WO2013027849A9 - 異形樹脂粒子およびその製造方法並びにその用途 - Google Patents
異形樹脂粒子およびその製造方法並びにその用途 Download PDFInfo
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- WO2013027849A9 WO2013027849A9 PCT/JP2012/071558 JP2012071558W WO2013027849A9 WO 2013027849 A9 WO2013027849 A9 WO 2013027849A9 JP 2012071558 W JP2012071558 W JP 2012071558W WO 2013027849 A9 WO2013027849 A9 WO 2013027849A9
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- 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
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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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
- A61K8/72—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
- A61K8/8141—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
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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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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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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- 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
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
- G02B5/0236—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
- G02B5/0242—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of dispersed particles
Definitions
- the present invention relates to irregularly shaped resin particles, a production method thereof and uses thereof (emulsifier, external preparation, emulsion, coating agent, light diffusion member, and optical member). More specifically, the present invention relates to odd-shaped resin particles containing two different resin components, one of which is unevenly distributed in the vicinity of the surface of the odd-shaped resin particles, a method for producing the same, and use thereof.
- Patent Document 1 a polymer compound obtained by polymerizing a methacrylic ester, a methacrylic ester and a radical polymerization initiator are mixed to obtain a mixture, and the mixture is dissolved in an aqueous solution in which a dispersion stabilizer is dissolved.
- the suspension polymerization method using a phase separation mechanism there are a lot of concave and convex acrylic resin particles (Examples 8 and 9) shaped like a golf ball and depressions of 1 micrometer or less. To obtain concavo-convex and partially porous acrylic resin particles (Example 10).
- Patent Document 2 discloses that a styrenic elastomer is dissolved in a mixture of a hydrophobic polymerizable vinyl monomer and a crosslinkable monomer, and has a regular wrinkled structure on the surface by suspension polymerization in an aqueous medium. Obtaining spherical polymer particles is described.
- the shape of the irregularly shaped resin particles described in Patent Documents 1 and 2 is limited to an irregular shape such as a golf ball, a porous surface portion, or a spherical shape having a regular wrinkled structure on the surface.
- the outer shape seen from any direction is substantially spherical, and is not an irregular shape (non-spherical) having shape anisotropy.
- Patent Documents 1 and 2 do not indicate at which position in the deformed resin particles a plurality of resin components constituting the deformed resin particles are present, but the shape of the deformed resin particles is isotropic. Therefore, it is presumed that the positions of the plurality of resin components constituting the irregular shaped resin particles are isotropic.
- the deformed resin particles described in Patent Documents 1 and 2 have no anisotropy in effects such as the light diffusion effect and the reflection effect due to the deformed resin particle surface and the interface between different resin components. Therefore, it is not expected that characteristics such as light diffusion characteristics are improved due to the anisotropy of the effect due to the irregular resin particle surface and the interface between different resin components.
- the present invention has been made in view of the above-mentioned problems, and its object is to provide deformed resin particles capable of improving characteristics such as light diffusion characteristics and reflection characteristics, a production method thereof, and uses thereof (emulsifiers, external preparations, emulsions, coatings). Providing an agent, a light diffusing member, and an optical member).
- the irregular shaped resin particles of the present invention have a circular outer shape when viewed from the direction in which the projected area is maximized, and when viewed from the direction in which the projected area is minimized.
- the second resin component is unevenly distributed near the surface of the resin particles.
- the deformed resin particles having the above configuration have a circular outer shape when viewed from the direction where the projected area is maximized, and a non-circular shape when viewed from the direction where the projected area is minimized. Therefore, it has shape anisotropy. Therefore, effects such as a light diffusion effect and a reflection effect on the surface of the irregular shaped resin particle have anisotropy. As a result, the odd-shaped resin particles having the above configuration can exhibit excellent characteristics such as light diffusion characteristics and reflection characteristics.
- the second resin component different from the first resin component is unevenly distributed near the surface of the deformed resin particles, two different resin components (the first resin component and the second resin component are different from each other). Resin component) is locally present in one deformed resin particle.
- Resin component is locally present in one deformed resin particle.
- effects such as a light diffusion (scattering) effect and a reflection effect due to the interface between these portions can be obtained. Therefore, the deformed resin particles having the above-described configuration are superior in characteristics such as light diffusion characteristics and reflection characteristics as compared with conventional resin particles made of a single resin component.
- the second resin component is unevenly distributed in the vicinity of the surface of the deformed resin particle and the presence position of the second resin component is anisotropic in the deformed resin particle having the above configuration, the light diffusion at the interface Effects such as effects and reflection effects have anisotropy.
- the irregular shaped resin particles having the above-described configuration can exhibit further excellent characteristics such as light diffusion characteristics and reflection characteristics.
- the second resin component is unevenly distributed in the vicinity of the surface of the deformed resin particles
- a cross section passing through the center of gravity of the deformed resin particles for example, perpendicular to the direction in which the projected area is maximized. Means that when the odd-shaped resin particles are cut into two pieces in the cross section), the amount of the second resin component in one piece is larger than the amount of the second resin component in the other piece.
- the non-spherical shape is a shape in which a part of a sphere is chipped, and at least a part of the surface of the chipped part in the deformed resin particle is formed of a second resin component.
- the remaining surface of the irregularly shaped resin particles is formed of the first resin component.
- Resin particles with multiple surfaces with different properties can be used to make diagnostic particle, medical substrate, biocompatible material, dental material, cosmetic substrate, antifouling paint, It is considered possible to apply to cloudy materials, antistatic agents, conductive adhesives, conductive sealing materials, magnetic particles, recording media, and chromatographic fillers.
- the second resin component forms at least a part of the surface of the chipped portion of the deformed resin particle, the chipped portion of the deformed resin particle is notched (recessed portion). ), A specific component having high affinity with the second resin component can be selectively adsorbed and held in the notch.
- the non-spherical shape is preferably a hemispherical shape, a biconvex lens shape, a mushroom shape, or a cross-section horseshoe shape.
- the shape since the shape has a high degree of irregularity, characteristics such as light diffusion characteristics and reflection characteristics can be further improved.
- the deformed resin particles having a cross-section horseshoe shape can realize a configuration in which the second resin component portion is localized in the notch.
- a specific component having a high affinity with the second resin component can be selectively adsorbed and held in the notch.
- the first resin component is a hydrophilic resin and the second resin component is a hydrophobic resin.
- the odd-shaped resin particles having the above structure a part of the hydrophilic resin and the hydrophobic resin is locally present in one odd-shaped resin particle, so that a part of the surface is formed of the hydrophilic resin and the remaining surface is hydrophobic.
- the structure may be formed of a resin component. Accordingly, the irregular shaped resin particles having the above-described configuration can have a hydrophilic surface and a hydrophobic surface, and thus are suitable for application to various uses described above.
- one surface is formed entirely or mainly with a hydrophobic resin.
- the other surface is formed entirely or mainly with a hydrophilic resin.
- one surface can be made hydrophobic and the other surface can be made hydrophilic.
- a part of the surface is formed of a hydrophobic resin and the remaining surface is formed of a hydrophilic resin, so that a part of the surface is hydrophobic and the remaining surface is hydrophilic. It can become the composition which is. Therefore, if the deformed resin particles having the above-described configuration are supplied to the interface between liquids having different hydrophilicities (different hydrophobicity) such as an interface between water and oil, one side of the deformed resin particles is more hydrophilic. Oriented to the higher liquid side, the opposite side of the irregular shaped resin particles is oriented to the more hydrophobic liquid side to form an alignment film. Since this alignment film weakens the interfacial tension, the deformed resin particles having the above-described structure also function as a surfactant.
- the method for producing irregularly shaped resin particles according to the present invention absorbs a polymerizable vinyl monomer in an aqueous emulsion into particles made of a resin, and absorbs the polymerizable vinyl monomer.
- the resin contains a portion derived from a (meth) acrylic acid ester containing a halogenated alkyl group having 2 to 10 carbon atoms or an alicyclic hydrocarbon group in the ester portion, and a weight average in the range of 150,000 to 1,000,000
- the resin since the resin contains a portion derived from a (meth) acrylic acid ester having a C 2-10 halogenated alkyl group or an alicyclic hydrocarbon group in the ester portion, it has strong hydrophobicity.
- the polymerizable vinyl monomer In the process in which the polymerizable vinyl monomer is polymerized, it phase-separates from the polymer of the polymerizable vinyl monomer and tends to be unevenly distributed near the surface of the irregular shaped resin particles.
- the resin since the resin has a weight average molecular weight of 150,000 or more, the resin is phase-separated from the polymer of the polymerizable vinyl monomer during the polymerization of the polymerizable vinyl monomer. It tends to be unevenly distributed near the surface of the particles. Further, according to the above method, since the resin has a weight average molecular weight of 1 million or less, the resin sufficiently absorbs the polymerizable vinyl monomer or is sufficiently dissolved in the polymerizable vinyl monomer.
- the polymerizable vinyl monomer contains 5 to 50% by weight of the crosslinkable monomer based on the total amount of the polymerizable vinyl monomer. In the process of polymerization of the monomer, it phase-separates from the polymer of the polymerizable vinyl monomer and tends to be unevenly distributed near the surface of the irregular shaped resin particles.
- the polymerizable vinyl-based monomer is phase-separated from the resin in the process of polymerization of the polymerizable vinyl-based monomer, and tends to be unevenly distributed near the surface of the deformed resin particles, and The polymerizable vinyl monomer is sufficiently absorbed by the particles made of the resin, or the resin is sufficiently dissolved. Due to these synergistic effects, the outer shape of the deformed resin particles when viewed from the direction where the projected area is maximized is circular, and the outer shape of the deformed resin particles when viewed from the direction where the projected area is minimized is noncircular.
- a non-spherical deformed resin particle comprising a first resin component and a second resin component different from the first resin component, and the second resin in the vicinity of the surface of the deformed resin particle
- the deformed resin particles of the present invention in which the components are unevenly distributed can be produced.
- (meth) acryl means acryl or methacryl
- (meth) acrylate means acrylate or methacrylate.
- a part derived from a (meth) acrylic acid ester containing a halogenated alkyl group having 2 to 10 carbon atoms or an alicyclic hydrocarbon group in an ester portion means “having 2 to 10 carbon atoms”. It means one or more repeating structural units obtained by polymerizing a (meth) acrylic acid ester containing a halogenated alkyl group or an alicyclic hydrocarbon group in the ester part.
