WO2012132533A1 - 着色樹脂粒子、その製造方法、及びその用途 - Google Patents
着色樹脂粒子、その製造方法、及びその用途 Download PDFInfo
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- WO2012132533A1 WO2012132533A1 PCT/JP2012/051967 JP2012051967W WO2012132533A1 WO 2012132533 A1 WO2012132533 A1 WO 2012132533A1 JP 2012051967 W JP2012051967 W JP 2012051967W WO 2012132533 A1 WO2012132533 A1 WO 2012132533A1
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- resin particles
- colored resin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0004—Coated particulate pigments or dyes
- C09B67/0008—Coated particulate pigments or dyes with organic coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0241—Containing particulates characterized by their shape and/or structure
- A61K8/0245—Specific shapes or structures not provided for by any of the groups of A61K8/0241
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
- A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/111—Anti-reflection coatings using layers comprising organic materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/42—Colour properties
- A61K2800/43—Pigments; Dyes
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/60—Particulates further characterized by their structure or composition
- A61K2800/61—Surface treated
- A61K2800/62—Coated
- A61K2800/624—Coated by macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/96—Applications coating of particles
- C08G2261/962—Applications coating of particles coating of organic particles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2339/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/254—Polymeric or resinous material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2998—Coated including synthetic resin or polymer
Definitions
- the present invention relates to colored resin particles and a method for producing the same, and more specifically, colored resin particles in which a polymer derived from a nitrogen-containing aromatic compound is coated on the surface of the resin particles, a method for producing the same, and a use thereof (resin Composition, molded body, light diffusion plate, paint, coated article, optical film, antiglare film, and external preparation).
- Patent Document 1 the shape of the fine particles coated with black pyrrole is not examined, and general spherical particles are used. Since the black particles obtained using the spherical fine particles are spherical, rolling friction is small and adhesion is inferior.
- a display device such as a liquid crystal display
- when the surroundings are bright there is a problem that external light is reflected on the display surface like a mirror, making it difficult to see information such as images and videos displayed on the display surface.
- an anti-glare film is provided on the display surface to diffuse the light reflected on the display surface, thereby giving the display surface an anti-glare property and reflecting external light by surface reflection. The technology which reduces is adopted.
- the conventional anti-glare film has a configuration in which an anti-glare property is imparted to the display surface of the display device by a fine uneven shape provided on the surface thereof.
- a coating liquid is formed by applying a dispersion liquid in which resin particles are dispersed in a binder resin and drying the film. The forming method has become mainstream.
- the conventional anti-glare film has a problem that the anti-glare layer (the coating film in which the resin particles are dispersed) looks whitish due to light scattering due to the unevenness of the surface, and the display contrast by the display device is lowered. is there. Further, the conventional anti-glare film has a problem that the display is glaring because the unevenness on the surface of the anti-glare layer acts like a lens. In addition, the conventional antiglare film has a problem in that display contrast is reduced by backscattering (light generated by scattering of light emitted from the display device by resin particles).
- Patent Document 2 proposes an antiglare member having an antiglare layer composed of black fine particles and a transparent binder.
- the antiglare member of Patent Document 2 has extremely low light transmittance because the black pigment fine particles used are dispersed throughout the entire particle, that is, the inside of the particle. Therefore, there exists a subject that the display of the display apparatus using this anti-glare member will become dark.
- the present invention has been made in view of the above problems, and is a colored resin particle having excellent adhesion and a method for producing the same, and a resin composition, a molded body, a light diffusion plate, a paint, a coated article, an optical film, An object is to provide an antiglare film and an external preparation.
- the colored resin particles (1) according to the present invention have a circular outer shape when viewed from the direction in which the projected area is maximized, and are viewed from the direction in which the projected area is minimized.
- the outer shape of the irregularly shaped resin particles is noncircular, and the surface of the irregularly shaped resin particles is coated with a polymer derived from a nitrogen-containing aromatic compound.
- the outer shape of the deformed resin particle when viewed from the direction where the projected area is maximum is circular
- the outer shape of the deformed resin particle when viewed from the direction where the projected area is minimum Is non-circular and has an irregular shape, and therefore has a larger rolling friction and excellent adhesion than the spherical resin particles. Therefore, for example, the colored resin particles (1) are attached to eyelashes, eyebrows, skin, hair or the like by using them in cosmetics such as makeup cosmetics such as mascara and dyeing compositions for hair. It is possible to realize a cosmetic that is excellent in adhesion and is difficult to peel off.
- the colored resin particles (1) are provided with a coating layer of a polymer derived from a nitrogen-containing aromatic compound on the surface of the resin particles, the colored resin particles (1) are colored while ensuring a certain degree of light transmittance. is doing. Therefore, the colored resin particles (1) can also be used as an antiglare member such as an antiglare film.
- an antiglare member such as an antiglare film.
- the irregular shape has a concave shape, a hemispherical shape, a double-sided convex lens shape, or a mushroom shape. It is characterized by the shape.
- the colored resin particles (3) are characterized in that, in the colored resin particles (1) or (2), the nitrogen-containing aromatic compound is pyrrole or a pyrrole derivative.
- a coating layer of a polymer derived from the nitrogen-containing aromatic compound can be uniformly formed on the surface of the resin particles.
- black colored resin particles can be provided.
- the black colored resin particles are suitable as cosmetics such as a cosmetic composition for makeup such as mascara and a dyeing composition for hair, and are also suitable as the antiglare member described above.
- the colored resin particles (4) according to a preferred embodiment of the present invention are the above-mentioned colored resin particles (1) to (3), wherein the resin particles have (meth) acrylic acid having an alkylene oxide group. It is obtained by polymerizing a polymerizable vinyl monomer containing an ester.
- the colored resin particle (4) it is possible to easily realize a desired irregularly shaped colored resin particle, particularly a colored resin particle having a hemispherical shape or a cross-section horseshoe shape.
- the outer shape of the deformed resin particles is circular when viewed from the direction where the projected area is maximized by polymerizing the polymerizable vinyl monomer.
- the colored resin particles (1) can be produced. Accordingly, colored resin particles having excellent adhesion can be produced.
- the manufacturing method (2) of the colored resin particles according to a preferred embodiment of the present invention is the manufacturing method (1), wherein the deformed shape is a shape having a concave portion, a hemispherical shape, a double-sided convex lens shape, or It is characterized by a mushroom shape.
- a polymerizable vinyl monomer is used as a seed particle. It is characterized in that resin particles are obtained by polymerizing the absorbed polymerizable vinyl monomer.
- colored resin particles controlled to have any irregular shape and size can be easily produced.
- a method (4) for producing colored resin particles according to a preferred embodiment of the present invention includes a polymer derived from the nitrogen-containing aromatic compound in any one of the production methods (1) to (3).
- the resin particles are dispersed in an aqueous medium containing an alkali metal salt of an inorganic peracid in an amount of 0.5 to 2.0 molar equivalents relative to the nitrogen-containing aromatic compound, and the dispersion liquid is obtained.
- a nitrogen aromatic compound is added to and stirred to coat the surface of the resin particles with the polymer of the nitrogen-containing aromatic compound.
- the production method (4) it is possible to produce colored resin particles in which a coating layer made of a polymer of the nitrogen-containing aromatic compound is uniformly formed on the entire surface of the resin particles.
- the resin composition of the present invention is characterized by including the colored resin particles of the present invention.
- the colored resin particles of the present invention are included, a colored molded body having light diffusibility can be obtained. Furthermore, according to the resin composition of the present invention, a molded body having higher transparency than a molded body using true spherical colored resin particles can be obtained without impairing physical properties required for the molded body.
- the molded product of the present invention is characterized by being formed by molding the resin composition of the present invention.
- a colored molded body having light diffusibility can be provided. Furthermore, it is possible to provide a molded body having higher transparency than a molded body using spherical colored resin particles without impairing physical properties required for the molded body.
- the light diffusion plate of the present invention is characterized by including the colored resin particles of the present invention.
- a colored light diffusion plate can be provided. Furthermore, a light diffusing plate having higher transparency than a light diffusing plate using spherical colored resin particles can be obtained without impairing physical properties required for the light diffusing plate.
- the paint of the present invention is characterized by including the colored resin particles of the present invention.
- the coating material of the present invention since the colored resin particles of the present invention are included, a colored coating film having light diffusibility can be obtained. Furthermore, according to the resin composition of the present invention, a coating film having higher transparency than a coating film using true spherical colored resin particles can be obtained without impairing physical properties required for the coating film.
- the coated article of the present invention is characterized in that the paint of the present invention is coated on a substrate.
- a colored coated article having light diffusibility can be provided. Furthermore, a coated article having higher transparency than a coated article using true spherical colored resin particles can be obtained without impairing physical properties required for the coated article.
- the optical film and antiglare film of the present invention are characterized in that the paint of the present invention is applied on a transparent substrate film.
- the colored resin particles of the present invention are coated with a polymer derived from a nitrogen-containing aromatic compound on the surface of the resin particles, so that a certain amount of light transmittance is ensured and the entire black pigment extends to the inside.
- the nitrogen-containing aromatic compound is pyrrole or a pyrrole derivative
- the above effect can be further emphasized.
- the colored resin particles when the colored resin particles have a sphere equivalent volume average particle diameter of 1 to 10 ⁇ m, it can be more suitably used as an antiglare member.
- the external preparation of the present invention is characterized by containing colored resin particles.
- the colored resin particles have an irregular shape, the rolling friction is large and the adhesion is excellent as compared with the spherical colored resin particles. Therefore, when an external preparation using the colored resin particles, for example, a cosmetic composition for makeup such as mascara, or a cosmetic composition such as a hair dyeing composition is attached to eyelashes, eyebrows, skin, or hair. Excellent adhesion and difficult to peel off.
- a cosmetic composition for makeup such as mascara
- a cosmetic composition such as a hair dyeing composition
- colored resin particles having excellent adhesion and a method for producing the same, and a resin composition, a molded body, a light diffusing plate, a paint, a coated article, an optical film, and an antiglare using the colored resin particles.
- a film and an external preparation can be provided.
- the colored resin particle according to the present invention is a colored resin particle in which the surface of the resin particle is coated with a polymer derived from a nitrogen-containing aromatic compound, and is a deformed resin when viewed from the direction in which the projected area is maximized
- the outer shape of the particles is circular, and the outer shape of the deformed resin particles is non-circular when viewed from the direction where the projected area is minimized.
- the resin particles are preferably obtained by polymerizing a polymerizable vinyl monomer, but are not particularly limited.
- the method for producing colored resin particles according to the embodiment includes a step of polymerizing a polymerizable vinyl monomer to obtain resin particles having an irregular shape, and a surface of the obtained resin particles having a nitrogen-containing aroma. And a step of coating a polymer derived from a group compound.
- the colored resin particles of the present invention, and the resin particles used for the production thereof, have a circular outer shape when the resin particles and the colored resin particles are viewed from the direction in which the projected area is maximized, and the projected area is minimized.
- the shape of the deformed resin particles is a non-circular particle having a non-circular shape when viewed from the direction (hereinafter referred to as a deformed particle).
- the irregular shape is preferably a shape having a concave portion, a hemispherical shape, a double-sided convex lens shape, or a mushroom shape.
- the shape having the concave portion examples include a concave cross section having a notch that communicates in the diametrical direction (hereinafter also referred to as a cross-section horseshoe shape), a concave lens shape that is not a cross-section horseshoe shape, and the like.
- the deformed shape is particularly preferably a horseshoe cross section, a hemispherical shape, a double-sided convex lens shape, or a mushroom shape.
- the colored resin particles of the present invention and the resin particles used for the production thereof preferably have the same irregular shape, and preferably have a regular irregular shape.
- FIG. 1A is a projected view showing irregularly shaped particles having a horseshoe cross section, where the upper figure shows a case where the projected area is maximized, and the lower figure shows a case where the projected area is minimized.
- the outer shape of the particle in the figure with the maximum projected area is circular.
- grain of the figure where a projection area becomes the minimum becomes a shape which the recessed part and sector corresponding to the projection figure of a notch part combined.
- the concave portion has a depth B that is 0.1 to 0.9 times the particle diameter A of the irregularly shaped particles, and has an opening that is 0.1 to 0.95 times larger. It has a width C.
- FIG. 1B is a projected view showing mushroom-like irregularly shaped particles
- the upper view is a view showing a case where the projected area is maximized
- the lower view is a view where the projected area is minimized.
- the outer shape of the particle in the figure with the maximum projected area is circular.
- the mushroom-shaped irregular particles can be considered to be composed of an umbrella portion and a shaft portion, and the width D1 of the bottom of the shaft portion is 0.1 to 0.8 times the particle diameter A of the resin particles.
- the width D2 of the intermediate part is 0.2 to 0.9 times the particle diameter A of the resin particles, and the height E in the axial length direction is 0.2 to 1. 5 times.
- FIG. 1C is a projected view showing hemispherical irregularly shaped particles, where the upper figure shows a case where the projected area is maximized, and the lower figure shows a case where the projected area is minimized.
- the outer shape of the particle in the figure with the maximum projected area is circular.
- the height F of the irregular shaped particles is 0.2 to 0.8 times the particle diameter A of the irregular shaped particles in the semicircular figure having the smallest projected area.
- FIG. 1D is a projection diagram showing irregularly shaped particles having a double-sided convex lens shape (meteorite shape), the upper diagram is a diagram showing a circular shape with the maximum projection area, and the lower diagram is a diagram showing a case where the projection area is minimum. It is.
- the heights H and I of the convex lenses are 0.2 to 0.8 times the particle diameter A of the irregular particles.
