin films had good solvent resistance. All of the resin films obtained in these Examples had an appropriate content of the fine particles (P), good mechanical strength, and good flex resistance. The resin films obtained in these examples were suitable for use as decorative films and the like.

[0102] The resin film made of the fine particle-containing resin composition obtained in Comparative Example EC1, in which comparative organic resin fine particles the surfaces of which did not contain fluorine elements were used as the fine particles (P), had poor solvent resistance. The resin film obtained in Comparative Example EC2, which used fine particles (P) with a D50 of more than 4.5 μm, had aggregates of the fine particles (P), a large number of foreign objects, and a poor appearance quality. The resin film obtained in Comparative Example EC3, in which the amount of fine particles (P) added was more than 20 mass %, had an excessive amount of fine particles in the resin film, and the mechanical strength of the resin film was reduced, resulting in poor flex resistance.

[0103] The present invention is not limited to the above-described embodiments and examples, and appropriate design changes are possible without departing from the spirit of the present invention.

Claims

1. A microparticle-containing resin composition comprising a thermoplastic resin (R) and microparticles (P), The microparticles (P) have a cumulative 10% particle diameter D10 [μm], a cumulative 50% particle diameter D50 [μm], and a cumulative 90% particle diameter D90 [μm] in a volume-based cumulative particle diameter distribution measured by a laser diffraction / scattering method that satisfy 2≦D50≦4.5 and 1.1≦(Log(D50 / D10)) / (Log(D90 / D50))≦2.0, and a surface fluorine content measured by X-ray fluorescence analysis of 1 to 20% by mass, A microparticle-containing resin composition having a thermoplastic resin (R) content of 50 to 99.5 mass % and a microparticle (P) content of 0.5 to 25 mass %.

2. 2. The microparticle-containing resin composition according to claim 1, wherein the microparticles (P) have a volume-based particle size distribution measured by a laser diffraction / scattering method, which has a first peak having a maximum particle size of 0.1 to 1 μm and a second peak having a maximum particle size of 2 to 8 μm.

3. The fine particle-containing resin composition according to claim 1, wherein the fine particles (P) are inorganic particles.

4. 4. The fine particle-containing resin composition according to claim 3, wherein the fine particles (P) are one or more kinds of inorganic particles selected from the group consisting of mica and talc.

5. 2. The fine particle-containing resin composition according to claim 1, wherein the thermoplastic resin (R) comprises a combination of a methacrylic resin and a rubber-like polymer, a polycarbonate resin, or a polypropylene resin.

6. A resin film comprising a microparticle-containing resin layer made of the microparticle-containing resin composition according to any one of claims 1 to 5.

7. The resin film according to claim 6, wherein the thickness of the fine particle-containing resin layer is 10 to 500 μm.

8. The resin film according to claim 6 , comprising the fine particle-containing resin layer and a printed layer.

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