- the emulsifier of the present invention is characterized by containing the irregular shaped resin particles of the present invention.
- one of the first resin component and the second resin component constituting the deformed resin particle is a hydrophobic resin and the other is a hydrophilic resin
- the deformed resin particle can function as an emulsifier. .
- the external preparation of the present invention is characterized by containing the irregular shaped resin particles of the present invention.
- the deformed resin particles function as an emulsifier. Therefore, when the external preparation of the present invention is an emulsion containing an aqueous phase component and an oil phase component, an external preparation in an emulsion state having excellent emulsification stability can be realized without using a surfactant.
- the emulsion of the present invention is characterized by containing the irregular shaped resin particles of the present invention.
- the deformed resin particle when one of the first resin component and the second resin component constituting the deformed resin particle is a hydrophobic resin and the other is a hydrophilic resin, the deformed resin particle is an emulsifier. Therefore, it is excellent in emulsion stability without using a surfactant.
- the coating agent of the present invention is characterized by containing the irregular shaped resin particles of the present invention.
- the coating agent of the present invention contains the irregular shaped resin particles of the present invention having excellent light diffusion characteristics, the coating agent has excellent light diffusion characteristics and can impart excellent matting properties to the coating film when used as a top coat.
- the light diffusing member of the present invention is characterized by including the irregular shaped resin particles of the present invention.
- the light diffusing member includes the deformed resin particles of the present invention having excellent light diffusing properties, the light diffusing members are excellent in light diffusing properties.
- the optical member of the present invention is an optical member including a base material and a plurality of the deformed resin particles of the present invention, wherein the plurality of deformed resin particles are hemispherical, and the plurality of deformed resin particles Is characterized in that the flat portions are arranged on the base material so as to face the base material.
- the plurality of odd-shaped resin particles are arranged on the base material such that their flat portions are opposed to the base material, so that the diffused light diffused on the surface of the odd-shaped resin particles
- the optical member of the said structure contains the irregular-shaped resin particle of this invention excellent in the light-diffusion characteristic, it is excellent in light diffusibility.
- odd-shaped resin particles capable of improving characteristics such as light diffusibility and reflection characteristics, a method for producing the same, and applications thereof (emulsifiers, external preparations, emulsions, coating agents, light diffusing members, and optics) Member) can be provided.
- FIG. 1 It is a diagram showing a cross-section horseshoe-shaped deformed resin particles according to an example of the present invention, (a) is a projection when the deformed resin particles are viewed from the direction where the projected area is maximum, (b), It is a projection view when the irregular resin particles are seen from the direction in which the projection area is minimized, and (c) is a sectional view when the irregular resin particles are cut in a section perpendicular to the direction in which the projection area is minimal. . It is a figure which shows the mushroom-shaped deformed resin particle which concerns on an example of this invention, (a) is a projection figure when looking at the deformed resin particle from the direction where a projection area becomes the maximum, (b) is a projection FIG.
- FIG. 4C is a projection when the deformed resin particles are viewed from a direction in which the area is minimized
- FIG. 5C is a cross-sectional view in which the deformed resin particles are cut in a section perpendicular to the direction in which the projection area is minimized.
- FIG. 4C is a projection when the deformed resin particles are viewed from a direction in which the area is minimized, and FIG.
- 5C is a cross-sectional view in which the deformed resin particles are cut in a section perpendicular to the direction in which the projection area is minimized.
- It is a diagram showing a deformed resin particle in the shape of a double-sided convex lens according to an example of the present invention, (a) is a projection when the deformed resin particles are viewed from the direction where the projected area is maximum, (b), It is a projection view when the irregular resin particles are viewed from the direction in which the projection area is minimized, and (c) is a sectional view when the irregular resin particles are cut in a section perpendicular to the direction in which the projection area is maximized. .
- the deformed resin particles of the present invention have a circular outer shape when viewed from the direction where the projected area is maximized, and a non-circular shape when viewed from the direction where the projected area is minimized.
- the non-spherical shape is a shape in which a part of a sphere is chipped, and at least a part of the surface of the chipped part in the deformed resin particle (more preferably, a part more than half of the surface of the chipped part). It is preferable that the remaining surface of the irregularly shaped resin particles is formed of the first resin component.
- Examples of the non-spherical shape lacking a part of the sphere include a hemispherical shape, a biconvex lens shape (meteorite shape), a mushroom shape, and a cross-section horseshoe shape (cross-sectional concave shape).
- the second resin component is preferably unevenly distributed integrally in the vicinity of the deformed surface (non-spherical surface) among the surfaces of the deformed resin particles.
- the deformed resin particles having a cross-section horseshoe shape according to an example of the present invention have a circular outer shape when viewed from the direction in which the projected area is maximized,
- the outer shape of the deformed resin particles when viewed from the direction in which the projected area is minimized is a horseshoe shape (a shape made up of a concave portion corresponding to a projection view of a cutout portion 3 described later and a fan shape).
- the odd-shaped resin particle includes a first resin component 1 and a second resin component 2 that are different from each other, and the second resin component 2 is unevenly distributed in the vicinity of the surface of the odd-shaped resin particle. is doing.
- the deformed resin particles have a shape in which a part of a sphere is missing, and have one cutout portion 3 communicating in the diameter direction.
- the odd-shaped resin particles are formed with the second resin component 2 in which more than half of the surface of the notch 3 (the chipped portion) is formed. The remaining surface of is formed of the first resin component 1.
- the second resin component 2 is integrated and unevenly distributed in the vicinity of the surface of the notch 3 (the deformed surface).
- the deformed resin particles can selectively adsorb and hold a specific component having a high affinity with the second resin component 2 on the surface of the cutout portion 3.
- the depth of the notch 3 (the depth of the recess corresponding to the projection of the notch 3) B is in the range of 0.1 to 0.9 times the particle diameter (major axis) A of the irregular shaped resin particle. It is more preferable that the particle diameter A is in the range of 0.2 to 0.5 times, and it is more preferable that the particle diameter A is in the range of 0.3 to 0.45 times.
- the depth B of the notch 3 is smaller than 0.1 times the particle diameter A, the shape anisotropy becomes small, so that the effect of improving the characteristics such as the light diffusion characteristics and the reflection characteristics due to the shape anisotropy is very small. It can no longer be obtained.
- the depth B of the notch 3 is larger than 0.9 times the particle diameter A, the manufacture becomes difficult.
- the width C of the opening of the notch 3 is preferably in the range of 0.1 to 0.95 times the particle diameter A, and is in the range of 0.4 to 0.7 times the particle diameter A. More preferably, it is more preferably in the range of 0.45 to 0.55 times the particle diameter A.
- the width C of the opening of the notch 3 is smaller than 0.1 times the particle diameter A, the shape of the irregularly shaped resin particles is close to a true spherical shape and the shape anisotropy is reduced. Only a small effect of improving characteristics such as light diffusion characteristics and reflection characteristics can be obtained.
- the width C of the opening of the notch 3 is larger than 0.95 times the particle diameter A, the shape of the deformed resin particles becomes close to a hemispherical shape. Only a small effect of selectively adsorbing and holding can be obtained.
- the depth B of the notch 3 is in the range of 0.1 to 0.9 times the particle diameter A, and the width C of the opening is 0.1 to 0.95 times the particle diameter A.
- the deformed resin particles having a horseshoe cross section within the range can be easily obtained by the production method of the present invention described later.
- the mushroom-shaped deformed resin particles according to an example of the present invention have a circular outer shape when viewed from the direction in which the projected area is maximized.
- the outer shape of the deformed resin particles when viewed from the direction where the area is minimized is non-circular.
- the odd-shaped resin particle includes a first resin component 4 and a second resin component 5 which are different from each other, and the second resin component 5 is unevenly distributed in the vicinity of the surface of the odd-shaped resin particle. is doing.
- the odd-shaped resin particles have a shape in which a part of a sphere is missing, and a hemispherical umbrella part 6 and a shaft part 7 in which a part of the hemisphere is missing. It consists of.
- the odd-shaped resin particle has a portion more than half of the surface of the shaft portion 7 (the chipped portion) formed of the second resin component 5. The remaining surface is formed of the first resin component 4.
- the second resin component 5 is integrated and unevenly distributed near the surface of the shaft portion 7 (the deformed surface).
- the width D1 of the tip (bottom) of the shaft portion 7 is preferably in the range of 0.1 to 0.8 times the particle diameter A (major axis) of the irregular shaped resin particles, and 0.15 to 0 of the particle diameter A. More preferably, it is in the range of .6 times, and more preferably in the range of 0.25 to 0.45 times the particle diameter A. If the width D1 of the tip of the shaft portion 7 is smaller than 0.1 times the particle diameter A, the shape of the irregular shaped resin particles becomes close to a hemispherical shape, so that only a few effects specific to the mushroom shape can be obtained.
- the width D1 at the tip of the shaft portion 7 is larger than 0.8 times the particle diameter A, the shape of the deformed resin particles becomes close to a true spherical shape and the shape anisotropy is reduced. Only a small effect of improving characteristics such as light diffusion characteristics and reflection characteristics can be obtained.
- the width D2 of the middle part of the shaft part 7 (the middle between the tip and the root of the shaft part 7) is preferably in the range of 0.2 to 0.9 times the particle diameter A of the irregular shaped resin particles. More preferably, it is in the range of 0.3 to 0.7 times A, and more preferably in the range of 0.45 to 0.6 times the particle diameter A.
- the width D2 of the intermediate part of the shaft part 7 is smaller than 0.2 times the particle diameter A, the shape of the deformed resin particles is close to a hemispherical shape, so that only a few effects specific to the mushroom shape can be obtained.
- the width D2 of the intermediate part of the shaft part 7 is larger than 0.9 times the particle diameter A, the shape of the deformed resin particles becomes close to a true spherical shape and the shape anisotropy becomes small. Only a slight effect of improving the characteristics such as the light diffusion characteristic and the reflection characteristic can be obtained.