- the particle diameter A can be set in the range of 0.5 to 30 ⁇ m.
- the spherical equivalent volume average particle diameter of the irregularly shaped particles can be set in the range of 0.5 to 30 ⁇ m.
- 1A to 1D are diagrams showing shapes for explaining the shapes of irregularly shaped particles in an easy-to-understand manner.
- irregularly shaped particles having different maximum diameters and minimum diameters in which some bulges and dents are present. are also within the scope of the present invention.
- the shape of the above-mentioned irregularly shaped particles can be made differently by appropriately adjusting the use ratio of the raw material for the resin particles, the polymerization conditions for obtaining the resin particles, and the like.
- the shape is made by adjusting the composition of the seed particles, the weight average molecular weight of the seed particles, the amount of the polymerizable vinyl monomer used for the seed particles, and the amount of the (meth) acrylic acid ester having an alkylene oxide group. Can be divided. For example, when the amount of the polymerizable vinyl monomer used for the seed particles is increased, deformed particles having a horseshoe cross-section are easily obtained.
- the molecular weight of the seed particles is low, it is easy to obtain horseshoe-shaped irregular particles, and when the molecular weight of the seed particles is increased, hemispherical irregular particles are easily obtained, and when the molecular weight of the seed particles is further increased, It is easy to obtain irregular shaped particles.
- Seed particles are (meth) acrylic acid esters (condensation of alkyl alcohols having 3 to 6 carbon atoms and (meth) acrylic acid) containing an alkyl group having 3 to 6 carbon atoms in the ester portion. It is preferable that it is a resin particle derived from the monomer containing).
- the monomer for forming the seed particles preferably contains 50% by weight or more of (meth) acrylic acid ester containing an alkyl group having 3 to 6 carbon atoms in the ester portion. Resin particles derived from such monomers are likely to be non-spherical (abnormal) particles.
- this alkyl group examples include linear alkyl groups such as n-propyl, n-butyl and n-pentyl, and branched alkyl groups such as isopropyl, isobutyl and t-butyl.
- Specific (meth) acrylic acid esters include n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) acrylic acid t. -Monomers such as butyl. These monomers may be used alone or in combination of two or more.
- (meth) acrylic acid ester having a branched alkyl group for example, isopropyl, isobutyl, t-butyl
- (meth) acrylic acid ester having a branched alkyl group is preferable because non-spherical (abnormal) resin particles are easily obtained.
- (meth) acryl means acryl or methacryl
- (meth) acrylate means acrylate or methacrylate
- the weight average molecular weight of the seed particles is preferably in the range of 150,000 to 1,000,000, and more preferably in the range of 200,000 to 800,000 as measured by GPC (gel permeation chromatography). If the weight average molecular weight is 1,000,000 or less, odd-shaped resin particles can be easily obtained, and mixing of spherical particles can be prevented. By setting the weight average molecular weight to 1,000,000 or less, it is possible to prevent a decrease in the monomer absorption capacity of the seed particles, and it is possible to prevent the monomers from being polymerized independently without being absorbed, and the target resin particles. Generation of different spherical resin particles can be prevented. On the other hand, by making the weight average molecular weight of the seed particles 150,000 or more, the phase separation between the seed particles and the polymerizable vinyl monomer is appropriately made, and it is difficult to obtain the desired deformed resin particles. it can.
- the size and shape of the seed particles are not particularly limited.
- As the seed particles spherical particles having a particle diameter of 0.1 to 5 ⁇ m are usually used.
- the method for producing seed particles is not particularly limited, and known methods such as emulsion polymerization, soap-free emulsion polymerization, seed polymerization, and suspension polymerization can be used.
- the production method is preferably an emulsion polymerization, a soap-free emulsion polymerization or a seed polymerization method in consideration of the uniformity of the particle diameter of the seed particles and the simplicity of the production method.
- the polymerization of the monomer for producing seed particles may be performed in the presence of a molecular weight modifier.
- molecular weight regulators include ⁇ -methylstyrene dimer; mercaptans such as n-octyl mercaptan and t-dodecyl mercaptan; terpenes such as ⁇ -terpinene and dipentene; halogenated hydrocarbons such as chloroform and carbon tetrachloride.
- chain transfer agents can be used.
- the molecular weight modifier is preferably used in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the monomer for producing seed particles.
- the polymerizable vinyl monomer is preferably a monomer containing 5 to 50% by weight of a crosslinkable monomer.
- the crosslinkable monomer is not particularly limited, and any known crosslinkable monomer can be used.
- Examples of the crosslinkable monomer include a polymer having two or more polymerizable vinyl groups (polymerizable vinyl group or substituted vinyl group) such as ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and divinylbenzene in one molecule. Functional monomers are used.
- the amount of the crosslinkable monomer used is 5 to 50% by weight based on the total amount of the polymerizable vinyl monomer. When the ratio of the crosslinkable monomer is less than 5% by weight or more than 50% by weight, particles having small deformation and almost spherical shape may be obtained. A more preferred use amount is 10 to 40% by weight.
- the polymerizable vinyl monomer may contain a monomer other than the crosslinkable monomer.
- Other monomers include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic acid t -(Meth) acrylic acid derivatives such as butyl, (meth) acrylamide, 2-hydroxylethyl (meth) acrylate and glycidyl (meth) acrylate; vinyl acetate; acrylonitrile and the like.
- (meth) acrylic acid ester having an alkylene oxide group is more preferable as another monomer because non-spherical (abnormal) particles are easily obtained.
- examples of such (meth) acrylic acid esters include compounds represented by the following general formula.
- R 1 represents H or CH 3
- R 2 and R 3 are different and represent an alkylene group selected from C 2 H 4 , C 3 H 6 , C 4 H 8 , and C 5 H 10.
- M is 0 to 50
- n is 0 to 50 (where m and n are not 0 simultaneously)
- R 4 represents H or CH 3 .
- n when m is larger than 50 and when n is larger than 50, the polymerization stability may be lowered and coalescence particles may be generated.
- a preferable range of m and n is 0 to 30, and a more preferable range of m and n is 0 to 15.
- a commercially available product can be used as the (meth) acrylic acid ester having an alkylene oxide group.
- Examples of commercially available products include the Bremer (registered trademark) series manufactured by NOF Corporation. Further, in the Blemmer (registered trademark) series, Blemmer (registered trademark) 50 PEP-300 (R 1 is CH 3 , R 2 is C 2 H 5 , R 3 is C 3 H 6 , m and n are averaged.
- the amount of the (meth) acrylic acid ester having an alkylene oxide group is preferably 0 to 40% by weight, more preferably 1 to 40% by weight, based on the total amount of the polymerizable vinyl monomer. Preferably, 5 to 30% by weight is more preferable, and 10 to 20% by weight is particularly preferable.
- the amount of the (meth) acrylic acid ester having an alkylene oxide group exceeds 40% by weight based on the total amount of the polymerizable vinyl monomer, the polymerization stability may be lowered and the number of coalesced particles may be increased. .
- seed particles are added to an aqueous emulsion composed of a polymerizable vinyl monomer and an aqueous medium.
- the aqueous medium include water and a mixed medium of water and a water-soluble solvent (for example, a lower alcohol having 5 or less carbon atoms).
- the aqueous medium preferably contains a surfactant.
- a surfactant any of anionic, cationic, nonionic and zwitterionic compounds can be used.
- anionic surfactants include fatty acid oils such as sodium oleate and castor oil, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, and alkylnaphthalene sulfone.
- Acid salts alkane sulfonates, dialkyl sulfosuccinates such as sodium dioctyl sulfosuccinate, alkenyl succinates (dipotassium salts), alkyl phosphate esters, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl phenyl ether sulfates Examples thereof include salts, polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate, and polyoxyethylene alkyl sulfate salts.
- cationic surfactant examples include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride.
- zwitterionic surfactants include lauryl dimethylamine oxide and phosphate ester or phosphite ester surfactants.
- the above surfactants may be used alone or in combination of two or more.
- anionic surfactants are preferred from the viewpoint of dispersion stability during polymerization.
- the aqueous emulsion can be prepared by a known method.
- an aqueous emulsion can be obtained by adding a polymerizable vinyl monomer to an aqueous medium and dispersing it with a fine emulsifier such as a homogenizer, an ultrasonic processor, or a nanomizer.
- the polymerizable vinyl monomer may contain a polymerization initiator as necessary.
- the polymerization initiator may be mixed with the polymerizable vinyl monomer in advance and then dispersed in an aqueous medium, or a mixture obtained by separately dispersing both in an aqueous medium.
- the droplet diameter of the polymerizable vinyl monomer in the obtained aqueous emulsion is preferably smaller than the seed particle because the polymerizable vinyl monomer is efficiently absorbed by the seed particle.
- the seed particles may be added directly to the aqueous emulsion, or may be added in a form in which the seed particles are dispersed in an aqueous dispersion medium.
- the polymerizable vinyl monomer is absorbed into the seed particles.
- This absorption can usually be carried out by stirring the aqueous emulsion after addition of seed particles at room temperature (about 20 ° C.) for 1 to 12 hours. Further, absorption may be promoted by heating the aqueous emulsion to about 30 to 50 ° C.
- the seed particles swell by absorbing the polymerizable vinyl monomer.
- the mixing ratio of the polymerizable vinyl monomer to the seed particles is preferably in the range of 5 to 150 parts by weight of the polymerizable vinyl monomer with respect to 1 part by weight of the seed particles. More preferred is the range of parts.
- the mixing ratio of the polymerizable vinyl monomer to the seed particles is small, the increase in particle diameter due to polymerization is small, and thus productivity may be lowered.
- the mixing ratio of the polymerizable vinyl monomer to the seed particles is increased, the polymerizable vinyl monomer is not completely absorbed by the seed particles, and is uniquely suspended and polymerized in an aqueous medium to generate abnormal particles. Sometimes. The end of absorption can be determined by confirming the enlargement of the particle diameter by observation with an optical microscope.
- a polymerization initiator can be added to the aqueous emulsion as necessary.
- the polymerization initiator include benzoyl peroxide, lauroyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexano , Organic peroxides such as di-t-butyl peroxide, 2,2′-azobisisobutyronitrile, 1,1′-azobiscyclohexanecarbonitrile, 2,2′-azobis (2,4- And azo compounds such as dimethylvaleronitrile).
- the polymerization initiator is preferably used in the range of 0.1 to 3 parts by weight with respect to 100 parts by weight of the polymerizable vinyl monomer.
- the polymerization temperature is appropriately selected according to the type of the polymerizable vinyl monomer and the polymerization initiator.
- the polymerization temperature is preferably in the range of 25 to 110 ° C, more preferably in the range of 50 to 100 ° C.
- the polymerization reaction is preferably performed by raising the temperature after the monomer and the polymerization initiator are completely absorbed by the seed particles.
- the irregularly shaped resin particles are centrifuged to remove the aqueous medium, washed with water and a solvent, and then dried and isolated.
- a polymer dispersion stabilizer may be added in order to improve the dispersion stability of the irregularly shaped resin particles.
- the polymer dispersion stabilizer for example, polyvinyl alcohol, polycarboxylic acid, celluloses (hydroxyethyl cellulose, carboxymethyl cellulose, etc.), polyvinyl pyrrolidone and the like can be used.
- these polymer dispersion stabilizers and inorganic water-soluble polymer compounds such as sodium tripolyphosphate can be used in combination.
- polyvinyl alcohol and polyvinyl pyrrolidone are preferable as the polymer dispersion stabilizer.
- the addition amount of the polymer dispersion stabilizer is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the polymerizable vinyl monomer.
- water-soluble polymerization inhibitors such as nitrites, sulfites, hydroquinones, ascorbic acids, water-soluble vitamin Bs, citric acid, and polyphenols may be used. Good.
- the surface of the irregularly shaped resin particles obtained by the seed polymerization method described above is coated with a polymer derived from a nitrogen-containing aromatic compound.
- a method for coating a polymer derived from a nitrogen-containing aromatic compound the resin particles are dispersed in an aqueous medium containing an oxidant to form a dispersion (emulsion or suspension), and the dispersion is subjected to nitrogen aroma.
- a method in which an aromatic compound is added and stirred, and the surface of the resin particles is coated with the polymer of the nitrogen-containing aromatic compound by oxidative polymerization is preferable.
- Nitrogen-containing aromatic compounds include nitrogen-containing heterocyclic aromatic compounds such as pyrrole, indole, imidazole, pyridine, pyrimidine and pyrazine, and primary amino group-substituted aromatic compounds such as aniline. , And these alkyl-substituted products (for example, substituted products with alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, and butyl), halogen-substituted products (for example, fluoro, chloro, and bromo groups) And a derivative such as a nitrile substitute.
- nitrogen-containing heterocyclic aromatic compounds such as pyrrole, indole, imidazole, pyridine, pyrimidine and pyrazine
- primary amino group-substituted aromatic compounds such as aniline.
- alkyl-substituted products for example, substituted products with alkyl groups having 1 to 4 carbon atoms such as methyl,
- These monomers can be used alone to form a homopolymer, or two or more types can be used in combination to form a copolymer. Since a more uniform coating layer is easily formed and black colored resin particles are obtained, pyrrole and a pyrrole derivative polymer are preferred as the nitrogen-containing aromatic compound.
- the addition amount of the nitrogen-containing aromatic compound may be set according to the desired degree of coloring and the like, and is preferably in the range of 1 to 30 parts by weight with respect to 100 parts by weight of the resin particles. More preferably. If the addition amount of the nitrogen-containing aromatic compound is 1 part by weight or more with respect to 100 parts by weight of the resin particles, the entire surface of the resin particles is uniformly coated with a polymer derived from the nitrogen-containing aromatic compound, and the desired coloration The degree can be obtained. On the other hand, if the addition amount of the nitrogen-containing aromatic compound is 30 parts by weight or less with respect to 100 parts by weight of the resin particles, the added nitrogen-containing aromatic compound is polymerized alone, and other than the intended colored resin particles. Can be prevented.
- Oxidizing agents As oxidizing agents, inorganic acids such as hydrochloric acid, sulfuric acid and chlorosulfonic acid, organic acids such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid, metal halides such as ferric chloride and aluminum chloride And halogen acids such as potassium perchlorate, potassium persulfate, ammonium persulfate, sodium persulfate, peroxides such as hydrogen peroxide, and the like. These may be used alone or in combination.
- an alkali metal salt of an inorganic peracid is preferable. Specific examples of the alkali metal salt of inorganic peracid include potassium persulfate and sodium persulfate.
- the amount of the oxidizing agent used is preferably 0.5 to 2.0 molar equivalents relative to the total amount of the nitrogen-containing aromatic compound. If the amount of the oxidizing agent used is 0.5 molar equivalent or more with respect to the total amount of the nitrogen-containing aromatic compound, the entire surface of the resin particles is uniformly coated with a coating layer containing a polymer of the nitrogen-containing aromatic compound, and is desired. It is possible to obtain a degree of coloring. On the other hand, if the amount of the oxidizing agent used is 2.0 molar equivalents or less based on the total amount of the nitrogen-containing aromatic compound, the added nitrogen-containing aromatic compound is polymerized alone, and other than the intended colored resin particles. Can be prevented.
- Aqueous medium to which the oxidizing agent is added is not particularly limited as long as it can dissolve or disperse the nitrogen-containing aromatic compound, but water or water and methanol, ethanol, n- Alcohols such as propanol, isopropanol, n-butanol and t-butanol; ethers such as diethyl ether, isopropyl ether, butyl ether, methyl cellosolve and tetrahydrofuran; mixed media with ketones such as acetone, methyl ethyl ketone and diethyl ketone Can be mentioned.
- the aqueous medium to which the oxidizing agent is added preferably has a pH of 3 or more.
- the pH is 3 or more, the entire surface of the resin particles is uniformly covered with a coating layer containing a polymer of a nitrogen-containing aromatic compound, and a desired coloring degree can be obtained.
- Surfactant may be added to the aqueous medium.
- the surfactant any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant can be used.
- anionic surfactant examples include fatty acid oils such as sodium oleate and castor oil, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, and alkylsulfonic acid.
- fatty acid oils such as sodium oleate and castor oil
- alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate
- alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate
- alkylsulfonic acid examples include fatty acid oils such as sodium oleate and castor oil, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as
- alkyl naphthalene sulfonate alkane sulfonate, succi sulfonate, dialkyl sulfo succinate, alkyl phosphate ester salt, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phenyl ether sulfate salt, polyoxyethylene alkyl Examples thereof include sulfate ester salts.
- Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxy And ethylene-oxypropylene block polymer.
- cationic surfactant examples include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride.
- the zwitterionic surfactant examples include lauryl dimethylamine oxide, phosphate ester-based or phosphite-based surfactant. You may use the said surfactant individually or in combination of 2 or more types.
- the addition amount of the surfactant is preferably in the range of 0.0001 to 1 part by weight with respect to 100 parts by weight of the aqueous medium.
- a polymer dispersion stabilizer may be added to the aqueous medium in addition to the surfactant.
- the polymer dispersion stabilizer include polyacrylic acid, copolymers thereof and neutralized products thereof, and polymethacrylic acid, copolymers thereof and neutralized products thereof, polyvinylpyrrolidone, hydroxypropylcellulose (HPC), and the like. Is mentioned.
- the polymer dispersion stabilizer may be used in combination with the above-described surfactant.
- the resin particles are dispersed in an aqueous medium containing an oxidizing agent to form a dispersion, and a nitrogen aromatic compound is added to the dispersion.
- a nitrogen aromatic compound is added to the dispersion.
- the temperature of oxidative polymerization is preferably in the range of ⁇ 20 to 40 ° C.
- the time of oxidative polymerization is preferably in the range of 0.5 to 10 hours.
- the emulsion in which the colored resin particles are dispersed is centrifuged as necessary to remove the aqueous medium, washed with water and a solvent, and then dried and isolated.
- the irregular shaped resin particles obtained by the seed polymerization method or the like are treated with nitrogen-containing aroma in an aqueous medium containing an alkali metal salt of an inorganic peracid.
- the method of coating the resin particles with the polymer is not limited to this method.
- a nitrogen-containing aromatic compound is polymerized in advance.
- a method of coating the obtained polymer on resin particles using a dry method may also be employed. Examples of the dry method include a method using a ball mill, a method using a V-type mixer, a method using a high-speed fluidized dryer, a method using a hybridizer, and a mechano-fusion method.
- the entire surface of the resin particles is uniformly covered with a coating layer containing a polymer derived from a nitrogen-containing aromatic compound.
- “uniform” means that the thickness fluctuation of the coating layer containing the polymer derived from the nitrogen-containing aromatic compound covering the resin particles is small.
- the runout is preferably 50% or less, and more preferably 40% or less.
- the thickness of the coating layer is preferably in the range of 30 to 300 nm, more preferably in the range of 50 to 200 nm. If the thickness of the coating layer is 30 nm or more, a sufficient degree of coloring can be obtained, and desired characteristics (for example, anti-glare property) can be obtained. On the other hand, when the thickness of the coating layer is 300 nm or less, it is possible to suppress a decrease in light transmittance. For example, it is possible to prevent the display of a display device provided with an antiglare member using this from becoming dark.
- the spherical equivalent volume average particle diameter of the colored resin particles is not particularly limited, but it is preferably 1 to 50 ⁇ m in consideration of the use as a cosmetic composition. More preferably, it is 1 to 30 ⁇ m. If the sphere equivalent volume average particle diameter of the colored resin particles is 1 ⁇ m or more, it is possible to obtain an effect of improving the adhesion as a cosmetic. On the other hand, if the sphere equivalent volume average particle diameter of the colored resin particles is 50 ⁇ m or less, it is possible to make a cosmetic that does not impair the applicability and the touch.
- the spherical equivalent volume average particle diameter of the colored resin particles is preferably 1 to 10 ⁇ m and more preferably 3 to 7 ⁇ m in consideration of the use as an antiglare member. If the sphere equivalent volume average particle diameter of the colored resin particles is 1 ⁇ m or more, fine unevenness is reliably formed on the antiglare member, and desired antiglare property can be obtained. On the other hand, if the sphere equivalent volume average particle diameter of the colored resin particles is 10 ⁇ m or less, fine irregularities can be easily adjusted, and the desired antiglare property can be obtained by the adjustment.
- the coefficient of variation (CV value) of the particle diameter of the colored resin particles is preferably 30% or less, and preferably 20% or less in order to improve the antiglare property, prevent glare and obtain a uniform coating film. Is more preferable.
- the colored resin particles according to the present invention have a circular outer shape when viewed from the direction where the projected area is maximized, and the outer shape of the deformed resin particles when viewed from the direction where the projected area is minimum.
- the surface of the resin particle is coated with a coating layer made of a polymer derived from a nitrogen-containing aromatic compound. Therefore, it can be set as the colored resin particle which has the coloring degree derived from this polymer (for example, black) and can be applied to various uses including cosmetics.
- the colored resin particles are colored only on the surface portion, the amount of light transmitted through the particles is not greatly reduced as compared with known colored particles colored up to the inside of the particles. Therefore, by dispersing the colored resin particles in a film or sheet, it can be suitably used in fields such as an antiglare member having a stable desired total light transmittance.
- an antiglare member can be obtained by applying a mixture containing the colored resin particles and the binder resin according to the present invention to a transparent base resin.
- the shape of the colored resin particles is such that the outer shape of the deformed resin particles is circular when viewed from the direction where the projected area is maximum, and the outer shape of the deformed resin particles is not viewed when viewed from the direction where the projected area is minimum. Adhesiveness is also improved because of the irregular shape that is circular.
- the resin composition of the present invention contains the colored resin particles of the present invention.
- the shape of the colored resin particles used in the resin composition of the present invention is not particularly limited as long as it is an irregular shape, but has a concave shape, a hemispherical shape, a double-sided convex lens shape, or a mushroom shape. Is preferable, and a double-sided convex lens shape is more preferable.
- the resin composition of the present invention preferably further contains a base resin. Since the resin composition of the present invention further including a base resin has light diffusibility, it can be used as a light diffusible resin composition for molding a light diffusing member such as a light diffusing plate.
- the base resin examples include polycarbonate resins; Vinyl chloride resins such as polyvinyl chloride and vinyl chloride-vinylidene chloride copolymer; Vinyl ester resins such as polyvinyl acetate and vinyl acetate-ethylene copolymer; Styrene resins such as polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer, styrene-butadiene block copolymer, styrene-isoprene block copolymer, styrene-methyl methacrylate copolymer; (Meth) acrylic acid ester resins such as poly (meth) acrylic acid ester, (meth) acrylic acid ester-acrylonitrile copolymer, (meth) acrylic acid ester-styrene copolymer; Polyester resins such as condensates of terephthalic acid and ethylene glycol, conden
- a base resin having a refractive index comparable to that of the colored resin particles If you want to obtain a resin composition with excellent transparency, select a base resin having a refractive index comparable to that of the colored resin particles. If you want to obtain a resin composition with excellent light diffusivity, use colored resin particles. A base resin having a refractive index sufficiently different from that of the above may be selected.
- a polycarbonate resin is preferable as the base resin.
- polycarbonate resin for example, an aromatic polycarbonate resin obtained by reacting an aromatic dihydroxy compound and phosgene or a carbonic acid diester by a melting method or a solution method can be used.
- aromatic dihydroxy compound examples include 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4 -Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-1-methylphenyl) propane, Bis (4-hydroxyphenyl) naphthylmethane, 1,1-bis (4-hydroxy-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis ( 4-hydroxy-3,5-tetramethylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propyl Bread, 2,2-bis (4-hydroxy-3,5-tetrachlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-tetrabromophenyl) bis (
- Bis (hydroxyaryl) cycloalkanes Dihydroxy aryl ethers such as 4,4′-dividroxyphenyl ether and 4,4′-dihydroxy-3,3′-dimethylphenyl ether; Dihydroxydiaryl sulfides such as 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide; Dihydroxydiaryl sulfoxides such as 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide; Dihydroxydiaryl sulfones such as 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone; And dihydroxydiphenyls such as 4,4′-dihydroxydiphenyl.
- aromatic dihydroxy compounds may be used alone or in combination of two or more.
- the aromatic dihydroxy compound may contain an arbitrary substituent or the like as long as it does not affect desired physical properties, and may be crosslinked with a crosslinking agent or the like.
- 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] is preferable because a resin composition having excellent impact resistance can be obtained.
- two or more polycarbonate resins may be used.
- the colored resin particles are preferably added in an amount of 0.1 to 30% by weight based on the resin composition.
- the addition amount of the colored resin particles is less than 0.1% by weight, it becomes difficult to obtain a desired effect (for example, a light diffusion effect) by the colored resin particles, and when the addition amount of the colored resin particles exceeds 30% by weight.
- the colored resin particles are not uniformly dispersed in the resin composition. In this case, it is difficult to obtain a desired effect (for example, a light diffusion effect) by the colored resin particles.
- the resin composition of the present invention may also contain various components such as a fluorescent brightener, a heat stabilizer, an organic or inorganic ultraviolet absorber. These various components can give the resin composition physical properties such as desired fluorescent whitening, thermal stability, and ultraviolet absorption.
- the fluorescent brightening agent is not particularly limited, and for example, an oxazole fluorescent brightening agent (for example, “Kayalite (registered trademark) OS” manufactured by Nippon Kayaku Co., Ltd.), an imidazole fluorescent brightening agent. Rhodamine fluorescent whitening agents and the like can be used.
- Such an optical brightener is preferably 0.0005 to 0.1 parts by weight, more preferably 0.001 to 0.1 parts by weight, and more preferably 0.001 to 0.1 parts by weight with respect to 100 parts by weight of the base resin in the resin composition. When the content is preferably 0.001 to 0.05 parts by weight, sufficient fluorescent whitening property can be imparted to the resin composition.
- the heat stabilizer is not particularly limited, and examples thereof include organic phosphorus heat stabilizers such as phosphate esters, phosphite esters, and phosphonate esters; hindered phenol heat stabilizers; lactone heat stabilizers.
- An phosphite antioxidant for example, “ADEKA STAB (registered trademark) PEP-36” manufactured by ADEKA Corporation
- Such a thermal stabilizer is preferably 0.005 to 0.5 part by weight, more preferably 0.01 to 0.5 part by weight, and still more preferably 100 parts by weight of the base resin in the resin composition. When it is contained in a proportion of 0.001 to 0.3 parts by weight, sufficient thermal stability can be imparted to the resin composition.