- the axial length E of the shaft portion 7 is preferably in the range of 0.2 to 1.5 times the particle diameter A of the irregular shaped resin particles, and is 0.2 to 0.7 times the particle diameter A. Is more preferable, and it is more preferable that the particle diameter is in the range of 0.2 to 0.6 times the particle diameter A.
- the height E in the axial length direction of the shaft portion 7 is smaller than 0.2 times the particle diameter A, the shape of the deformed resin particles is close to a hemispherical shape, so that only a small effect specific to the mushroom shape can be obtained.
- the height E in the axial length direction of the shaft portion 7 is larger than 1.5 times the particle diameter A, the manufacture becomes difficult.
- the width D1 of the tip of the shaft portion 7 is in the range of 0.1 to 0.8 times the particle diameter A
- the width D2 of the intermediate portion of the shaft portion 7 is 0.2 to 0.9 of the particle diameter A.
- the mushroom-shaped deformed resin particles that are in the double range and the height E in the axial length direction of the shaft portion 7 is in the range of 0.2 to 1.5 times the particle diameter A are described later in the present invention. It can be easily obtained by this manufacturing method.
- the hemispherical deformed resin particles As shown in FIGS. 3A and 3B, the hemispherical deformed resin particles according to an example of the present invention have a circular outer shape when viewed from the direction in which the projected area is maximized. The outer shape of the deformed resin particles when viewed from the direction where the area is minimized is a semicircular shape. As shown in FIG. 3C, the odd-shaped resin particle includes a first resin component 11 and a second resin component 12 that are different from each other, and the second resin component 12 is unevenly distributed in the vicinity of the surface of the odd-shaped resin particle. is doing.
- the odd-shaped resin particles have a shape in which half of the sphere is missing, and have a flat portion 13 in a portion in which the half of the sphere is missing.
- FIG. 3 (c) almost all of the surface of the flat surface portion 13 (the chipped portion) is formed of the second resin component 12, and the remaining surface of the deformed resin particles is formed in the deformed resin particles. Is formed of the first resin component 11.
- the second resin component 12 is integrated and unevenly distributed in the vicinity of the surface (the deformed surface) of the flat portion 13.
- the short diameter (height in the direction in which the projected area is maximum in FIG. 3B) F of the irregular shaped resin particles is in the range of 0.2 to 0.8 times the particle diameter A (long diameter) of the irregular shaped resin particles. It is preferable that the average particle size is 0.4 to 0.7 times the particle size A, and more preferably 0.5 to 0.6 times the particle size A. If the minor diameter F is smaller than 0.2 times the particle diameter A, the production becomes difficult. On the other hand, when the minor axis F is larger than 0.8 times the particle diameter A, the shape of the deformed resin particles is close to a true spherical shape and the shape anisotropy is reduced. Only a slight effect of improving characteristics such as characteristics can be obtained.
- hemispherical irregular shaped resin particles whose minor axis F is in the range of 0.2 to 0.8 times the particle diameter A can be easily obtained by the production method of the present invention described later.
- the biconvex lens-shaped deformed resin particles As shown in FIGS. 4 (a) and 4 (b), the biconvex lens-shaped deformed resin particles according to an example of the present invention have a circular outer shape when viewed from the direction in which the projected area is maximized, The outer shape of the deformed resin particles when viewed from the direction in which the projected area is minimized is non-circular. As shown in FIG. 4C, the odd-shaped resin particle includes a first resin component 14 and a second resin component 15 which are different from each other, and the second resin component 15 is unevenly distributed in the vicinity of the surface of the odd-shaped resin particle. is doing.
- the odd-shaped resin particle has a shape in which a part of a sphere is missing, and is composed of two plano-convex lens-shaped portions 16 and 17, and is a flat surface of the plano-convex lens-shaped portion 16. And the plane part of the plano-convex lens-shaped part 17 are joined.
- Each of the plano-convex lens-shaped portions 16 and 17 has the shape of the smaller one of the two pieces obtained by cutting the sphere in a cross section that does not pass through its center.
- the height H of the plano-convex lens-shaped part 16 in the direction in which the projection area is maximized may be equal to the height I of the plano-convex lens-shaped part 17 in the direction in which the projection area is maximized. It is larger than the height I of the plano-convex lens-shaped portion 17 in the direction.
- almost all of the surface 17 a of the plano-convex lens-shaped portion 17 (usually the smaller plano-convex lens-shaped portion) is formed of the second resin component 15.
- the remaining surface of the irregular shaped resin particles is formed of the first resin component 14.
- the second resin component 15 is integrated and unevenly distributed in the vicinity of the surface of the plano-convex lens-shaped portion 17 (the deformed surface).
- the height H of the plano-convex lens-shaped portion 16 in the direction in which the projected area is maximized is preferably in the range of 0.2 to 0.8 times the particle diameter (major axis) A of the irregularly shaped resin particles. Is more preferably in the range of 0.2 to 0.7 times, more preferably in the range of 0.35 to 0.55 times the particle diameter A.
- the height H of the plano-convex lens-shaped part 16 is smaller than 0.2 times the particle diameter A, or when the height H of the plano-convex lens-shaped part 16 is larger than 0.8 times the particle diameter A, the manufacture becomes difficult. .
- the height I of the plano-convex lens-shaped portion 17 in the direction in which the projected area is maximized is preferably in the range of 0.1 to 0.8 times the particle diameter A, and 0.1 to 0.8. More preferably, it is in the range of 5 times, more preferably in the range of 0.1 to 0.3 times the particle diameter A.
- the height I of the plano-convex lens-shaped portion 17 is smaller than 0.1 times the particle diameter A, the shape of the deformed resin particles is close to a hemispherical shape, so that only a few effects specific to the biconvex lens shape can be obtained.
- the height I of the plano-convex lens-shaped portion 17 is larger than 0.8 times the particle diameter A, the manufacture becomes difficult.
- the height I of the plano-convex lens-shaped portion 17 is larger than 0.3 times the particle diameter A, the shape of the irregularly shaped resin particles is close to a true spherical shape. Only a slight effect of improving the characteristics can be obtained.
- the height H of the plano-convex lens-shaped portion 16 is in the range of 0.2 to 0.8 times the particle diameter A, and the height H of the plano-convex lens-shaped portion 16 is 0.1 to 0.1 of the particle diameter A.
- the biconvex lens-shaped deformed resin particles in the range of 0.8 times can be easily obtained by the production method of the present invention described later.
- the particle diameter A is preferably in the range of 0.5 to 50 ⁇ m.
- 1 to 4 are diagrams showing ideal shapes for explaining the shape of the deformed resin particles, and the deformed resin particles that actually have some bulges and dents are also within the scope of the present invention. Is within.
- the deformed resin particles of the present invention preferably have a sphere equivalent volume average particle diameter in the range of 0.5 to 50 ⁇ m. Thereby, it becomes a particle suitable for various uses.
- the irregular shaped resin particle of the present invention is used as a component (light diffusing agent) of an antiglare film, it is more preferable that the sphere equivalent volume average particle diameter is in the range of 1.5 to 8 ⁇ m. Thereby, the anti-glare film which has favorable anti-glare property is realizable.
- the irregular shaped resin particle of the present invention when used as a component (light diffusing agent) of a light diffusing member, it is more preferable that the sphere converted volume average particle diameter is in the range of 1 to 50 ⁇ m, and the sphere converted volume average particle More preferably, the diameter is in the range of 1 to 10 ⁇ m. Thereby, the light-diffusion member which has favorable light diffusibility is realizable.
- the spherical equivalent volume average particle diameter is preferably in the range of 1 to 50 ⁇ m. Thereby, a favorable external preparation can be realized.
- the irregular shaped resin particle of the present invention when used as a paper coating agent, it is preferable that the sphere equivalent volume average particle diameter is in the range of 0.5 to 10 ⁇ m. Thereby, a good paper coating agent can be realized. Further, when the volume-average particle diameter in terms of the sphere is within the range of 1 to 10 ⁇ m, the deformed resin particles having the above structure can easily control the shape of the deformed resin particles to a desired deformed shape. Manufacturing is easy.
- the first resin component is preferably a hydrophilic resin.
- the hydrophilic resin is preferably a resin having at least one hydrophilic substituent selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfo group, and an amino group.
- the resin having a hydrophilic substituent is, for example, homopolymerized or copolymerized with a polymerizable vinyl monomer having at least one hydrophilic substituent selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfo group, and an amino group. Obtained by polymerization.
- the polymerizable vinyl monomer is a compound having at least one polymerizable alkenyl group (broadly-defined vinyl group) in one molecule.
- examples of the polymerizable vinyl monomer having a hydrophilic substituent include (meth) acrylic acid, (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, and an alkylene oxide group containing a hydroxyl group (meth).
- examples include (meth) acrylic acid derivatives such as acrylic acid esters.
- hydrophilic resin a resin obtained by homopolymerizing or copolymerizing a polymerizable vinyl monomer having a solubility in water at 20 ° C. of 1% by weight or more is also preferable.
- the compounds exemplified as the polymerizable vinyl monomer having a hydrophilic substituent ((meth) acrylic acid, (meth) acrylamide) , (Meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid ester having a hydroxyl group-containing alkylene oxide group), (meth) acrylic acid ester having a hydroxyl group-free alkylene oxide group, (meth) acrylic (Meth) acrylic acid derivatives such as methyl acid, ethyl (meth) acrylate, glycidyl (meth) acrylate, acrylonitrile; vinyl acetate and the like.
- the (meth) acrylic acid ester having an alkylene oxide group containing a hydroxyl group and the (meth) acrylic acid ester having an alkylene oxide group not containing a hydroxyl group are variants unique to the present invention. It is more preferable because odd-shaped resin particles having a shape and an uneven distribution structure are easily obtained.
- R 1 represents H or CH 3
- R 2 and R 3 are different alkylene groups having 2 to 5 carbon atoms (C 2 H 4 , C 3 H 6 , C 4 H 8 , or C 5 H 10 )
- m is a number from 0 to 50
- n is a number from 0 to 50 (provided that m and n cannot be 0 at the same time
- R 4 represents H or CH 3
- m and n are preferably in the range of 0 to 30, and more preferably in the range of 0 to 15.
- poly (ethylene glycol-propylene glycol) monomethacrylate, polypropylene glycol monomethacrylate, methoxypolyethylene glycol monomethacrylate and the like are suitable.