- the organic ultraviolet absorber is not particularly limited, and examples thereof include benzophenone ultraviolet absorbers such as 2-hydroxy-4-methoxy-5-sulfobenzophenone; 2,2′-methylenebis [4- ( 1,1,3,3-tetramethylbutyl) -6- [2H- Benzotriazol-2-yl] phenol]] (“ADEKA STAB (registered trademark) LA-31” manufactured by ADEKA Corporation), 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy- Benzotriazole ultraviolet absorbers such as 5-t-butylphenyl) benzotriazole and 2- (2-hydroxy-3-5-dit-butylphenyl) -5-chlorobenzotriazole; hydroxyphenyltriazine ultraviolet absorbers; salicylic acid UV absorbers such as pt-butylphenyl salicylate and p-octylphenyl salicylate; 2-ethylhexyl-2-cyano-3,3
- the organic ultraviolet absorbent is preferably 0.01 to 2.0 parts by weight, more preferably 0.03 to 2.0 parts by weight, and more preferably 100 parts by weight of the base resin in the resin composition. When it is preferably contained in a proportion of 0.05 to 1.0 part by weight, sufficient ultraviolet absorption can be imparted to the resin composition.
- the inorganic ultraviolet absorber examples include inorganic fine particles such as zinc oxide fine particles, titanium oxide fine particles, cerium oxide fine particles, zirconium oxide fine particles (particle diameter is 0.003 to 0.1 ⁇ m, preferably 0.003 to 0.05 ⁇ m). Particles) can be used.
- the inorganic ultraviolet absorber is contained in the resin composition in a proportion of 0.001 to 24% by weight, sufficient ultraviolet absorption can be imparted to the resin composition.
- the inorganic ultraviolet absorber may be included in the colored resin particles at a ratio of 1 to 80% by weight. These ultraviolet absorbers may be used alone or in admixture of two or more.
- the molded article of the present invention is formed by molding the resin composition of the present invention.
- a molding method of the resin composition a method of obtaining a molded body by molding a pellet-shaped resin composition by a molding method such as injection molding, injection compression molding, or extrusion molding from the viewpoint of productivity. be able to. Further, it is possible to employ a method in which a resin composition is extruded to obtain a sheet-like molded body, and this sheet-like molded body is molded by a molding method such as vacuum molding or pressure molding to obtain a molded body.
- Such a molded article of the present invention has light diffusibility, it can be used as a light diffusing member such as a light diffusing plate containing colored resin particles.
- the light diffusing plate of the present invention includes colored resin particles.
- the molded body of the present invention includes electrical and electronic parts such as lighting covers, automobile parts such as automobile interior panels, machine parts, packaging films for packaging miscellaneous goods, foods and medicines, foods and medicines, etc. It can also be used as a building such as a container, fiber, board or roof.
- the colored resin particles contain a polymer derived from pyrrole or a pyrrole derivative
- the molded article of the present invention has conductivity and an antistatic function.
- the molded article of the present invention includes, as necessary, as an auxiliary agent for enhancing weather resistance and processing performance, as a plasticizer, a stabilizer, an antioxidant, a flame retardant, an antistatic agent, a lubricant, a polymer.
- a plasticizer for enhancing weather resistance and processing performance
- a stabilizer for enhancing weather resistance and processing performance
- an antioxidant for enhancing weather resistance and processing performance
- a flame retardant for enhancing weather resistance and processing performance
- an antistatic agent e.g., antistatic agent for enhancing weather resistance and processing performance
- a lubricant e.g., a poly(ethylene glycol)
- polymer e.g., poly(ethylene glycol)
- An appropriate amount of a modifier or the like can be blended as necessary.
- extender pigments, color pigments, dyes, and the like can be added to the molded body as long as the transparency of the molded body is not impaired.
- the paint of the present invention contains the colored resin particles of the present invention.
- the shape of the colored resin particles used in the paint of the present invention is not particularly limited as long as it is an irregular shape, but a shape having a recess, a hemispherical shape, a double-sided convex lens shape, or a mushroom shape is preferable. More preferably, it is a double-sided convex lens shape.
- the paint of the present invention preferably contains a resin binder.
- the resin binder include (meth) acrylic ester resins (acrylic resins), polycarbonate resins, polyester resins, urethane resins, epoxy resins, polypropylene resins, silicone resins, styrene resins, and fluorine resins.
- Various polymers capable of forming a film such as resins, cellulose resins, other vinyl resins (vinyl chloride resins, etc.), modified products thereof, precursors of these polymers (monomers, oligomers) Or a mixture thereof).
- These resin binders may be dissolved in a solvent or may exist as an emulsion in the solvent, and are appropriately selected according to the purpose of use.
- a vehicle component having a refractive index comparable to that of the colored resin particles may be selected.
- a vehicle component having a refractive index sufficiently different from the refractive index of the colored resin particles may be selected.
- a combination of colored resin particles mainly composed of acrylic resin and a resin binder of acrylic resin can provide a coating film with excellent transparency, and colored resin particles mainly composed of styrene resin. If it is a combination of a resin binder of an acrylic resin, the coating film excellent in matteness can be obtained.
- a liquid paint in which a solid resin binder is dissolved in a solvent and colored resin particles are dispersed in the solvent a liquid in which the solid resin binder and colored resin particles are dispersed in the solvent Paint; powder paint containing solid resin binder and colored resin particles, and no solvent; liquid paint containing liquid resin binder and no solvent; liquid paint obtained by diluting liquid resin binder with solvent Is mentioned.
- a polymer precursor monomer, oligomer, or mixture thereof
- capable of ultraviolet curing and electron beam curing can be used.
- the solvent used as necessary in the coating material of the present invention can be appropriately selected depending on the properties of the film formed by the colored resin particles and the resin binder.
- water, alcohols ethyl alcohol, methyl alcohol
- esters ethyl acetate, isopropyl acetate, butyl acetate, etc.
- ketones acetone, methyl ethyl ketone [MEK], methyl isobutyl ketone
- ethers cellosolve, butylcellosolve
- terpe Such as tarpentin and dipentene.
- an organic or inorganic ultraviolet absorber as an auxiliary agent for enhancing the paintability and the performance of the coating film, an organic or inorganic ultraviolet absorber, a dispersant, a surfactant, an anti-settling agent, a wetting agent, an anti-sagging agent, An antifoaming agent, antioxidant, etc. can be mix
- examples of the compound that can be used as the ultraviolet absorber and a preferable range of the blending amount of the ultraviolet absorber are the same as those of the ultraviolet absorber that is used as necessary in the resin composition described in the section of the resin composition. It is. Further, extender pigments, color pigments, dyes, and the like can be added to the paint of the present invention as long as the transparency of the coating film is not impaired.
- the paint has fluidity that can be made uniform, and the solid content needs to be integrated by curing the resin binder. Therefore, the components that form the coating film in the paint (components excluding the solvent, that is, components)
- the content of the colored resin particles in the solid content) is preferably 95% by weight or less.
- the content of the colored resin particles in the component forming the coating film in the coating exceeds 95% by weight, the coating film becomes extremely brittle.
- content of the colored resin particle in the component which forms the coating film in the said coating material is 0.5 weight% or more. Thereby, the matte effect and coloring effect by a colored resin particle can fully be acquired.
- the coated article of the present invention is obtained by coating (coating) the coating material of the present invention on a substrate. That is, the coated article of the present invention includes a base material and a coating film formed by the paint of the present invention coated on the base material.
- the coated article of the present invention has conductivity and an antistatic function.
- base material examples include transparent base film, window glass, show window, agricultural house, transparent food packaging paper, transparent food packaging film, showcase, lighting shade, poster, signboard, color photograph, pharmaceutical bottle, PET (Polyethylene terephthalate)
- Plastic base materials such as bottles, glass, paper, metal films, plates made of various materials, threads, molded products made of various materials, and the like.
- Examples of the coating method of the paint include, for example, roll coating method, bar coating method, spray coating method, air knife coating method, flow coating method, spin coating method, dipping method (dip coating), doctor blade method, electrostatic coating, Letterpress printing, gravure printing, screen printing, pad printing, lithographic printing, plexo printing, and the like can be used.
- the thickness of the coating film formed from the coating material is preferably in the range of 1 to 100 ⁇ m.
- the coated article of the present invention can be used as an optical film having light diffusibility when a transparent substrate film is used as the substrate.
- the optical film of the present invention is formed by coating a transparent coating material of the present invention on a transparent substrate film. That is, the optical film of the present invention comprises a transparent base film and a light-diffusible coating film (hereinafter referred to as “optical functional layer”) formed on the transparent base film by application of the paint of the present invention. Contains.
- the paint used for the optical film of the present invention preferably contains a resin binder functioning as a binder component of the colored resin particles as the binder in addition to the colored resin particles of the present invention.
- the resin binder is a thermoplastic resin binder and / or a thermosetting resin binder.
- the optical functional layer in the optical film of the present invention is, for example, The colored resin particles in the optical film of the present invention are blended in a transparent paint and used for forming an optical functional layer.
- the said optical function layer is not specifically limited, It can utilize as an optical function layer for a display.
- the optical functional layer is, for example, an antiglare layer, a hard coat layer, an antireflection layer, or the like in an optical film such as a surface film or a screen installed on the surface of a display (particularly a display for high-definition images).
- the optical functional layer has conductivity, and can be used as an antistatic layer in the various optical films.
- the optical film of the present invention can be used as an antiglare film when the coating film has an uneven surface formed by the colored resin particles of the present invention.
- the antiglare film of the present invention is formed by coating a transparent coating material of the present invention on a transparent substrate film. That is, the anti-glare film of the present invention includes a transparent base film and an anti-glare coating film (hereinafter referred to as “anti-glare layer”) formed on the transparent base film by application of the paint of the present invention. Is included.
- the average particle diameter of the colored resin particles used for the optical film is preferably in the range of 0.5 to 10 ⁇ m.
- the average particle diameter of the colored resin particles is less than 0.5 ⁇ m, the particle diameter of the colored resin particles is less than the wavelength of the incident light, and light diffusion on the colored resin particle surface is less likely to occur, and the colored resin of the present invention
- the range of selection of light that can be applied to the optical functional layer using particles is limited.
- an optical functional layer having sufficiently excellent optical functions (such as antiglare property and black reproducibility) may not be obtained.
- the optical function (suppression of glare) of the optical functional layer becomes insufficient (for example, glare is likely to occur), and an optical film using the colored resin particles of the present invention is obtained.
- the quality of the applied display may be reduced.
- the optical film comprising the colored resin particles of the present invention is applied to a display, the lower limit of the average particle diameter of the colored resin particles that is preferable for improving the contrast of the display is 0.8 ⁇ m. More preferably, the upper limit of the average particle diameter of the colored resin particles is 8 ⁇ m.
- the shape of the colored resin particles used in the optical film of the present invention is not particularly limited as long as it is an irregular shape, but is preferably a double-sided convex lens shape.
- the addition amount of the colored resin particles in the optical film is preferably in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the resin binder. If the amount of the colored resin particles is less than 0.5 parts by weight based on 100 parts by weight of the resin binder, the amount of the colored resin particles added is small, so that an effect such as suppression of glare by the optical functional layer is sufficient. I can't get it. When the addition amount of the colored resin particles exceeds 20 parts by weight with respect to 100 parts by weight of the resin binder, the black portion of the optical film increases, and the transparency of the optical film is insufficient.
- the addition amount of the colored resin particles in the optical film is more preferably in the range of 1 to 10 parts by weight with respect to 100 parts by weight of the resin binder.
- Plastic films such as a polyester resin film, a polycarbonate resin film, a polyvinyl chloride resin film, a polyethylene resin film, a polypropylene resin film, a polystyrene resin film; Glass film etc. Can be used.
- the thickness of the transparent substrate film is not particularly limited, but is usually about 10 to 250 ⁇ m.
- the thickness of the optical functional layer in the optical film is not particularly limited, but is preferably in the range of 1 to 10 ⁇ m.
- the thickness of the antiglare layer in the antiglare film is not particularly limited as long as the uneven surface caused by the colored resin particles of the present invention is formed on the surface, but is preferably in the range of 1 to 10 ⁇ m. .
- the resin binder is not particularly limited as long as it has a transparent function capable of dispersing colored resin particles.
- an ionizing radiation curable resin a solvent-drying resin that is a resin curable by ultraviolet rays or an electron beam
- a thermoplastic resin, a thermosetting resin, etc. are mentioned.
- Examples of the ionizing radiation curable resin include one or two or more unsaturated bonds such as a compound having one or more (meth) acrylate functional groups ((meth) acryloyloxy group). The compound which has is mentioned.
- Examples of the compound having one unsaturated bond include ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, styrene, ⁇ -methylstyrene, N-vinylpyrrolidone and the like.
- Examples of the compound having two or more unsaturated bonds include a polyfunctional compound having a plurality of functional groups (such as hydroxyl groups) capable of reacting with a carboxy group, and an unsaturated carboxylic acid such as (meth) acrylic acid. And a reaction product of a plurality of these.
- Examples of the reaction product include poly (meth) acrylates of polyhydric alcohols.
- Examples of the poly (meth) acrylate of the polyhydric alcohol include polymethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and pentaerythritol.
- Examples include tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like.
- polyester resins having unsaturated double bonds in addition to the above-mentioned compounds, relatively low molecular weight polyester resins having unsaturated double bonds, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, Polybutadiene resin, polythiol polyene resin, and the like can also be used.
- the resin binder is preferably made of an ultraviolet curable resin which is a kind of the ionizing radiation curable resin.
- the paint for forming the optical functional layer contains a photopolymerization initiator.
- the photopolymerization initiator examples include acetophenones, benzophenones, thioxanthones, Michler benzoylbenzoate, ⁇ -amyloxime esters, thioxanthones, propiophenones, benzyls, benzoins (benzoin, benzoin). Methyl ether, etc.), acylphosphine oxides, aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene compounds, benzoin sulfonic acid esters and the like.
- the photopolymerization initiator is preferably used by mixing with a photosensitizer.