- the second resin component is preferably a hydrophobic resin.
- the hydrophobic resin is preferably a resin having a halogenated alkyl group such as an alkyl fluoride, alkyl chloride, alkyl bromide or alkyl iodide group, or a resin having an alicyclic hydrocarbon group such as a cyclohexyl group.
- the resin having a halogenated alkyl group can be obtained by homopolymerizing or copolymerizing a polymerizable vinyl monomer having a halogenated alkyl group.
- Examples of such polymerizable vinyl monomers having a halogenated alkyl group include trifluoromethyl methacrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, acrylic Acid 2,2,3,3-tetrafluoropropyl, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, acrylic acid 1H, 1H , 5H-octafluoropentyl, 1H, 1H, 5H-octafluoropentyl methacrylate, perfluorooctylethyl methacrylate, perfluorooctylethyl acrylate, etc.
- the resin having an alicyclic hydrocarbon group can be obtained by homopolymerizing or copolymerizing a polymerizable vinyl monomer having an alicyclic hydrocarbon group.
- a polymerizable vinyl monomer having an alicyclic hydrocarbon group an alicyclic hydrocarbon group such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, etc. is included in the ester part (meth).
- An acrylic ester is mentioned.
- These polymerizable vinyl monomers may be used alone or in combination of two or more.
- the polymerizable vinyl monomer having a halogenated alkyl group is preferably a polymerizable vinyl monomer having a fluorinated alkyl group. This makes it easy to obtain deformed resin particles having a low refractive index and high transparency.
- the polymerizable vinyl monomer having a halogenated alkyl group is preferably a (meth) acrylic acid ester having a halogenated alkyl group having 2 to 10 carbon atoms in the ester portion, and a fluorinated fluoride having 2 to 10 carbon atoms.
- a (meth) acrylic acid ester containing an alkyl group in the ester portion is more preferable.
- the number of halogen atoms contained in the halogenated alkyl group is preferably 40% or more, more preferably 50% or more, based on the total number of hydrogen atoms in the corresponding alkyl group.
- the polymer of the monomer mixture is easily phase-separated from the resin particles in the process of polymerizing the monomer mixture, and the irregular shape and the uneven distribution structure peculiar to the present invention are easily obtained.
- the corresponding alkyl group has 5 total hydrogen atoms and 3 halogen atoms, so the corresponding alkyl group has a proportion of 60%. Of hydrogen is replaced by a halogen atom.
- the method for producing irregularly shaped resin particles comprises absorbing a polymerizable vinyl monomer in an aqueous emulsion into particles made of resin (hereinafter referred to as “resin particles”) and absorbing the polymerizable vinyl monomer.
- resin particles particles made of resin
- the resin contains a portion derived from a (meth) acrylic acid ester having a halogenated alkyl group having 2 to 10 carbon atoms or an alicyclic hydrocarbon group in the ester portion, and in the range of 150,000 to 1,000,000
- Rack It includes sexual monomer.
- the resin particles are allowed to absorb the polymerizable vinyl monomer in the aqueous emulsion, and the absorbed polymerizable vinyl monomer is polymerized.
- a method for obtaining irregular shaped resin particles that is, a method for producing irregular shaped resin particles using seed polymerization will be described.
- a method for producing irregularly shaped resin particles using seed polymerization is a polymerizable vinyl monomer containing a (meth) acrylic acid ester containing a halogenated alkyl group having 2 to 10 carbon atoms or an alicyclic hydrocarbon group in the ester part. (Hereinafter referred to as “hydrophobic monomer”) is polymerized to produce resin particles having a weight average molecular weight (measured by gel permeation chromatography) in the range of 150,000 to 1,000,000.
- Polymerizable vinyl in aqueous emulsion containing resin particle production process and resin particles obtained in resin particle process containing 5 to 50% by weight of crosslinkable monomer based on the total amount of polymerizable vinyl monomer A seed polymerization step of absorbing a system monomer (hereinafter referred to as “monomer mixture”) and polymerizing the absorbed monomer mixture.
- monomer mixture system monomer
- resin particles are obtained by polymerizing a hydrophobic monomer containing a (meth) acrylic acid ester having a C 2-10 halogenated alkyl group or alicyclic hydrocarbon group in the ester portion.
- Examples of the (meth) acrylic acid ester containing a halogenated alkyl group having 2 to 10 carbon atoms or an alicyclic hydrocarbon group in the ester portion include various types having 2 to 10 carbon atoms exemplified in the section of [Hydrophobic resin] Examples include (meth) acrylic acid esters containing a halogenated alkyl group in the ester part, and (meth) acrylic acid esters containing various alicyclic hydrocarbon groups in the ester part.
- the amount of the (meth) acrylic acid ester containing an alkyl halide group having 2 to 10 carbon atoms or an alicyclic hydrocarbon group in the ester portion is 50% by weight or more based on the total amount of the hydrophobic monomer. It is preferably 80% by weight or more.
- the hydrophobic monomer includes a polymerizable vinyl monomer other than a (meth) acrylic acid ester having a halogenated alkyl group having 2 to 10 carbon atoms or an alicyclic hydrocarbon group in an ester portion. May be.
- Other polymerizable vinyl monomers include monofunctional (meth) acrylic acids other than (meth) acrylic acid esters containing a halogenated alkyl group having 2 to 10 carbon atoms or an alicyclic hydrocarbon group in the ester moiety. Esters ((meth) acrylic acid esters having only one polymerizable alkenyl group per molecule) are preferred.
- Examples of the monofunctional (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate.
- examples thereof include n-octyl, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, and the like. These compounds may be used alone or in combination of two or more.
- the hydrophobic monomer preferably does not contain a crosslinkable monomer (a compound having two or more polymerizable alkenyl groups in one molecule).
- a crosslinkable monomer a compound having two or more polymerizable alkenyl groups in one molecule.
- the polymerization of the hydrophobic monomer may be performed in the presence of a molecular weight modifier.
- the molecular weight modifier include mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan and tert-dodecyl mercaptan; ⁇ -methylstyrene dimers; terpenes such as ⁇ -terpinene and dipentene; halogens such as chloroform and carbon tetrachloride. Chain transfer agents such as fluorinated hydrocarbons can be used.
- mercaptans are preferable.
- the amount of the molecular weight modifier used may be adjusted so that the weight average molecular weight of the obtained resin particles is in the range of 150,000 to 1,000,000, but it is 0 with respect to 100 parts by weight of the hydrophobic monomer. It is preferably in the range of 1 to 10 parts by weight, more preferably in the range of 0.1 to 0.9 parts by weight, and in the range of 0.1 to 0.5 parts by weight. Further preferred. Thereby, it becomes easier to obtain the irregular shape and uneven distribution characteristic of the present invention.
- the weight average molecular weight of the resin particles may be a value measured by GPC (gel permeation chromatography) within a range of 150,000 to 1,000,000, but is preferably within a range of 200,000 to 800,000.
- GPC gel permeation chromatography
- the weight average molecular weight of the resin particles is less than 150,000, phase separation between the polymer of the monomer mixture and the resin particles hardly occurs in the process of polymerization of the monomer mixture. An uneven distribution structure is difficult to obtain.
- the weight average molecular weight of the resin particles is larger than 1,000,000, it is difficult to obtain the irregular shape and uneven distribution structure peculiar to the present invention, and spherical resin particles may be mixed.
- the weight average molecular weight is greater than 1,000,000
- the monomer absorption capacity of the resin particles decreases.
- the monomer mixture is independently polymerized without being absorbed, spherical resin particles different from the deformed resin particles of the present invention may be generated.
- emulsion polymerization including soap-free emulsion polymerization
- suspension polymerization and the like
- emulsion polymerization is preferred.
- the method using emulsion polymerization is described below, it is not limited to this method.
- the hydrophobic monomer is dispersed in an aqueous medium to prepare an aqueous emulsion.
- the aqueous medium examples include water and a mixed medium of water and a water-soluble solvent (for example, a lower alcohol (alcohol having 5 or less carbon atoms)).
- a surfactant described later in the section of [Seed polymerization step] may or may not be added.
- the hydrophobic monomer is added to an aqueous medium, and the hydrophobic monomer is dispersed in the aqueous medium by a main emulsifier, a homogenizer, a sonicator, a nanomizer, or the like to prepare an aqueous emulsion.
- the aqueous emulsion is heated to the polymerization temperature. After purging (replacement) the reaction system with an inert gas such as nitrogen, resin particles are obtained by performing polymerization while sequentially adding a polymerization initiator dissolved in water to the dispersion.
- polymerization initiator examples include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; benzoyl peroxide, lauroyl peroxide, benzoyl peroxide, orthomethoxybenzoyl peroxide, 3,5,5- Organic peroxides such as trimethylhexanoyl peroxide, tert-butylperoxy-2-ethylhexanoate, and di-tert-butyl peroxide; 2,2′-azobisisobutyronitrile, 1,1′- And azo compounds such as azobiscyclohexanecarbonitrile and 2,2′-azobis (2,4-dimethylvaleronitrile).
- the polymerization initiator is preferably used within a range of 0.1 to 3 parts by weight with respect to 100 parts by weight of the hydrophobic monomer.
- resin particles are obtained by polymerizing the hydrophobic monomer in the aqueous emulsion.
- the polymerization temperature can be appropriately selected according to the type of the hydrophobic monomer and the type of 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. If necessary, after completion of the polymerization, the resin particles may be separated from the aqueous medium by filtration or the like, the aqueous medium may be removed from the resin particles by centrifugation or the like, washed with water and a solvent, and then dried.
- hydrophobic resin particles containing a portion derived from a (meth) acrylic acid ester containing a halogenated alkyl group having 2 to 10 carbon atoms or an alicyclic hydrocarbon group in the ester portion can be obtained.
- the polymerization of the hydrophobic monomer may be performed in the presence of a polymer of (meth) acrylic acid ester.
- a method for polymerizing a hydrophobic monomer in the presence of a polymer of (meth) acrylic acid ester will be described.
- the polymer of (meth) acrylic acid ester is preferably used in an amount of 100 parts by weight or less with respect to 100 parts by weight of the hydrophobic monomer, and is used in a range of 1 part by weight to 80 parts by weight. More preferably.