- the photosensitizer include n-butylamine, triethylamine, poly-n-butylphosphine and the like.
- the ionizing radiation curable resin is a resin having a radical polymerizable unsaturated group
- acetophenones, benzophenones, thioxanthones, and benzoins are used alone or in combination as the photopolymerization initiator. Is preferred.
- the photopolymerization initiator includes an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metallocene compound, and a benzoin. It is preferable to use sulfonic acid esters alone or in combination.
- the addition amount of the photopolymerization initiator is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin.
- the ionizing radiation curable resin can be used in combination with a solvent-drying resin.
- the solvent-drying resin include thermoplastic resins.
- thermoplastic resin various general thermoplastic resins can be used. By using the solvent-drying resin in combination, coating film defects on the coated surface can be effectively prevented.
- thermoplastic resin used as a solvent-drying resin together with the ionizing radiation curable resin include, for example, a styrene resin, a (meth) acrylic resin, a vinyl acetate resin, a vinyl ether resin, and a halogen-containing resin. , Alicyclic olefin-based resin, polycarbonate-based resin, polyester-based resin, polyamide-based resin, cellulose derivative, silicone-based resin, rubber, or elastomer.
- the thermoplastic resin it is usually preferable to use a resin that is non-crystalline and soluble in an organic solvent (particularly a common solvent capable of dissolving a plurality of polymers and curable compounds).
- resins with high moldability or film formability, transparency and weather resistance such as styrene resins, (meth) acrylic resins, alicyclic olefin resins, polyester resins, cellulose derivatives (cellulose esters, etc.) Etc. are preferred.
- styrene resins (meth) acrylic resins, alicyclic olefin resins, polyester resins, cellulose derivatives (cellulose esters, etc.) Etc.
- thermosetting resin used as the resin binder examples include phenol resin, urea resin, diallyl phthalate resin, melanin resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea. Examples thereof include a cocondensation resin, a silicon resin, and a polysiloxane resin.
- hardening agents such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, etc. as needed.
- additives such as a leveling agent, an ultraviolet absorber and an antioxidant may be added. Further, particles other than the colored resin particles may be added to the coating material for forming the optical functional layer.
- the coating material for forming the optical functional layer can be prepared, for example, by dissolving or dispersing the components of the optical functional layer in a suitable solvent to obtain a solution or dispersion (coating liquid).
- a liquid binder (coating liquid) is prepared by dissolving or dispersing the resin binder constituting the optical functional layer in an appropriate solvent and dispersing the colored resin particles in the solvent.
- a method of applying and drying the coating liquid on a transparent substrate film by a known method such as a roll coating method, a bar coating method, a spray coating method, an air knife coating method, etc .; melting a resin binder constituting the optical functional layer
- a method of forming the sheet by adding the colored resin particles and, if necessary, an additive such as a pigment (molding into a sheet shape), and the like can be given.
- optical function layers such as a glare-proof layer
- the solvent used for forming the optical functional layer include various solvents used in the above-described coating material.
- the external preparation of the present invention contains the colored resin particles of the present invention.
- the shape of the colored resin particles used for the external preparation of the present invention is not particularly limited as long as it is an irregular shape, but a shape having a concave portion, a hemispherical shape, a double-sided convex lens shape, or a mushroom shape is used. Preferably, it is a double-sided convex lens shape.
- Examples of external preparations that can be blended with colored resin particles include cosmetics and external medicines.
- Specific cosmetics that can be blended with colored resin particles include eyelashes such as mascara, eyebrow, or skin makeup cosmetic composition, hair dyeing composition, blusher, foundation and other solid cosmetics, Examples thereof include powdery cosmetics such as body powders and liquid cosmetics such as creams.
- a desired coloring degree for example, black
- an external preparation such as a cosmetic that is excellent in adhesion and hardly peeled off can be realized.
- dosage forms such as lotions, gels, creams, powders, compressed powders, and rods, sprays, foams, and aerosols can be employed.
- inorganic compounds such as mica, talc and organic hectorite, iron oxide, titanium oxide and the like may be added in order to improve the optical function and feel.
- the liquid medium is not particularly limited, but water, alcohol, hydrocarbon, silicone oil, vegetable oil or animal oil or the like can also be used.
- These external preparations include, in addition to the above-mentioned other components, waxes (paraffin wax, carnauba wax, beeswax etc.) and film-forming polymers (polyvinyl laurate, generally used for external preparations such as cosmetics).
- the weight average molecular weight is measured using gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- a weight average molecular weight means a polystyrene (PS) conversion weight average molecular weight.
- PS polystyrene
- Sample 50 mg is dissolved in 10 ml of tetrahydrofuran (THF), filtered through a non-aqueous 0.45 ⁇ m chromatographic disk, and then measured using a gel permeation chromatograph.
- THF tetrahydrofuran
- the chromatographic conditions are as follows.
- Carrier gas Tetrahydrofuran (THF)
- Carrier gas flow rate 1 ml / min
- Injection / pump temperature 35 ° C
- Detection RI
- Injection amount 100 microliters Standard polystyrene for calibration curve: manufactured by Showa Denko KK, trade name “Shodex (registered trademark)” weight average molecular weight: 1030000 and manufactured by Tosoh Corporation, weight average molecular weight: 5480000, 3840000, 355000, 102000, 37900, 9100, 2630, 870 (Measurement method of average particle size of seed particles)
- the average particle size of the seed particles is measured with a LS230 type manufactured by Beckman Coulter, Inc.
- test tube is dispersed for 10 minutes using a commercially available ultrasonic cleaner ULTRASONIC CLEARNER VS-150 manufactured by VervoCrea.
- the dispersed material is measured while irradiating ultrasonic waves with an LS230 type manufactured by Beckman Coulter, Inc. The optical model at that time is matched with the refractive index of the produced particles.
- the lengths A to I of each part of the irregularly shaped particle are measured as follows.
- the measured average particle diameter is a volume average particle diameter (arithmetic average value) measured by Beckman Coulter Co., Ltd. Coulter Multisizer II. In the measurement, calibration is performed using an aperture suitable for the particle diameter of the particle to be measured according to REFERENCE MANUAL FOR THE COULTER MULTISIZER (1987) issued by Coulter Electronics Limited.
- 0.1 g of particles and 10 ml of 0.1% nonionic surfactant solution are put into a commercially available glass test tube.
- the input material was mixed for 2 seconds with a touch mixer TOUCHMIXER MT-31 manufactured by Yamato Scientific Co., Ltd.
- the contents of the test tube were used with a commercially available ultrasonic cleaner, ULTRASONIC CLEANER VS-150 manufactured by VervoCrea.
- a beaker filled with ISOTON II manufactured by Beckman Coulter Co., Ltd .: electrolyte for measurement
- drop it with a dropper while gently stirring, and the concentration meter reading on the body screen is 10% Fit back and forth.
- the aperture size, Current, Gain, and Polarity are input to the Multisizer II body according to the REFERENCE MANUAL FOR THE MULTILIZER MULTISIZER (1987) issued by Coulter Electronics Limited and measured manually. During the measurement, the beaker is stirred gently to the extent that bubbles do not enter, and the measurement is terminated when 100,000 particles are measured.
- the coefficient of variation (CV value) of the particle diameter of the colored resin particles is calculated by the following formula.
- Coefficient of variation of particle diameter of colored resin particles (standard deviation of particle size distribution of colored resin particles / volume average particle diameter in terms of sphere of colored resin particles) ⁇ 100 (Synthesis example 1 of emulsion for seed particle formation)
- a separable flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 600 g of water, 100 g of methyl methacrylate and 0.5 g of n-dodecyl mercaptan, purged with nitrogen under stirring, and heated to 70 ° C.
- the internal temperature of the flask was maintained at 70 ° C., 0.5 g of potassium persulfate was added as a polymerization initiator to the stirred product, and then the polymerization reaction was carried out for 8 hours to obtain an emulsion.
- the resulting emulsion contained 14% solids.
- the solid content consisted of true spherical particles having an average particle size of 0.4 ⁇ m and a weight average molecular weight of 600,000.
- the obtained mixture was mixed with 1 L of ion-exchanged water containing 10 g of sodium succinate as a surfactant, and treated with TK homomixer (manufactured by Primics Co., Ltd.) at 8000 rpm for 10 minutes to obtain an aqueous emulsion. It was. To this aqueous emulsion, 360 g of a seed particle-containing emulsion having an average particle diameter of 1.1 ⁇ m obtained in Seed Particle Production Example 1 was added with stirring.
- Resin particles were prepared in the same manner as in Resin Particle Production Example 1 except that 700 g of methyl methacrylate and 300 g of ethylene glycol dimethacrylate were used as the polymerizable vinyl monomer, and poly (ethylene glycol-propylene glycol) monomethacrylate was not used. Obtained.
- Resin particles were obtained in the same manner as in Resin Particle Production Example 1 except that the swelling ratio was about 40 times.
- the sphere conversion volume average particle diameter of the irregularly shaped particles was 3.10 ⁇ m.
- Resin particles were obtained in the same manner as in the resin particle production example 1 except that the seed particle-containing emulsion produced in the seed particle production example 2 was used.
- the sphere conversion volume average particle diameter of the irregularly shaped particles was 2.71 ⁇ m.
- Example 1 In a solution of 20 g of potassium persulfate dissolved in 300 g of water (1.0 molar equivalent with respect to pyrrole), 50 g of the resin particles (hemispherically shaped particles) obtained in Resin Particle Production Example 1 were dispersed in 50 g of isopropanol. The resulting suspension was added and stirred. This suspension was cooled to 5 ° C., a solution consisting of 5 g of pyrrole and 50 g of isopropanol was further added, and the mixture was stirred for 3 hours for polymerization. Then, solid content was obtained by filtration. The solid content was taken out, washed with water and isopropanol, and dried at 60 ° C. for 12 hours with a vacuum dryer to obtain black colored resin particles whose surface was coated with a pyrrole polymer.
- FIG. 2 shows a cross-sectional photograph of the colored resin particles according to Example 1 using a transmission electron microscope. A photograph taken by a scanning electron microscope of the colored resin particles according to Example 1 is shown in FIG.
- the coefficient of variation (CV value) of the particle diameter of the obtained colored resin particles was 11.3%.
- Example 2 The surface of the resin particle is pyrrole in the same manner as in Example 1 except that 50 g of the resin particle of the resin particle production example 2 (atypical particle having a double-sided convex lens shape) is used instead of the resin particle of the resin particle production example 1. Black colored resin particles coated with the polymer were obtained.
- FIG. 5 shows a cross-sectional photograph of the colored resin particles according to Example 2 using a transmission electron microscope.
- the coefficient of variation (CV value) in the particle diameter of the obtained colored resin particles was 10.8%.
- Example 3 Example 1 except that 50 g of resin particles of resin particle production example 3 (deformed particles having a concave cross section having one notch communicating with the diameter direction) were used in place of the resin particles of resin particle production example 1. In the same manner as above, black colored resin particles whose surface was coated with a pyrrole polymer were obtained.
- FIG. 7 shows a sectional photograph of the colored resin particles according to Example 3 taken with a transmission electron microscope.
- the coefficient of variation (CV value) of the particle diameter of the obtained colored resin particles was 11.6%.
- Example 4 The surface of the resin particle is pyrrole in the same manner as in Example 1 except that 50 g of the resin particle (mushroom-shaped irregularly shaped particle) of Resin Particle Production Example 4 was used instead of the resin particle of Resin Particle Production Example 1. Black colored resin particles coated with a polymer were obtained.
- FIG. 9 shows a sectional photograph of the colored resin particles according to Example 4 taken with a transmission electron microscope.
- the coefficient of variation (CV value) of the particle diameter of the obtained colored resin particles was 10.9%.
- Comparative Example 1 Method for producing true spherical colored resin particles
- a black true spherical colored resin particle coated with was obtained.
- the coefficient of variation (CV value) in the particle diameter of the obtained colored resin particles was 10.8%.
- Example 5 Preparation of hard coat layer coating solution 200 parts by weight of an acrylic monomer (trade name “KAYARAD (registered trademark) DPHA”, dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) as a resin binder, and a photopolymerization initiator (Irgacure (registered trademark) 184 (BASF) Obtained by Example 2), 25 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone), 110 parts by weight of propylene glycol monomethyl ether as a solvent, and 110 parts by weight of ethyl acetate as a solvent.
- a hard coat layer coating solution As a paint was prepared.
- the above-mentioned coating layer (hard coating layer coating solution) is formed by coating the above-mentioned coating layer using a micro gravure coater.
- a micro gravure coater was dried at 90 ° C.
- the said application layer was hardened by irradiating the said application layer with the ultraviolet-ray so that the illumination intensity of an irradiation part might be set to 0.1 W / cm ⁇ 2 > and the irradiation amount might be set to 0.1 J / cm ⁇ 2 > using the ultraviolet lamp.
- the anti-glare hard coat layer having a thickness of 5 ⁇ m is formed on the PET film, and the PET film and the anti-glare property as an anti-glare film which is one of optical films (one type of coated article).
- An antiglare hard coat film comprising a hard coat layer was produced.
- Example 6 A hard coat film was produced in the same manner as in Example 5, except that the amount of the double-sided convex lens-shaped colored resin particles obtained in Example 2 was changed from 20 parts by weight to 16 parts by weight.
- Example 7 A hard coat film was produced in the same manner as in Example 5 except that the amount of the double-sided convex lens-like colored resin particles obtained in Example 2 was changed from 20 parts by weight to 12 parts by weight.
- Example 2 A hard coat film was produced in the same manner as in Example 6 except that the double-sided convex lens-like resin particles obtained in Resin Particle Production Example 2 were used in place of the double-sided convex lens-like colored resin particles obtained in Example 2. .
- Comparative Example 3 A hard coat film was produced in the same manner as in Example 7 except that the true spherical colored resin particles obtained in Comparative Example 1 were used in place of the double-sided convex lens-like colored resin particles obtained in Example 2.
- Each of the hard coat films obtained in Examples 5 to 7 and Comparative Examples 2 and 3 has a coating surface (surface on which the antiglare hard coat layer is formed) on the tablet terminal surface during image display. It was placed in contact with the tablet terminal surface. The glare of the image at that time was visually evaluated. A case where there was no glare was indicated by “ ⁇ ”, a case where slight glare was observed was indicated by “ ⁇ ”, and a case where there was a lot of glare was indicated by “X”. The evaluation results are shown in Table 2.
- the antiglare film obtained using the irregular shaped colored resin particles of the present invention uses true spherical transparent resin particles and true spherical colored resin particles. Compared with the antiglare film obtained in this way, display brightness is greatly reduced without significantly reducing the brightness of display by the display device and without greatly reducing the effect of preventing external light from being reflected on the display surface. It turned out that it can suppress. Moreover, since the glare-proof film of this invention can suppress the glare of a display, it is thought that the fall of the contrast of the display by an anti-glare film can also be suppressed.
- Example 8 A mascara was made with the following formulation according to the preparation process normally used for the preparation of cosmetics.
- Comparative Example 4 A mascara was prepared in the same manner as in Example 8, except that the spherical resin particles obtained in Comparative Example 1 were used in place of the double-sided convex lens-like colored resin particles obtained in Example 2.
- the external preparation using the colored resin particles of the present invention has better adhesion to the eyelashes and is less likely to peel off from the eyelashes than the external preparation using the true spherical colored resin particles. I understood.
- Example 9 Manufacture of compounds
- Aromatic polycarbonate resin obtained by reaction of 2,2-bis (4-hydroxyphenyl) propane and a carbonate precursor as a base resin product name “Taflon (registered trademark) A2500” manufactured by Idemitsu Kosan Co., Ltd.)
- 100 parts by weight and 5 parts by weight of the double-sided convex lens-shaped colored resin particles obtained in Example 2 as polymer particles (light diffusing agent) were mixed for 15 minutes with a Henschel mixer.
- the obtained mixture was extruded using a single screw extruder (product name “R50” manufactured by Hoshi Plastic Co., Ltd.) under the conditions of a temperature of 250 to 280 ° C.
- the obtained pellet-like light diffusing resin composition was pre-dried at 120 ° C. for 5 hours to sufficiently remove moisture. Thereafter, by using an injection molding machine (product name “K-80” manufactured by Kawaguchi Tekko Co., Ltd.), the light diffusing resin composition is injection molded under the condition of a cylinder temperature of 255 to 280 ° C.
- a light diffusing plate (one type of molded body) having a thickness of 2 mm, a width of 50 mm, and a length of 100 mm was produced.
- the obtained pellet-like light diffusing resin composition was pre-dried at 120 ° C. for 5 hours to sufficiently remove moisture. Thereafter, by using an injection molding machine (product name “K-80” manufactured by Kawaguchi Tekko Co., Ltd.), the light diffusing resin composition is injection molded under the condition of a cylinder temperature of 255 to 280 ° C.
- a light diffusing plate (one type of molded body) having a thickness of 2 mm, a width of 50 mm, and a length of 100 mm was produced.
- Example 9 and Comparative Example 5 In order to evaluate the conductivity of the light diffusing plates obtained in Example 9 and Comparative Example 5, using a high resistivity meter (equipment name “Hiresta UP”, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) according to JIS K6911. The surface specific resistance value (unit: ⁇ ) was measured under the conditions of an applied voltage of 500 V and 1 minute. For the light diffusing plate obtained in Example 9 and Comparative Example 5, the total light transmittance was measured according to JIS K7136. Table 4 shows the measurement results of the surface resistivity and the total light transmittance.
- the molded body using the irregular shaped colored resin particles of the present invention has a higher total light transmittance than the molded body using true spherical colored resin particles, and has a surface-specific property. It was found that the resistance value was low.
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Abstract
Description
本発明の着色樹脂粒子、およびその製造に用いる樹脂粒子は、樹脂粒子および着色樹脂粒子が、投影面積が最大となる方向から見たときの異形樹脂粒子の外形が円形であり、投影面積が最小となる方向から見たときの異形樹脂粒子の外形が非円形である、異形形状を有する粒子(以下、異形粒子と呼ぶ)である。前記異形形状は、凹部を有する形状、半球状の形状、両面凸レンズ状の形状、又はキノコ状の形状であることが好ましい。前記凹部を有する形状としては、直径方向に連通する1つの切り欠き部を有する断面凹状(以下、断面馬蹄状とも記す)、断面馬蹄状でない凹レンズ状などが挙げられる。前記異形形状は、断面馬蹄状、半球状の形状、両面凸レンズ状の形状、又はキノコ状の形状であることが特に好ましい。また、本発明の着色樹脂粒子、およびその製造に用いる樹脂粒子は、同一の異形形状を有することが好ましく、また、規則的な異形形状を有することも好ましい。
次に、樹脂粒子の製造用原料及び製造方法を説明する。樹脂粒子の製造方法としては、種粒子に、水性乳化液中の重合性ビニル系単量体を吸収させ、吸収させた重合性ビニル系単量体を重合させる、いわゆるシード重合法が好適である。
種粒子は、炭素数3以上6未満のアルキル基をエステル部に含む(メタ)アクリル酸エステル(炭素数3以上6未満のアルキルアルコールと(メタ)アクリル酸とが縮合したもの)を含む単量体に由来する樹脂粒子であることが好ましい。種粒子を形成するための単量体は、炭素数3以上6未満のアルキル基をエステル部に含む(メタ)アクリル酸エステルを50重量%以上含むことが好ましい。このような単量体に由来する樹脂粒子は、非真球状(異形)粒子となり易い。このアルキル基としては、n-プロピル、n-ブチル、n-ペンチル等の直鎖アルキル基、イソプロピル、イソブチル、t-ブチル等の分岐アルキル基が挙げられる。具体的な(メタ)アクリル酸エステルとしては、(メタ)アクリル酸n-プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸t-ブチル等の単量体が挙げられる。これら単量体は、一種を用いてもよいし、二種以上を混合して用いてもよい。中でも分岐アルキル基(例えば、イソプロピル、イソブチル、t-ブチル)を有する(メタ)アクリル酸エステルは、樹脂粒子は、非真球状(異形)の樹脂粒子が得られ易いため、好ましい。
種粒子の製造方法は、特に限定されないが、乳化重合、ソープフリー乳化重合、シード重合、懸濁重合等の公知の方法を用いることができる。製造法は、種粒子の粒子径の均一性や製造法の簡便性を考慮すると、乳化重合、ソープフリー乳化重合、シード重合法が好ましい。
重合性ビニル系単量体は、架橋性単量体を5~50重量%含む単量体であることが好ましい。架橋性単量体としては、特に限定されず、公知の架橋性単量体を何れも使用できる。架橋性単量体としては、例えば、エチレングリコールジメタクリレート、トリメチロールプロパントリメタクリレート、ジビニルベンゼン等の重合性ビニル基(重合性のビニル基または置換ビニル基)を1分子中に2つ以上有する多官能性単量体が用いられる。架橋性単量体の使用量は、重合性ビニル単量体全量に対して、5~50重量%である。架橋性単量体の比率が5重量%未満や50重量%より大きい場合は、異形化が小さく球状に近い粒子が得られることがある。より好ましい使用量は10~40重量%である。
以下に、一例として、シード重合法を用いた樹脂粒子の製造方法を述べるが、樹脂粒子の製造方法は、この方法に限定されるものではない。
本発明の着色樹脂粒子の製造方法では、上記説明したシード重合法等により得られた異形の樹脂粒子の表面に、含窒素芳香族化合物に由来する重合体を被覆する。含窒素芳香族化合物に由来する重合体を被覆する方法としては、酸化剤を含む水性媒体中に前記樹脂粒子を分散させて分散液(乳化液または懸濁液)とし、該分散液に窒素芳香族化合物を添加し攪拌して、酸化重合により前記樹脂粒子の表面に前記含窒素芳香族化合物の重合体を被覆させる方法が好ましい。