- the polymer of (meth) acrylic acid ester is 100 parts by weight or less with respect to 100 parts by weight of the hydrophobic monomer, the polymer of the monomer mixture and the resin particles in the process of polymerizing the monomer mixture. Phase separation is likely to occur, and it becomes easy to form a deformed shape and uneven distribution structure peculiar to the present invention, and an increase in particle diameter due to polymerization is sufficiently increased, thereby improving productivity.
- the hydrophobic monomer is absorbed by the polymer of (meth) acrylic acid ester. It is possible to avoid the generation of abnormal particles by suspension polymerization in an aqueous medium.
- the hydrophobic monomer is absorbed into the (meth) acrylic acid ester polymer particles and polymerized.
- a seed polymerization method That is, in the resin particle production process, a (meth) acrylic acid ester is polymerized to obtain a (meth) acrylic acid ester polymer particle, and the hydrophobic monomer is mixed with the (meth) acrylic acid ester weight.
- the resin particles are preferably prepared in two stages, that is, the second stage in which the coalesced particles are absorbed and polymerized. Thereby, it becomes easy to obtain the irregular shaped resin particles having the irregular shape and the uneven distribution structure peculiar to the present invention in the seed polymerization step described later.
- grain is mentioned later.
- an aqueous emulsion is prepared by dispersing the hydrophobic monomer in an aqueous medium, and (meth) acrylate polymer particles are added as seed particles to the aqueous emulsion.
- the aqueous medium the aforementioned medium can be used.
- a surfactant described later in the section of [Seed polymerization step] may be added to the aqueous medium.
- the polymerization of the hydrophobic monomer may be performed in the presence of a molecular weight modifier.
- the above-described hydrophobic monomer may be mixed with the above-described polymerization initiator as necessary.
- the preferable range of the amount of the polymerization initiator used is as described above.
- the polymerization initiator may be preliminarily mixed with the hydrophobic monomer and then dispersed in an aqueous medium, or a mixture obtained by separately dispersing both in an aqueous medium.
- the hydrophobic monomer droplet diameter in the obtained aqueous emulsion is smaller than that of the (meth) acrylic acid ester polymer particles, and the hydrophobic monomer is (meth) acrylic acid ester. This is preferable because it is efficiently absorbed by the polymer particles.
- the (meth) acrylic acid ester polymer particles may be directly added to the aqueous emulsion, and the aqueous emulsion is in the form in which the (meth) acrylic acid ester polymer particles are dispersed in an aqueous medium (for example, in the form of an aqueous emulsion). It may be added to the liquid.
- an aqueous emulsion containing acrylic ester polymer particles obtained by emulsion polymerization is used as an aqueous emulsion containing the hydrophobic monomer. It may be added to the liquid.
- Acrylic ester polymer particles may be added to the aqueous medium at the same time as the hydrophobic monomer is dispersed in the aqueous medium.
- the hydrophobic monomer may be added to the aqueous medium before being dispersed in the aqueous medium.
- the (meth) acrylate polymer particles are added to the aqueous emulsion. Absorbs hydrophobic monomers.
- This absorption can usually be carried out by stirring the aqueous emulsion after adding the (meth) acrylic acid ester polymer 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.
- (Meth) acrylate polymer particles swell due to absorption of the hydrophobic monomer.
- the end of absorption can be determined by confirming the enlargement of the particle diameter by observation with an optical microscope.
- resin particles are obtained by polymerizing the hydrophobic monomer absorbed in the (meth) acrylic acid ester polymer particles.
- the polymerization temperature can be appropriately selected according to the type of the hydrophobic monomer and the type of 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 hydrophobic monomer is completely absorbed by the (meth) acrylic acid ester polymer particles.
- the resin particles may be separated from the aqueous medium by filtration or the like, the aqueous medium may be removed from the resin particles by centrifugation or the like, washed with water and a solvent, and then dried.
- Hydrophobic resin particles containing a site derived from an ester are obtained.
- the size and shape of the resin particles are not particularly limited.
- As the resin particles spherical particles having an average particle diameter of 0.1 to 5 ⁇ m are usually used.
- (meth) acrylic acid ester is polymerized.
- (Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Isobutyl acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate,
- the ester moiety contains 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, a halogenated alky
- (meth) acrylate ester As a polymerization method of (meth) acrylate ester, known methods such as emulsion polymerization (including soap-free emulsion polymerization) and suspension polymerization can be used, but the particle diameter of (meth) acrylate polymer particles In view of uniformity and simplicity of the production method, emulsion polymerization is preferred. Although the method using emulsion polymerization is described below, it is not limited to this method.
- (meth) acrylic acid ester polymer particles by emulsion polymerization of (meth) acrylic acid ester first, (meth) acrylic acid ester is dispersed in an aqueous medium to prepare an aqueous emulsion.
- the aqueous medium include the above-described medium.
- a surfactant described later in the section of [Seed polymerization step] may be added to the aqueous medium.
- the aqueous emulsion can be prepared, for example, by the method using the fine emulsifier described above.
- the (meth) acrylic acid ester may be mixed with the above-described polymerization initiator as necessary.
- the polymerization initiator may be mixed in advance in (meth) acrylic acid ester and then dispersed in an aqueous medium, or may be mixed in which both are separately dispersed in an aqueous medium.
- the polymerization initiator is preferably used within a range of 0.1 to 3 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester.
- the polymerization of (meth) acrylic acid ester is preferably performed in the presence of the chain transfer agent described above.
- the chain transfer agent mercaptans are preferable.
- the chain transfer agent is preferably used in the range of 0.1 to 0.9 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester. More preferably, it is used in the range of 0.1 to 0.5 parts by weight.
- (meth) acrylic acid ester polymer particles are obtained by polymerizing the (meth) acrylic acid ester in the aqueous emulsion.
- the polymerization temperature can be appropriately selected according to the type of (meth) acrylic acid ester and the type of polymerization initiator.
- the polymerization temperature is preferably 25 to 110 ° C, more preferably 50 to 100 ° C.
- the (meth) acrylic acid ester polymer particles are separated from the aqueous medium by filtration or the like, and the aqueous medium is removed from the (meth) acrylic acid ester polymer particles by centrifugation or the like as necessary. Wash with water and solvent and dry.
- (meth) acrylic acid ester polymer particles are obtained.
- size and shape of a (meth) acrylic acid ester polymer particle are not specifically limited.
- the (meth) acrylic acid ester polymer particles spherical particles having a particle diameter of 0.1 to 5 ⁇ m are usually used.
- the resin mixture obtained in the resin particle manufacturing process absorbs the monomer mixture in the aqueous emulsion containing 5 to 50% by weight of the crosslinkable monomer with respect to the total amount of the monomer mixture. And allowing the absorbed monomer mixture to polymerize.
- the monomer mixture is composed of 50 to 95% by weight of a monofunctional polymerizable vinyl monomer based on the total amount of the monomer mixture and 5 to 50% by weight of a cross-linkage based on the total amount of the monomer mixture. And a sex monomer.
- the monofunctional polymerizable vinyl monomer is a compound having one polymerizable alkenyl group (a broad vinyl group) in one molecule.
- the monofunctional polymerizable vinyl monomer is preferably different from the hydrophobic monomer used in the resin particle production process, and the monofunctional polymerizable vinyl monomer is the resin particle production process.
- the hydrophilicity is higher than the hydrophobic monomer used in (high solubility in water at 20 ° C.), and at least one selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfo group, and an amino group More preferably, it contains at least one of a polymerizable vinyl monomer having a hydrophilic substituent and a polymerizable vinyl monomer having a solubility in water at 20 ° C. of 1% by weight or more.
- the irregular-shaped resin particle containing the 1st resin component which consists of hydrophilic resin, and the 2nd resin component which consists of hydrophobic resin can be manufactured.
- Polymerizable vinyl monomer having at least one hydrophilic substituent selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfo group, and an amino group, and a polymerizability having a solubility in water at 20 ° C. of 1% by weight or more
- the vinyl monomer various compounds exemplified in the section of [Hydrophilic resin] can be used, and (meth) acrylic acid ester having an alkylene oxide group represented by the general formula (1) is used. preferable.
- the polymer of the monomer mixture is easily phase-separated from the resin particles in the process of polymerizing the monomer mixture, and the irregular shape and uneven distribution structure peculiar to the present invention are easily obtained.
- the amount of the (meth) acrylic acid ester having an alkylene oxide group represented by the general formula (1) is preferably in the range of 0 to 40% by weight with respect to the total amount of the monomer mixture. More preferably, it is more than 0 and not more than 40% by weight, more preferably 1 to 40% by weight, still more preferably 5 to 30% by weight, and still more preferably 10 to Most preferably, it is in the range of 20% by weight.
- the amount of the (meth) acrylic acid ester having an alkylene oxide group represented by the general formula (1) is less than 1% by weight based on the total amount of the monomer mixture, the general formula (1) The effect by using the (meth) acrylic acid ester which has the alkylene oxide group represented is hardly acquired.
- the crosslinkable monomer is a compound having two or more polymerizable alkenyl groups (broadly defined vinyl groups) in one molecule.
- the crosslinkable monomer is not particularly limited, and any known monomer can be used. Examples thereof include ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and divinylbenzene. .
- the amount of the crosslinkable monomer used is in the range of 5 to 50% by weight with respect to the total amount of the monomer mixture, but in the range of 10 to 40% by weight with respect to the total amount of the monomer mixture. More preferably, it is within.
- the weight of the monomer mixture is increased during the polymerization of the monomer mixture. Phase separation between the coalesced resin particles and the resin particles is difficult to occur, and it becomes difficult to obtain a deformed shape and an unevenly distributed structure unique to the present invention.
- the monomer mixture has a solubility in water at 20 ° C., a polymerizable vinyl monomer having at least one hydrophilic substituent selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfo group, and an amino group.
- a polymerizable vinyl monomer having at least one hydrophilic substituent selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfo group, and an amino group.
- Other polymerizable vinyl monomers that are not at least one of the polymerizable vinyl monomers at 1% by weight or more may be included.
- the other polymerizable vinyl monomers include (meth) acrylic acid derivatives such as n-butyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl (meth) acrylate.
- the other polymerizable vinyl monomer is preferably a (meth) acrylic acid ester, and more preferably a linear alkyl (meth) acrylate. These compounds may be used alone or in combination of two or more.
- the amount of the other polymerizable vinyl monomer used is preferably 20% by weight or less, and more preferably 10% by weight or less, based on the total amount of the monomer mixture.
- the monomer mixture is dispersed in an aqueous medium to prepare an aqueous emulsion.
- the aqueous medium include the media mentioned in the section of the resin particle production process.
- the aqueous emulsion can be prepared, for example, by the method using the fine emulsifier described above.
- the aqueous emulsion contains a surfactant.
- a surfactant any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a zwitterionic surfactant can be used.
- anionic surfactants include fatty acid soaps such as sodium oleate and castor oil potassium soap, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, and alkylnaphthalene.
- Dialkylsulfosuccinates such as sulfonate, alkanesulfonate, sodium dioctylsulfosuccinate, alkenyl succinate (dipotassium salt), alkyl phosphate ester salt, naphthalene sulfonate formalin condensate, polyoxyethylene alkylphenyl ether sulfate Salt, polyoxyethylene alkyl ether sulfate such as sodium polyoxyethylene lauryl ether sulfate, polyoxyethylene alkyl sulfate ester salt, etc. .
- cationic surfactant examples include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride.
- zwitterionic surfactants examples include lauryl dimethylamine oxide, phosphate ester surfactants, phosphite ester surfactants, and the like. Only 1 type may be used for the said surfactant and it may use it in combination of 2 or more type. Of the above surfactants, anionic surfactants are preferred in that the dispersion stability during polymerization can be increased. These surfactants vary depending on the type thereof, but are preferably used within a range of 0.1 to 5 parts by weight, based on 100 parts by weight of the monomer mixture, and 0.3 to 3 parts by weight. It is more preferable to use within the range.
- a polymerization initiator may be mixed as necessary.
- the polymerization initiator may be mixed in advance in the monomer mixture and then dispersed in an aqueous medium, or may be mixed in which both are separately dispersed in an aqueous medium.
- polymerization initiator examples include benzoyl peroxide, lauroyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, tert-butylperoxy-2-ethylhexano Organic peroxides such as diates and di-tert-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 within a range of 0.1 to 3 parts by weight with respect to 100 parts by weight of the monomer mixture.
- the particle diameter of the droplets of the monomer mixture in the obtained aqueous emulsion is preferably smaller than the resin particles because the monomer mixture is efficiently absorbed by the resin particles.
- the resin particles may be added directly to the aqueous emulsion, or may be added to the aqueous emulsion in a form in which the resin particles are dispersed in an aqueous medium (for example, an aqueous emulsion).
- an aqueous emulsion containing resin particles obtained by emulsion polymerization in the resin particle production process is added to the aqueous emulsion containing the monomer mixture. May be.
- the resin particles may be added to the aqueous medium at the same time as the monomer mixture is dispersed in the aqueous medium, and the monomer mixture is added to the aqueous medium. It may be added to the aqueous medium before being dispersed therein.
- the resin particles are allowed to absorb the monomer mixture in the aqueous emulsion. This absorption can usually be carried out by stirring the aqueous emulsion after addition of the resin 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.
- Resin particles swell due to absorption of the monomer mixture.
- the amount of the monomer mixture absorbed in 1 part by weight of the resin particles is preferably in the range of 1 to 125 parts by weight, more preferably in the range of 2 to 60 parts by weight. More preferably, it is within the range of parts.
- the amount of the monomer mixture to be absorbed by 1 part by weight of the resin particles is less than 1 part by weight, the increase in particle diameter due to polymerization is reduced, thereby reducing productivity.
- the amount of the monomer mixture to be absorbed by 1 part by weight of the resin particles is more than 125 parts by weight, the monomer mixture is not completely absorbed by the resin particles, and is uniquely suspended and polymerized in an aqueous medium. May be generated. The end of absorption can be determined by confirming the enlargement of the particle diameter by observation with an optical microscope.
- a polymer dispersion stabilizer may be added to the aqueous emulsion in order to improve the dispersion stability of the formed irregular shaped resin particles.
- the polymer dispersion stabilizer include polyvinyl alcohol, polycarboxylic acid, celluloses (such as hydroxyethyl cellulose and carboxymethyl cellulose), and polyvinyl pyrrolidone.
- a polymer dispersion stabilizer and an inorganic water-soluble polymer compound such as sodium tripolyphosphate can be used in combination.
- polyvinyl alcohol and polyvinyl pyrrolidone are preferred.
- the addition amount of the polymer dispersion stabilizer is preferably in the range of 1 to 10 parts by weight with respect to 100 parts by weight of the monomer mixture.
- the aqueous emulsion is mixed with nitrites such as sodium nitrite, sulfites, hydroquinones, ascorbic acids, water-soluble vitamin Bs, Water-soluble polymerization inhibitors such as acids and polyphenols may be added.
- nitrites such as sodium nitrite, sulfites, hydroquinones, ascorbic acids, water-soluble vitamin Bs, Water-soluble polymerization inhibitors such as acids and polyphenols may be added.
- the addition amount of the polymerization inhibitor is preferably in the range of 0.02 to 0.2 parts by weight with respect to 100 parts by weight of the aqueous medium.
- the polymerization temperature can be appropriately selected according to the kind of the monomer mixture and the kind of 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 carried out by raising the temperature after the monomer mixture is completely absorbed by the resin particles.
- the irregular shaped resin particles are separated from the aqueous medium by filtration or the like, and if necessary, the aqueous medium is removed from the irregular shaped resin particles by centrifugation or the like, and if necessary, washed with water and a solvent and then dried.
- This production method is performed by polymerizing a hydrophobic monomer containing a (meth) acrylic acid ester containing a halogenated alkyl group having 2 to 10 carbon atoms or an alicyclic hydrocarbon group in an ester portion, to 150,000 to 100
- An aqueous polymerization step of polymerizing in a medium is performed by polymerizing a hydrophobic monomer containing a (meth) acrylic acid ester containing a halogenated alkyl group having 2 to 10 carbon atoms or an alicyclic hydrocarbon group in an ester portion.
- the resin production process in the production method using the resin solution can be performed in the same manner as the resin particle production process in the production method using the seed polymerization described above.
- a polymerization method of the resin production process emulsion polymerization is performed. It is preferable to use suspension polymerization rather than use.
- solution polymerization, bulk polymerization, and the like can be used as a polymerization method in the resin production process. A method for obtaining a particulate resin (resin particles) using suspension polymerization will be described below, but is not limited to this method.
- the hydrophobic monomer described in the section of the resin particle production process is subjected to suspension polymerization in an aqueous medium to obtain particles made of resin.
- an oil phase and an aqueous medium are prepared in separate containers.
- the oil phase is obtained by mixing and stirring the hydrophobic monomer and other oil phase components used as necessary.
- examples of other oil phase components used as necessary include the polymerization initiators and molecular weight regulators mentioned in the section of the resin particle production process. It is preferable that the usage-amount of a polymerization initiator and a molecular weight modifier exists in the numerical range demonstrated by the term of the said resin particle manufacturing process.
- the mixing and stirring means used at this time is preferably a mixing and stirring means that is uniform as a whole, and examples thereof include general mixers and homogenizers.
- the aqueous medium mentioned in the resin particle production process can be used.
- the amount of the aqueous medium used is preferably in the range of 150 to 1000 parts by weight with respect to 100 parts by weight of the hydrophobic monomer.
- a dispersion stabilizer for stabilizing the hydrophobic monomer in a suspended state in the aqueous medium may be added and mixed and stirred.
- the dispersion stabilizer include various polymer dispersion stabilizers (water-soluble polymers) listed in the above-mentioned seed polymerization step; tricalcium phosphate, magnesium hydroxide, magnesium pyrophosphate, barium sulfate, calcium carbonate, A sparingly water-soluble inorganic salt such as silica can be used.
- the mixing and stirring means used at this time is preferably a mixing and stirring means that is uniform as a whole, and examples thereof include a general mixer and a homogenizer.
- the resin particles can be easily removed from the resin, and the resin particles can be polymerized with a narrow particle size distribution compared to the case where other dispersion stabilizers are used.
- a sparingly water-soluble inorganic salt having a solubility of about 3 mg or less is preferred.
- tricalcium phosphate having a solubility in water at room temperature of 2.5 mg is suitable as the dispersion stabilizer.
- the amount of the dispersion stabilizer used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the hydrophobic monomer.
- a surfactant for stabilizing the hydrophobic monomer in a suspended state in the aqueous medium may be added and mixed and stirred.
- the surfactant the surfactants mentioned in the section of the seed polymerization step can be used.
- Anionic surfactants are preferable in that particles made of resin can be polymerized with a narrow particle size distribution as compared with other surfactants.
- the surfactant is preferably blended in the aqueous medium to a concentration of 0.005 to 0.3% by weight.
- the mixing and stirring means used at this time is preferably a mixing and stirring means that is uniform as a whole, and examples thereof include a general mixer and a homogenizer.
- the oil phase is added to the aqueous medium, mixed and stirred to obtain a suspension.
- the oil phase forms oil droplets.
- the agitation conditions such as the agitation time and the number of revolutions can be changed to easily adjust the oil droplet size and other agitation means.
- the ability to adjust the oil droplet size means that the size of the particles obtained from the oil droplets can be adjusted.
- the oil phase is polymerized by heating to obtain particles made of resin.
- the suspension may be heated with a heating device such as an autoclave.
- the particles made of the obtained resin may be removed from the aqueous medium by filtering, if necessary, washing the filtrate with water, and drying. Further, if necessary, the dispersion stabilizer may be removed before washing with water.
- the resin is preferably used in the next aqueous polymerization step in the form of particles, but may be formed into another shape such as a pellet and used in the next aqueous polymerization step.
- the resin obtained in the resin production process is dissolved in the monomer mixture described in the section of the seed polymerization process, and the obtained solution is polymerized in an aqueous medium.
- the resin may be mixed with the monomer mixture.
- the amount of the monomer mixture mixed with 1 part by weight of the resin is preferably in the range of 1 to 125 parts by weight, more preferably in the range of 5 to 50 parts by weight. More preferably, it is in the range.
- the amount of the monomer mixture mixed with 1 part by weight of the resin is less than 1 part by weight, the resin may not be sufficiently dissolved.