含窒素芳香族化合物としては、ピロール、インドール、イミダゾール、ピリジン、ピリミジン、ピラジン等の含窒素複素環式芳香族化合物、アニリンのような1級アミノ基置換芳香族化合物、及びこれらのアルキル置換体(例えば、メチル基、エチル基、プロピル基、ブチル等の炭素数1~4のアルキル基による置換体)、ハロゲン置換体(例えば、フルオロ基、クロロ基、ブロモ基等のハロゲン基による置換体)、ニトリル置換体といった誘導体が挙げられる。これらの単量体は単独で使用して、単独重合体とすることができ、あるいは2種類以上を併用して、共重合体とすることもできる。より均一な被覆層が形成されやすいこと、および黒色の着色樹脂粒子が得られることから、ピロール及びピロールの誘導体の重合体が含窒素芳香族化合物として好ましい。
酸化剤としては、塩酸、硫酸、クロロスルホン酸のような無機酸、アルキルベンゼンスルホン酸、アルキルナフタレンスルホン酸のような有機酸、塩化第二鉄、塩化アルミニウムのような金属ハロゲン化物、過塩素酸カリウムのようなハロゲン酸、過硫酸カリウム、過硫酸アンモニウム、過硫酸ナトリウム、過酸化水素のような過酸化物等が挙げられる。これらは単独または混合して使用してもよい。酸化剤としては、無機過酸のアルカリ金属塩が好ましい。無機過酸のアルカリ金属塩としては、具体的には、過硫酸カリウム、過硫酸ナトリウム等が挙げられる。
酸化剤が添加される水性媒体は、含窒素芳香族化合物を溶解又は分散できるものであれば特に限定されるものではないが、水又は、水と、メタノール、エタノール、n-プロパノール、イソプロパノール、n-ブタノール、t-ブタノール等のアルコール類;ジエチルエーテル、イソプロピルエ一テル、ブチルエーテル、メチルセロソルブ、テトラヒドロフラン等のエーテル類;アセトン、メチルエチルケトン、ジエチルケトン等のケトン類との混合媒体が挙げられる。
また、水性媒体には、界面活性剤を添加してもよい。界面活性剤としては、アニオン性界面活性剤、カチオン性界面活性剤、両性イオン性界面活性剤、ノニオン性界面活性剤をいずれも使用できる。
上述した酸化重合を用いた着色樹脂粒子の製造方法では、酸化剤を含む水性媒体中に前記樹脂粒子を分散させて分散液とし、該分散液に窒素芳香族化合物を添加し、攪拌して酸化重合することにより、異形の樹脂粒子表面が含窒素芳香族化合物に由来する重合体で被覆された着色樹脂粒子を得る。次いで、酸化重合の温度は-20~40℃の範囲であることが好ましく、酸化重合の時間は、0.5~10時間の範囲であることが好ましい。
着色樹脂粒子は、樹脂粒子の表面全体が均一に含窒素芳香族化合物に由来する重合体を含む被覆層で覆われていることが好ましい。ここで、「均一」とは、樹脂粒子を覆う含窒素芳香族化合物に由来する重合体を含む被覆層の厚さの振れが少ないことを言う。振れは50%以下であることが好ましく、40%以下であることがより好ましい。
本発明に係る着色樹脂粒子は、投影面積が最大となる方向から見たときの異形樹脂粒子の外形が円形であり、投影面積が最小となる方向から見たときの異形樹脂粒子の外形が非円形である、異形形状を有し、かつ樹脂粒子の表面が含窒素芳香族化合物に由来する重合体からなる被覆層で被覆されている。そのため、この重合体に由来する着色度(例えば黒色)を有する、化粧料を初めとする各種用途への適用が可能な着色樹脂粒子とすることができる。
本発明の樹脂組成物は、本発明の着色樹脂粒子を含んでいる。本発明の樹脂組成物に用いる着色樹脂粒子の形状は、異形形状であれば特に限定されるものではないが、凹部を有する形状、半球状の形状、両面凸レンズ状の形状、又はキノコ状の形状が好ましく、両面凸レンズ状であることがさらに好ましい。
ポリ塩化ビニル、塩化ビニル-塩化ビニリデン共重合体等の塩化ビニル系樹脂;
ポリ酢酸ビニル、酢酸ビニル-エチレン共重合体等のビニルエステル系樹脂;
ポリスチレン、スチレン-アクリロニトリル共重合体、スチレン-ブタジエン-アクリロニトリル共重合体、スチレン-ブタジエンブロック共重合体、スチレン-イソプレンブロック共重合体、スチレン-メタクリル酸メチル共重合体等のスチレン系樹脂;
ポリ(メタ)アクリル酸エステル、(メタ)アクリル酸エステル-アクリロニトリル共重合体、(メタ)アクリル酸エステル-スチレン共重合体等の(メタ)アクリル酸エステル系樹脂;
テレフタル酸とエチレングリコールとの縮合体、アジピン酸とエチレングリコールとの縮合体等のポリエステル系樹脂;
ポリエチレン、ポリプロピレン、塩素化ポリエチレン、塩素化ポリプロピレン、カルボキシル変性ポリエチレン、ポリイソブチレン、ポリブタジエン等のポリオレフィン系樹脂;
ウレタン系樹脂;エポキシ系樹脂;シリコーン系樹脂;フッ素系樹脂等が挙げられる。これら基材樹脂は、単独で用いてもよく、2種以上を併用してもよい。
1,1-ビス(4-ヒドロキシフェニル)シクロペンタン、1,1-ビス(4-ビドロキシフェニル)シクロヘキサン、1,1-ビス(4-ヒドロキシフェニル)-3,5,5-トリメチルシクロヘキサン等のビス(ヒドロキシアリール)シクロアルカン類;
4,4’-ジビドロキシフェニルエーテル、4,4’-ジヒドロキシ-3,3’-ジメチルフェニルエーテル等のジヒドロキシアリールエーテル類;
4,4’-ジヒドロキシジフェニルスルフィド、4,4’-ジヒドロキシ-3,3’-ジメチルジフェニルスルフィド等のジヒドロキシジアリールスルフィド類;
4,4’-ジヒドロキシジフェニルスルホキシド、4,4’-ジヒドロキシ-3,3’-ジメチルジフェニルスルホキシド等のジヒドロキシジアリールスルホキシド類;
4,4’-ジヒドロキシジフェニルスルホン、4,4’-ジヒドロキシ-3,3’-ジメチルジフェニルスルホン等のジヒドロキシジアリールスルホン類;
4,4’-ジヒロキシジフェニルなどのジヒドロキシジフェニル類等が挙げられる。
ベンゾトリアゾール-2-イル]フェノール]](株式会社ADEKA製の「アデカスタブ(登録商標)LA-31」)、2-(2-ヒドロキシ-5-メチルフェニル)ベンゾトリアゾール、2-(2-ヒドロキシ-5-t-ブチルフェニル)ベンゾトリアゾール、2-(2-ヒドロキシ-3-5-ジt-ブチルフェニル)-5-クロロベンゾトリアゾール等のベンゾトリアゾール系紫外線吸収剤;ヒドロキシフェニルトリアジン系紫外線吸収剤;p-t-ブチルフェニルサリシレート、p-オクチルフェニルサリシレート等のサリチル酸系紫外線吸収剤;2-エチルヘキシル-2-シアノ-3,3-ジフェニルアクリレート、エチル-2-シアノ-3,3-ジフェニルアクリレート等のシアノアクリレート系紫外線吸収剤等を用いることができる。前記有機系の紫外線吸収剤を、樹脂組成物中に、基材樹脂100重量部に対し、好ましくは0.01~2.0重量部、より好ましくは0.03~2.0重量部、さらに好ましくは0.05~1.0重量部の割合で含めると、樹脂組成物に十分な紫外線吸収性を付与することができる。
本発明の成形体は、本発明の樹脂組成物を成形してなるものである。樹脂組成物の成形方法としては、生産性の点から、ペレット状の樹脂組成物を射出成形、射出圧縮成形、又は、押出成形等の成形法により成形して、成形体を得る方法を採用することができる。また、樹脂組成物を押出成形してシート状成形体を得て、このシート状成形体を真空成形、圧空成形等の成形法により成形して成形体を得る方法を採用することができる。
本発明の塗料は、本発明の着色樹脂粒子を含んでいる。本発明の塗料に用いる着色樹脂粒子の形状は、異形形状であれば特に限定されるものではないが、凹部を有する形状、半球状の形状、両面凸レンズ状の形状、又はキノコ状の形状が好ましく、両面凸レンズ状がであることがさらに好ましい。
本発明の塗工物品は、本発明の塗料を基材上に塗工(塗布)してなる。すなわち、本発明の塗工物品は、基材と、基材上に塗工された本発明の塗料によって形成された塗膜とを含んでいる。上記着色樹脂粒子がピロールまたはピロール誘導体に由来する重合体を含む場合には、本発明の塗工物品は、導電性及び帯電防止機能を有している。
本発明の塗工物品は、上記基材として透明基材フィルムを用いた場合、光拡散性を有する光学フィルムとして用いることができる。本発明の光学フィルムは、透明な本発明の塗料を透明基材フィルム上に塗工してなる。すなわち、本発明の光学フィルムは、透明基材フィルムと、本発明の塗料の塗工によって透明基材フィルム上に形成された光拡散性の塗膜(以下「光学機能層」と称する)とを含んでいる。
本発明の光学フィルム中における着色樹脂粒子は、透明な塗料中に配合されて光学機能層の形成に用いられるものである。上記光学機能層は、特に限定されないが、ディスプレイ用光学機能層として利用できる。上記光学機能層は、より詳細には、例えば、ディスプレイ(特に高精細画像用ディスプレイ)の表面に設置される表面フィルムやスクリーン等の光学フィルムにおける、防眩層、ハードコート層、反射防止層等として利用することができる。上記着色樹脂粒子がピロールまたはピロール誘導体に由来する重合体を含む場合には、上記光学機能層は、導電性を有するので、上記各種光学フィルムにおける帯電防止層としても利用できる。
本発明の外用剤は、本発明の着色樹脂粒子を含んでいる。本発明の外用剤に用いる着色樹脂粒子の形状は、異形形状であれば特に限定されるものではないが、凹部を有する形状、半球状の形状、両面凸レンズ状の形状、又はキノコ状の形状が好ましく、両面凸レンズ状であることがさらに好ましい。
重量平均分子量(Mw)の測定は、ゲルパーミエーションクロマトグラフィー(GPC)を用いて行われる。なお、重量平均分子量はポリスチレン(PS)換算重量平均分子量を意味する。具体的には以下のようにして重量平均分子量を測定する。
カラム:東ソー株式会社製、商品名「TSKgel GMH-XL-L」φ7.8mm×30cm×2本
カラム温度:40℃
キャリアーガス:テトラヒドロフラン(THF)
キャリアーガス流量:1ミリリットル/分
注入・ポンプ温度:35℃
検出:RI
注入量:100マイクロリットル
検量線用標準ポリスチレン:昭和電工株式会社製、商品名「Shodex(登録商標)」重量平均分子量:1030000と東ソー株式会社製、重量平均分子量:5480000、3840000、355000、102000、37900、9100、2630、870
(種粒子の平均粒子径の測定方法)
種粒子の平均粒子径は、ベックマン・コールター株式会社のLS230型で測定する。具体的には、粒子0.1gと0.1%ノニオン性界面活性剤溶液10mを投入し、ヤマト科学株式会社製タッチミキサーTOUCHMIXER MT-31で2秒間混合する。この後、試験管を市販の超音波洗浄器である株式会社ヴェルヴォクリーア製ULTRASONIC CLEARNER VS-150を用いて10分間分散させる。分散させたものをベックマン・コールター株式会社製のLS230型にて超音波を照射しながら測定する。そのときの光学モデルは、作製した粒子の屈折率にあわせる。
異形粒子の各部位の長さA~Iは、以下のようにして測定する。
孔径50~280μmの細孔に電解質溶液を満たし、当該電解質溶液を粒子が通過する際の電界質溶液の導電率変化から体積を求め、平均粒子径(異形粒子及び着色樹脂粒子の球換算体積平均粒子径並びに真球状粒子の平均粒子径)を計算する。具体的には、測定した平均粒子径は、ベックマン・コールター株式会社製のコールターマルチサイザーIIによって測定した体積平均粒子径(算術平均値)である。なお、測定に際してはCoulter Electronics Limited発行のREFERENCE MANUAL FOR THE COULTER MULTISIZER(1987)に従って、測定する粒子の粒子径に適合したアパチャーを用いてキャリブレーションを行い測定する。
着色樹脂粒子の粒子径の変動係数(CV値)を、以下の式によって算出する。
÷着色樹脂粒子の球換算体積平均粒子径)×100
(種粒子形成用エマルジョンの合成例1)
攪拌機、温度計及び還流コンデンサーを備えたセパラブルフラスコに、水600g、メタクリル酸メチル100g、及びn-ドデシルメルカプタン0.5gを仕込み、攪拌下に窒素置換し、70℃に昇温した。フラスコの内温を70℃に保ち、攪拌物に、重合開始剤として過硫酸カリウム0.5gを添加した後、8時間重合反応させてエマルジョンを得た。得られたエマルジョンは固形分を14%含有していた。固形分は、平均粒子径0.4μm、重量平均分子量60万の真球状粒子からなっていた。
攪拌機、温度計及び還流コンデンサーを備えたセパラブルフラスコに、水600gとメタクリル酸メチル100gとを仕込み、攪拌下に窒素置換し70℃に昇温した。フラスコの内温を70℃に保ち、攪拌物に、重合開始剤として過硫酸カリウム0.5gを添加した後、12時間重合反応させてエマルジョンを得た。得られたエマルジョンは固形分を14%含有していた。固形分は、平均粒子径0.43μm、重量平均分子量82万の真球状粒子からなっていた。
攪拌機、温度計及び還流コンデンサーを備えたセパラブルフラスコに、水600gと、メタクリル酸メチル100gと、n-オクチルメルカプタン1.1gとを仕込み、攪拌下に窒素置換し70℃に昇温した。フラスコの内温を70℃に保ち、攪拌物に、重合開始剤として過硫酸カリウム0.5gを添加した後、12時間重合反応させてエマルジョンを得た。得られたエマルジョンは固形分を14%含有していた。固形分は、平均粒子径0.43μm、重量平均分子量3万の真球状粒子からなっていた。
攪拌機、温度計及び還流コンデンサーを備えたセパラブルフラスコに、水550g、合成例1で得られたエマルジョン70g、メタクリル酸イソブチル100g、及びn-ドデシルメルカプタン0.3gを仕込み、攪拌下に窒素置換し、70℃に昇温した。内温を70℃に保ち、重合開始剤として過硫酸カリウムを0.5g添加した後、8時間重合反応させた。得られたエマルジョンは固形分を14%含有し、その固形分は、平均粒子径1.1μm、重量平均分子量61万の真球状粒子(種粒子)からなっていた。
攪拌機、温度計及び還流コンデンサーを備えたセパラブルフラスコに、水550g、合成例2で得られたエマルジョン70g、及びメタクリル酸イソブチル100gを仕込み、攪拌下に窒素置換し、70℃に昇温した。内温を70℃に保ち、重合開始剤として過硫酸カリウム0.5gを添加した後、8時間重合反応させた。得られたエマルジョンは固形分14%含有し、その固形分は、平均粒子径1.0μm、重量平均分子量83万の真球状粒子(種粒子)からなっていた。
攪拌機、温度計を備えた5Lの反応器に、重合性ビニル系単量体として、メタクリル酸メチル600g、エチレングリコールジメタクリレート300g、ポリ(エチレングリコール-プロピレングリコール)モノメタクリレート(製品名:ブレンマー(登録商標)50PEP-300/日油株式会社製、一般式[化1]中、R1=CH3、R2=C2H4、R3=C3H6、R4=Hであり、m及びnは平均してm=3.5及びn=2.5の混合物である)100g、重合開始剤として2,2’-アゾビスイソブチロニトリル6gを入れて混合した。得られた混合物を、界面活性剤としてコハクスルホン酸ナトリウム10gが含まれたイオン交換水1Lと混合し、TKホモミキサー(プライミクス株式会社製)にて8000rpmで10分間処理して水性乳化液を得た。この水性乳化液に、種粒子製造例1で得た平均粒子径が1.1μmの種粒子含有エマルジョン360gを攪拌しながら加えた。
重合性ビニル系単量体として、メタクリル酸メチル700g及びエチレングリコールジメタクリレート300gを用い、ポリ(エチレングリコール-プロピレングリコール)モノメタクリレートを使用しないこと以外は樹脂粒子製造例1と同様にして樹脂粒子を得た。得られた樹脂粒子を走査型電子顕微鏡で観察したところ、両面凸レンズ状(A=2.88μm、H=1.27μm、I=0.64μm)の異形粒子であった。また、異形粒子の球換算体積平均粒子径は、2.61μmであった。