- the proportion of the second resin component in the obtained deformed resin particles becomes too small, and the second resin component is unevenly distributed. There may be little effect.
- the same method as suspension polymerization in the resin production step can be used. That is, a resin and monomer mixture may be used instead of the hydrophobic monomer in the suspension polymerization in the resin production process.
- the resin and monomer mixture may be added separately to the oil phase, or may be mixed in advance and added to the oil phase.
- the outer shape of the deformed resin particles when viewed from the direction where the projected area is maximum is circular
- the outer shape of the deformed resin particles when viewed from the direction where the projected area is minimum is non-circular.
- the shape of the deformed resin particles obtained by the production method of the present invention can be controlled by appropriately adjusting the use ratio of raw materials, polymerization conditions, and the like.
- a hemispherical shape, a biconvex lens shape, a mushroom shape, and a cross section Horseshoe-shaped deformed resin particles can be made separately.
- the amount of the monomer mixture used for the resin particles is large, it is easy to obtain a cross-section horseshoe-shaped deformed resin particle.
- the amount of the monomer mixture used for the resin particles is small, hemispherical shaped resin particles are obtained. It is easy to be done. Moreover, when the monomer mixture does not contain a (meth) acrylic acid ester having an alkylene oxide group, it is easy to obtain odd-shaped resin particles having a double-sided convex lens shape. When the monomer mixture contains a small amount of (meth) acrylic acid ester having an alkylene oxide group, hemispherical shaped resin particles are easily obtained. When the monomer mixture contains a large amount of (meth) acrylic acid ester having an alkylene oxide group, odd-shaped resin particles having a horseshoe cross section are easily obtained.
- the weight average molecular weight of the resin particles when the weight average molecular weight of the resin particles is low, it is easy to obtain cross-section horseshoe-shaped deformed resin particles, and when the weight average molecular weight of the resin particles is higher than before, it is easy to obtain hemispherical shaped resin particles, When the weight average molecular weight of the resin particles is higher than the previous case, mushroom-shaped deformed resin particles are easily obtained.
- the deformed resin particles of the present invention are coating agents (coating compositions) used as coating agents for coating materials, paper coating agents, information recording paper coating agents, light diffusion members for light diffusion films (optical sheets), etc. It is useful as a light diffusing agent constituting a light diffusing resin composition for producing a light diffusing plate; an additive for external preparations such as cosmetics; a surfactant and the like.
- the deformed resin particles of the present invention can be contained in a coating agent as a coating film softening agent, a paint matting agent, a light diffusing agent, and the like.
- the coating agent of the present invention contains the irregular shaped resin particles of the present invention.
- the coating agent contains a binder resin as necessary.
- a binder resin an organic solvent or water-soluble resin, or an emulsion-type aqueous resin that can be dispersed in water can be used, and any known binder resin can be used.
- the binder resin include acrylic resins such as trade names “Dianal (registered trademark) LR-102” and “Dianar (registered trademark) BR-106” manufactured by Mitsubishi Rayon Co., Ltd., alkyd resins, polyester resins, Examples include polyurethane resins, chlorinated polyolefin resins, and amorphous polyolefin resins. These binder resins can be appropriately selected depending on the adhesion of the paint to the substrate to be coated, the environment in which it is used, and the like.
- the blending amount of the irregular shaped resin particles is appropriately adjusted depending on the film thickness of the coating film formed in the coating agent containing the binder resin, the average particle diameter of the irregular shaped resin particles, the coating method, the usage to be used, etc. It is preferably within the range of 0.1 to 1000 parts by weight with respect to parts.
- the blending amount of the irregular shaped resin particles may be within a range of 5 to 50% by mass with respect to the total of the binder resin (solid content when using an emulsion type aqueous resin) and the irregular shaped resin particles. More preferably, it is more preferably in the range of 10 to 50% by mass, and still more preferably in the range of 20 to 40% by mass.
- the matte effect may not be sufficiently obtained. Further, when the content of the irregular shaped resin particles exceeds 50% by mass, the dispersion of the irregular shaped resin particles may occur because the viscosity of the coating agent becomes too high. Therefore, appearance defects of the coating surface may occur, such as micro cracks occurring on the coating surface obtained by applying the coating agent, or roughness on the resulting coating surface.
- the coating agent contains a medium as necessary.
- a medium it is preferable to use a solvent (solvent) capable of dissolving the binder resin or a dispersion medium capable of dispersing the binder resin.
- a solvent solvent capable of dissolving the binder resin
- a dispersion medium capable of dispersing the binder resin.
- any of an aqueous medium and an oily medium can be used.
- Oil-based media include hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; dioxane, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, etc. And ether solvents.
- hydrocarbon solvents such as toluene and xylene
- ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone
- ester solvents such as ethyl acetate and butyl acetate
- dioxane ethylene glycol diethyl ether
- ethylene glycol monobutyl ether etc.
- ether solvents ethyl acetate and butyl acetate
- dioxane ethylene glycol diethyl ether
- coating agents include curing agents, colorants, extenders, color pigments, metal pigments, mica powder pigments, dyes, antistatic agents, leveling agents, fluidity modifiers, ultraviolet absorbers, and light stabilizers. Other additives such as may be included.
- the substrate to which the coating agent is applied is not particularly limited, and a substrate according to the application can be used.
- a transparent substrate such as a glass substrate or a transparent substrate resin is used as a substrate to be coated.
- a transparent substrate as the substrate to be coated and coating the transparent substrate with a coating agent that does not contain a colorant (a coating agent for light diffusion) to form a transparent coating film, such as a light diffusion film
- a light diffusing member can be manufactured.
- the irregular shaped resin particles function as a light diffusing agent.
- the transparent base resin examples include polyesters such as acrylic resins, alkyl (meth) acrylate-styrene copolymers, polycarbonate, polyethylene terephthalate (hereinafter abbreviated as “PET”), polyethylene, polypropylene, polystyrene, and the like. It is done.
- acrylic resin, alkyl (meth) acrylate-styrene copolymer, polycarbonate, polyester, and polystyrene are preferable when excellent transparency is required for the transparent base resin.
- These transparent base resins can be used alone or in combination of two or more.
- the manufactured light diffusion member can be used as an illumination cover (light emitting diode (LED) illumination illumination cover, fluorescent lamp illumination illumination cover, etc.), a light diffusion member (light diffusion film, light diffusion plate, etc.) and the like.
- matte paper can be produced by using paper as a substrate to be coated and applying a coating agent (paper coating agent) that does not contain a colorant to form a transparent coating film.
- paper coating agent paper coating agent
- the formation method of the coating film using a coating agent is not specifically limited, Any well-known method can be used. Examples of the method for forming the coating film include methods such as spray coating, roll coating, and brush coating.
- the coating agent may be diluted by adding a diluent in order to adjust the viscosity as necessary.
- Diluents include hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as dioxane and ethylene glycol diethyl ether; water An alcohol solvent or the like. These diluents may be used alone or in combination of two or more. When manufacturing a light-diffusion member, it is preferable to use the method in which the unevenness
- Light diffusing resin composition It can be used as a light diffusing resin composition by dispersing the irregular shaped resin particles of the present invention in a transparent base resin (transparent resin) as a light diffusing agent. That is, the light diffusing resin composition contains the irregular shaped resin particles of the present invention and a transparent base resin.
- the light diffusing resin composition is a raw material for lighting covers (light emitting diode (LED) lighting lighting covers, fluorescent lamp lighting lighting covers, etc.) and light diffusion members (light diffusion sheets, light diffusion films, light diffusion plates, etc.). Can be used as
- thermoplastic resin a thermoplastic resin different from the polymer particle component constituting the irregular shaped resin particles is usually used.
- the thermoplastic resin used as the transparent base resin include acrylic resins, alkyl (meth) acrylate-styrene copolymers, polycarbonate, polyester, polyethylene, polypropylene, polystyrene, and the like.
- acrylic resin, alkyl (meth) acrylate-styrene copolymer, polycarbonate, polyester, and polystyrene are preferred when excellent transparency is required for the transparent base resin.
- These thermoplastic resins can be used alone or in combination of two or more.
- the addition ratio of the irregular shaped resin particles to the transparent base resin is preferably in the range of 0.01 to 40 parts by weight, and in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the transparent base resin. More preferably, it is within.
- the odd-shaped resin particles are less than 0.01 parts by mass, it may be difficult to impart light diffusibility to the light diffusing member.
- the number of irregular shaped resin particles is more than 40 parts by mass, the light diffusing member can be given light diffusibility, but the light diffusing member may have low light transmittance.
- the method for producing the light diffusing resin composition is not particularly limited, and can be produced by mixing the irregularly shaped resin particles and the transparent base resin by a conventionally known method such as a mechanical pulverization and mixing method.
- a mechanical pulverization and mixing method for example, by using a device such as a Henschel mixer, a V-type mixer, a turbula mixer, a hybridizer, or a rocking mixer, the irregular shaped resin particles and the transparent base resin are mixed and stirred to obtain light.
- a diffusible resin composition can be produced.
- a light diffusing member such as a lighting cover or a light diffusing sheet can be produced by molding the light diffusing resin composition.
- a light diffusing agent and a transparent base resin are mixed with a mixer, and a pellet made of a light diffusing resin composition is obtained by kneading with a melt kneader such as an extruder.
- a light diffusing member having an arbitrary shape can be obtained by extrusion molding or injection molding after melting the pellet.
- the light diffusion sheet can be used as, for example, a light diffusion sheet of a liquid crystal display device.
- the configuration of the liquid crystal display device is not particularly limited as long as it includes a light diffusion sheet.
- the liquid crystal display device includes at least a liquid crystal display panel having a display surface and a back surface, a light guide plate disposed on the back surface side of the liquid crystal display panel, and a light source that makes light incident on the side surface of the light guide plate.
- the liquid crystal display device includes a light diffusion sheet on a surface of the light guide plate facing the liquid crystal display panel, and a reflection sheet on the surface opposite to the surface of the light guide plate facing the liquid crystal display panel. This arrangement of light sources is generally referred to as an edge light type backlight arrangement.
- this arrangement is an arrangement in which a light source is arranged on the back side of the liquid crystal display panel and at least a light diffusion sheet arranged between the liquid crystal display panel and the light source.