膨潤倍率を約40倍とすること以外は樹脂粒子製造例1と同様にして樹脂粒子を得た。得られた樹脂粒子は、走査型電子顕微鏡で観察したところ、直径方向に連通する1つの切り欠き部を有する断面凹状(A=3.45μm、B=1.15μm、C=1.74μm)の異形粒子であった。また、異形粒子の球換算体積平均粒子径は、3.10μmであった。
種粒子製造例2で作製した種粒子含有エマルジョンを使用すること以外は樹脂粒子製造例1と同様にして樹脂粒子を得た。得られた樹脂粒子は、走査型電子顕微鏡で観察したところ、キノコ状(A=3.26μm、D1=1.43μm、D2=1.87μm、E=1.80μm)の異形粒子であった。また、異形粒子の球換算体積平均粒子径は、2.71μmであった。
重合性ビニル系単量体として、メタクリル酸メチル700g及びエチレングリコールジメタクリレート300gを用い、種粒子製造例1で得た種粒子含有エマルジョンに代えて種粒子形成用エマルジョンの合成例3で得られたエマルジョン41.6gを使用し、ポリ(エチレングリコール-プロピレングリコール)モノメタクリレートを使用しないこと以外は樹脂粒子製造例1と同様にして樹脂粒子を得た。得られた樹脂粒子を走査型電子顕微鏡で観察したところ、真球状粒子であった。樹脂粒子の平均粒子径は2.51μmであった。
水300gに過硫酸カリウム20g(ピロールに対して1.0モル当量)を溶解させた溶液に、樹脂粒子製造例1で得られた50gの樹脂粒子(半球状の異形粒子)をイソプロパノール50gに分散させた懸濁液を添加して攪拌した。この懸濁液を5℃まで冷却し、ピロール5gとイソプロパノール50gとからなる溶液を更に加え、3時間攪拌して重合をさせた。その後、濾過により固形分を得た。固形分を取り出し、水、イソプロパノールで洗浄し、真空乾燥機により60℃で12時間乾燥を行って、樹脂粒子の表面がピロールの重合体で被覆された黒色の着色樹脂粒子を得た。
樹脂粒子製造例1の樹脂粒子に代えて、樹脂粒子製造例2の樹脂粒子(両面凸レンズ状の異形粒子)を50g用いたこと以外は、実施例1と同様にして、樹脂粒子の表面がピロールの重合体で被覆された黒色の着色樹脂粒子を得た。
樹脂粒子製造例1の樹脂粒子に代えて、樹脂粒子製造例3の樹脂粒子(直径方向に連通する1つの切り欠き部を有する断面凹状の異形粒子)を50g用いたこと以外は、実施例1と同様にして、樹脂粒子の表面がピロールの重合体で被覆された黒色の着色樹脂粒子を得た。
樹脂粒子製造例1の樹脂粒子に代えて、樹脂粒子製造例4の樹脂粒子(キノコ状の異形粒子)を50g用いたこと以外は、実施例1と同様にして、樹脂粒子の表面がピロールの重合体で被覆された黒色の着色樹脂粒子を得た。
樹脂粒子製造例1の樹脂粒子に代えて、樹脂粒子製造例5の樹脂粒子(真球状粒子)を50g用いたこと以外は、実施例1と同様にして、樹脂粒子の表面がピロールの重合体で被覆された黒色の真球状着色樹脂粒子を得た。
(ハードコート層塗布液の作製)
樹脂バインダーとしての、アクリルモノマー(商品名「KAYARAD(登録商標)DPHA」、ジペンタエリスリトールヘキサアクリレート、日本化薬株式会社製)200重量部と、光重合開始剤(イルガキュア(登録商標)184(BASFジャパン株式会社製)、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン)25重量部と、溶剤としてのプロピレングリコールモノメチルエーテル110重量部と、溶剤としての酢酸エチル110重量部と、実施例2で得られた両面凸レンズ状の着色樹脂粒子(球換算体積平均粒子径2.61μm)20重量部とを攪拌し混合することによって、塗料としてのハードコート層塗布液を作製した。
透明基材フィルムとしての厚さ188μmのPETフィルム上に、マイクログラビアコーターを用いて上記ハードコート層塗布液を塗布して塗布層(ハードコート層塗布液の層)を形成した後、上記塗布層を90℃で乾燥した。その後、紫外線ランプを用いて、照射部の照度が0.1W/cm2、照射量が0.1J/cm2となりように紫外線を上記塗布層に照射して上記塗布層を硬化させた。これにより、上記PETフィルム上に厚さ5μmの防眩性ハードコート層が形成され、光学フィルム(塗工物品の1種)の1種である防眩フィルムとしての、上記PETフィルム及び防眩性ハードコート層からなる防眩性ハードコートフィルムが作製された。
実施例2で得られた両面凸レンズ状の着色樹脂粒子の使用量を20重量部から16重量部に変更した以外は実施例5と同様にして、ハードコートフィルムを作製した。
実施例2で得られた両面凸レンズ状の着色樹脂粒子の使用量を20重量部から12重量部に変更した以外は実施例5と同様にして、ハードコートフィルムを作製した。
実施例2で得られた両面凸レンズ状の着色樹脂粒子に代えて樹脂粒子製造例2で得られた両面凸レンズ状の樹脂粒子を用いる以外は実施例6と同様にして、ハードコートフィルムを作製した。
実施例2で得られた両面凸レンズ状の着色樹脂粒子に代えて比較例1で得られた真球状着色樹脂粒子を用いる以外は実施例7と同様にして、ハードコートフィルムを作製した。
実施例5~7及び比較例2・3で得られたハードコートフィルムのそれぞれのヘイズ(ヘーズ)及び全光線透過率を、ヘイズメーターNDH-2000を使用して測定した。ヘイズの測定はJIS K 7136に、全光線透過率の測定はJIS K 7361-1に、それぞれ従って実施した。測定結果を表2に示す。
実施例5~7及び比較例2・3で得られたハードコートフィルムのそれぞれを、画像表示中のタブレット端末表面に、塗工面(防眩性ハードコート層が形成されている側の面)がタブレット端末表面に当接するように置いた。そのときの画像のギラツキについて目視で評価を行い、ギラツキが全くない場合を「○」とし、ギラツキがわずかにみられる場合を「△」とし、ギラツキが多く存在する場合を「×」とした。評価結果を表2に示す。
下記の配合により、化粧品の調製に通常使用される調製プロセスに従って、マスカラを作成した。
カルナバワックス 4g
蜜蝋 8g
ポリビニルラウレート 0.8g
(Chimex社製の「Mexomer PP」)
酢酸ビニル/ステアリン酸アリルコポリマー(65/35) 2g
コメデンプン 1g
有機ヘクトライト(エレメンティススペシャリティーズ社製) 4g
(商品名「ベントーン(登録商標)(BENTONE(登録商標))」)
プロピレンカーボネート 2g
実施例2で得られた両面凸レンズ状の着色樹脂粒子 4g
保存剤 適量
イソドデカン 適量で100g
前記マスカラの塗布具としては、まつ毛用化粧料に通常用いられる、繊維を針金でねじったブラシで、塗布部全長25mm、最大径5.0mm、先端径3.5mm、根元径4.0mm、形状がR55(曲率半径55mm)の弓型のものを用いた。
実施例2で得られた両面凸レンズ状の着色樹脂粒子に代えて比較例1で得られた真球状着色樹脂粒子を用いる以外は実施例8と同様にして、マスカラを作成した。
次に、試験者(選定したパネラー)10人が、実施例8及び比較例4のマスカラを前記塗布具を用いて自分のまつ毛に塗布し、塗布直後のまつ毛の状態を目視評価し、カールアップ力に優れると評価した試験者の人数により各マスカラのカールアップ力を評価した。カールアップ力に優れると評価した試験者の人数が8~10人の場合を「○」とし、カールアップ力に優れると評価した試験者の人数が5~7人の場合を「△」とし、カールアップ力に優れると評価した試験者の人数が0~4人の場合を「×」とする。得られた結果を表3に示す。
また、試験者10人が、実施例8及び比較例4のマスカラを前記塗布具を用いて自分のまつ毛に塗布し、8時間経過時点のまつ毛の状態を目視評価し、にじまなさに優れると評価した試験者の人数により各マスカラの化粧持ちを評価した。にじまなさに優れると評価した試験者の人数が8~10人の場合を「○」とし、にじまなさに優れると評価した試験者の人数が5~7人の場合を「△」とし、にじまなさに優れると評価した試験者の人数が0~4人の場合を「×」とする。得られた結果を表3に示す。
(コンパウンドの製造)
基材樹脂としての、2,2-ビス(4-ヒドロキシフェニル)プロパンとカーボネート前駆体との反応によって得られた芳香族ポリカーボネート樹脂(出光興産株式会社製、製品名「タフロン(登録商標)A2500」)100重量部と、重合体粒子(光拡散剤)としての実施例2で得られた両面凸レンズ状の着色樹脂粒子5重量部とを、ヘンシェルミキサーで15分間混合した。得られた混合物を単軸押し出し機(株式会社星プラスチック製、製品名「R50」)を用いて、温度250~280℃、吐出量10~25kg/hrの条件で押し出し、押し出した混合物を水冷して、樹脂組成物としてのコンパウンドを得た。コンパウンドをペレタイザーにてカットして、ペレット状の光拡散性樹脂組成物を得た。
得られたペレット状の光拡散性樹脂組成物を120℃で5時間かけて予備乾燥し、水分を十分に除去した。その後、射出成形機(川口鉄工株式会社製、製品名「K-80」)を用いて、シリンダー温度255~280℃の条件で光拡散性樹脂組成物を射出成形することにより、光拡散部材としての、厚さ2mm、幅50mm、長さ100mmの光拡散板(成形体の1種)を製造した。
(コンパウンドの製造)
基材樹脂としての、2,2-ビス(4-ヒドロキシフェニル)プロパンとカーボネート前駆体との反応によって得られた芳香族ポリカーボネート樹脂(出光興産株式会社製、製品名「タフロン(登録商標)A2500」)100重量部、重合体粒子(光拡散剤)としての比較例1で得られた真球状着色樹脂粒子5重量部とを、ヘンシェルミキサーで15分間混合した。得られた混合物を単軸押し出し機(株式会社星プラスチック製、製品名「R50」)を用いて、温度250~280℃、吐出量10~25kg/hrの条件で押し出し、押し出した混合物を水冷して、樹脂組成物としてのコンパウンドを得た。コンパウンドをペレタイザーにてカットして、ペレット状の光拡散性樹脂組成物を得た。
得られたペレット状の光拡散性樹脂組成物を120℃で5時間かけて予備乾燥し、水分を十分に除去した。その後、射出成形機(川口鉄工株式会社製、製品名「K-80」)を用いて、シリンダー温度255~280℃の条件で光拡散性樹脂組成物を射出成形することにより、光拡散部材としての、厚さ2mm、幅50mm、長さ100mmの光拡散板(成形体の1種)を製造した。
Claims (16)
- 樹脂粒子の表面に、含窒素芳香族化合物に由来する重合体が被覆された着色樹脂粒子であって、
投影面積が最大となる方向から見たときの異形樹脂粒子の外形が円形であり、投影面積が最小となる方向から見たときの異形樹脂粒子の外形が非円形である、異形形状を有することを特徴とする着色樹脂粒子。 - 請求項1に記載の着色樹脂粒子であって、
前記異形形状が、凹部を有する形状、半球状の形状、両面凸レンズ状の形状、又はキノコ状の形状であることを特徴とする着色樹脂粒子。 - 請求項1又は2に記載の着色樹脂粒子であって、
前記含窒素芳香族化合物が、ピロールまたはピロール誘導体であることを特徴とする着色樹脂粒子。 - 請求項1~3のいずれか1項に記載の着色樹脂粒子であって、
前記樹脂粒子が、アルキレンオキサイド基を有する(メタ)アクリル酸エステルを含む重合性ビニル系単量体を重合させて得られたものであることを特徴とする着色樹脂粒子。 - 重合性ビニル系単量体を重合させて、投影面積が最大となる方向から見たときの異形樹脂粒子の外形が円形であり、投影面積が最小となる方向から見たときの異形樹脂粒子の外形が非円形である、異形形状を有する樹脂粒子を得る工程と、
得られた樹脂粒子の表面に、含窒素芳香族化合物に由来する重合体を被覆する工程とを含むことを特徴とする着色樹脂粒子の製造方法。 - 請求項5に記載の着色樹脂粒子の製造方法であって、
前記異形形状が、凹部を有する形状、半球状の形状、両面凸レンズ状の形状、又はキノコ状の形状であることを特徴とする着色樹脂粒子の製造方法。 - 請求項5又は6に記載の着色樹脂粒子の製造方法であって、
前記樹脂粒子を得る工程では、種粒子に重合性ビニル系単量体を吸収させ、吸収させた重合性ビニル系単量体を重合させることにより樹脂粒子を得ることを特徴とする着色樹脂粒子の製造方法。 - 請求項5~7のいずれか1項に記載の着色樹脂粒子の製造方法であって、
前記の含窒素芳香族化合物に由来する重合体を被覆する工程では、含窒素芳香族化合物に対して0.5~2.0モル当量の無機過酸のアルカリ金属塩を含む水性媒体中に前記樹脂粒子を分散させて分散液とし、該分散液に窒素芳香族化合物を添加し攪拌して、前記樹脂粒子の表面に前記含窒素芳香族化合物の重合体を被覆させることを特徴とする着色樹脂粒子の製造方法。 - 請求項1~4のいずれか1項に記載の着色樹脂粒子を含むことを特徴とする樹脂組成物。
- 請求項9に記載の樹脂組成物を成形してなることを特徴とする成形体。
- 請求項1~4のいずれか1項に記載の着色樹脂粒子を含むことを特徴とする光拡散板。
- 請求項1~4のいずれか1項に記載の着色樹脂粒子を含むことを特徴とする塗料。
- 請求項12に記載の塗料を基材上に塗工してなることを特徴とする塗工物品。
- 請求項12に記載の塗料を透明基材フィルム上に塗工してなることを特徴とする光学フィルム。
- 請求項12に記載の塗料を透明基材フィルム上に塗工してなることを特徴とする防眩フィルム。
- 請求項1~4のいずれか1項に記載の着色樹脂粒子を含むことを特徴とする外用剤。
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US14/008,099 US20140086862A1 (en) | 2011-03-31 | 2012-01-30 | Colored resin particles, method for producing the same, and use thereof |
JP2013507224A JP5722434B2 (ja) | 2011-03-31 | 2012-01-30 | 着色樹脂粒子、その製造方法、及びその用途 |
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WO2019176521A1 (ja) * | 2018-03-16 | 2019-09-19 | 積水化成品工業株式会社 | 着色有機樹脂粒子及びその製造方法 |
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EP2692779B1 (en) | 2017-01-25 |
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TW201241055A (en) | 2012-10-16 |
JPWO2012132533A1 (ja) | 2014-07-24 |
EP2692779A1 (en) | 2014-02-05 |
US20140086862A1 (en) | 2014-03-27 |
EP2692779A4 (en) | 2014-10-15 |
CN103459471B (zh) | 2016-04-27 |
JP5722434B2 (ja) | 2015-05-20 |
WO2012132533A9 (ja) | 2013-01-24 |
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KR20130105737A (ko) | 2013-09-25 |
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