- the deformed resin particles of the present invention can be used as a raw material for an external preparation, for example, as a slipping improver for an external preparation.
- the external preparation of the present invention contains the deformed resin particles of the present invention. Examples of the external preparation include cosmetics (cosmetics) and external medicines.
- the cosmetic is not particularly limited as long as it has an effect due to the inclusion of the deformed resin particles.
- solid cosmetics such as funny and foundation; powder cosmetics such as baby powder and body powder; Liquid cosmetics such as water, emulsion, cream, liquid foundation, body lotion, pre-shave lotion, body shampoo, antiperspirant, etc .; cosmetics for cleaning such as soap and scrub facial cleanser; packs; shave cream; lipstick; lip balm Blusher; eyebrow cosmetics; manicure cosmetics; hair-washing cosmetics; hair dyes; hair styling; aromatic cosmetics; toothpaste; bath preparations; sunscreen products;
- the blending ratio of the irregular shaped resin particles to these cosmetics varies depending on the type of cosmetic.
- the proportion of the irregular shaped resin particles to the cosmetic is preferably in the range of 1 to 20% by weight, and in the range of 3 to 15% by weight. It is more preferable.
- the blending ratio of the deformed resin particles to the cosmetics is preferably in the range of 1 to 20% by weight, and in the range of 3 to 15% by weight.
- the blending ratio of the irregular shaped resin particles to the cosmetics is preferably in the range of 1 to 15% by weight. More preferably, it is within the range of 3 to 10% by weight.
- the external medicine is not particularly limited as long as it is applied to the skin, and examples thereof include pharmaceutical creams, ointments, pharmaceutical emulsions, and pharmaceutical lotions.
- the content of the deformed resin particles in the external medicine can be appropriately set according to the type of the external medicine, but is preferably in the range of 1 to 80% by weight, and more preferably in the range of 5 to 70% by weight.
- the content of the deformed resin particles is less than 1% by weight with respect to the total amount of the external medicine, a clear effect due to the inclusion of the deformed resin particles may not be recognized.
- the content of the irregular shaped resin particles exceeds 80% by weight, a remarkable effect commensurate with the increase in content may not be recognized, which is not preferable in terms of production cost.
- main agents or additives can be blended according to the purpose within a range not impairing the effects of the present invention.
- a main agent or additive include clay minerals (components having several functions such as gloss improvement and touch improvement; mica, talc, etc.), coloring pigments (red iron oxide, yellow iron oxide, Titanium oxide, ultramarine blue, bitumen, carbon black, etc.), synthetic dyes such as azo dyes, water, lower alcohols (alcohols having 5 or less carbon atoms), higher alcohols (alcohols having 6 or more carbon atoms such as cetyl alcohol), hydrocarbons (Vaseline, liquid paraffin, etc.), silicone oil, vegetable oils, animal oils, waxes, higher fatty acids (fatty acids having 12 or more carbon atoms such as stearic acid), sterols, fatty acid esters (octyldodecyl myristate, oleic acid esters
- the irregular shaped resin particle of the present invention is formed of a first resin component made of a hydrophilic resin, and the remaining surface is made of a second resin component made of a hydrophobic resin.
- the irregular shaped resin particles of the present invention are obtained by dispersing an oily medium (or oil phase component) such as oil in an aqueous medium (or aqueous phase component) and emulsifying it, or by making an aqueous medium (or aqueous phase component) oily.
- emulsifier a detergent, an antistatic agent, a lubricant, a softening agent, an antifogging / spreading agent, a mordant and the like for dispersing and emulsifying in a medium (or oil phase component).
- Emulsion of the present invention contains the irregular shaped resin particles of the present invention.
- the deformed resin particles of the present invention function as an emulsifier.
- the emulsion of the present invention contains an aqueous phase component and an oil phase component, and an oil-in-water emulsion in which droplets of an oily component are dispersed in an aqueous component, and droplets of an aqueous component are dispersed in an oily component. Any of the water-in-oil emulsion may be used.
- oil component examples include higher alcohols (alcohols having 6 or more carbon atoms such as cetyl alcohol), hydrocarbons (petrol, liquid paraffin, etc.), silicone oils, vegetable oils, animal fats, waxes, higher fatty acids ( Fatty acids having 12 or more carbon atoms such as stearic acid), sterols, fragrances, preservatives and the like.
- aqueous component examples include water, a pH adjuster (such as triethanolamine), and clay minerals.
- the emulsion of the present invention can be used, for example, as an emulsified foundation that is a form of the external preparation.
- the optical member of the present invention is an optical member including a base material and a plurality of deformed resin particles of the present invention, and each of the plurality of deformed resin particles has a hemispherical shape having a hemispherical portion and a flat portion.
- the plurality of irregularly shaped resin particles are arranged on the base material such that their flat portions face the base material.
- the substrate examples include a transparent film substrate such as a film made of various resins mentioned as examples of the transparent substrate resin in the section “(1) Coating agent”; a transparent resin plate made of the various resins; Light transmissive substrates other than transparent film substrates such as glass plates; light reflecting substrates such as metal films and metal plates can be used.
- a light-transmitting substrate such as a transparent film substrate
- the optical member of the present invention functions as a light-transmitting member having a light diffusing property and a light collecting property. It can be used as a member.
- the optical member of the present invention When a transparent film substrate is used as the substrate, the optical member of the present invention functions as a light transmissive film having light diffusibility and light condensing property, and thus can be used as a light diffusing film, a light condensing film, and the like.
- the optical member of the present invention When a light reflecting substrate is used as the substrate, the optical member of the present invention functions as a reflecting member having a light diffusing property and a condensing property, and thus can be used as a light diffusing reflecting member, a condensing member and the like.
- a dispersion liquid (coating agent) in which hemispherical irregular shaped resin particles are dispersed in an aqueous dispersion medium is spread on the liquid surface of a container (for example, a beaker) containing an aqueous medium such as water. Then, it can manufacture by the method of putting a base material in the said liquid surface, transferring the developed dispersion liquid on a base material, and drying.
- aqueous dispersion medium for example, alcohols such as isopropanol can be used.
- the development of the dispersion may be performed gently using, for example, a dropper.
- the weight average molecular weight was measured using gel permeation chromatography (GPC).
- the measured weight average molecular weight is a polystyrene (PS) conversion weight average molecular weight.
- the measuring method is as follows. First, 50 mg of a sample was dissolved in 10 ml of tetrahydrofuran (THF). The resulting solution was filtered using a 0.45 ⁇ m non-aqueous chromatographic disk. The obtained filtrate was analyzed by GPC and the weight average molecular weight in terms of PS was measured.
- GPC measurement conditions were as follows.
- GPC apparatus trade name “Gel Permeation Chromatograph HLC-8020” manufactured by Tosoh Corporation Column: Two trade names “TSKgel GMH XL-L” (diameter 7.8 mm ⁇ length 30 cm) manufactured by Tosoh Corporation Column temperature: 40 ° C.
- Carrier gas Tetrahydrofuran (THF)
- Carrier gas flow rate 1 mL / min
- Injection / pump temperature 35 ° C
- Detection RI (differential refractive index detector)
- Injection volume 100 ⁇ L
- the average particle size of the seed particles was measured with a laser diffraction / scattering particle size distribution analyzer (LS230 type, manufactured by Beckman Coulter, Inc.).
- 0.1 g of seed particles and 10 ml of a 0.1% by weight nonionic surfactant solution are put into a test tube, and the touch mixer (manufactured by Yamato Kagaku Co., Ltd., “TOUCHMIXER MT-31”) is used for 2 seconds. Mixed. Thereafter, the seed particles in the test tube were dispersed for 10 minutes using a commercially available ultrasonic cleaner (“ULTRASONIC CLEARNER VS-150” manufactured by VervoCrea Inc.) to obtain a dispersion.
- ULTRASONIC CLEARNER VS-150 manufactured by VervoCrea Inc.
- the average particle size of the seed particles in the dispersion was measured with a laser diffraction / scattering particle size distribution analyzer (LS230, manufactured by Beckman Coulter, Inc.). The optical model at the time of measurement was adjusted to the refractive index of the produced seed particles.
- the refractive index of the homopolymer of the monomer was used as the refractive index of the seed particles.
- the average value obtained by weighted average of the refractive index of the homopolymer of each monomer by the amount of each monomer used as the refractive index of the seed particles was used.
- the lengths A to I of the irregular shaped resin particles were measured as follows. Using a scanning electron microscope “JSM-6360LV” (manufactured by JEOL Ltd.), arbitrary 30 deformed resin particles were observed at a magnification of 5,000 to 10,000 times, and each portion of each deformed resin particle ( The length of portions corresponding to A to I) was measured, and the average value of 30 measured values was defined as lengths A to I.
- the sphere equivalent volume average particle diameter of the irregular shaped resin particles was calculated by filling the electrolyte solution into pores having a pore diameter of 50 to 280 ⁇ m and determining the volume from the change in conductivity of the electrolyte solution when the particles pass through the electrolyte solution. .
- the sphere-converted volume average particle diameter of the irregular shaped resin particles is the volume average particle diameter (volume) measured by the Coulter method using a Coulter type precision particle size distribution analyzer Multisizer II (manufactured by Beckman Coulter, Inc.). (Arithmetic mean diameter in the standard particle size distribution). In the measurement, Multisizer II was calibrated using an aperture suitable for the particle size of the particles to be measured according to Reference MANUAL FOR THE COULTER MULTISIZER (1987) published by Coulter Electronics Limited.
- 0.1 g of deformed resin particles and 10 ml of a 0.1 wt% nonionic surfactant aqueous solution are introduced into a commercially available glass test tube, and a touch mixer “TOUCMIXER MT-31” manufactured by Yamato Scientific Co., Ltd. is used. After mixing for 2 seconds, preliminarily disperse the irregular shaped resin particles in the test tube for 10 seconds using “ULTRASONIC CLEANER VS-150” manufactured by VervoCrea Co., Ltd., which is a commercially available ultrasonic cleaner. .
- emulsion aqueous emulsion
- the obtained emulsion contained 14% by weight of a solid content (methyl methacrylate polymer), and the solid content consisted of true spherical particles having an average particle diameter of 0.4 ⁇ m and a weight average molecular weight of 600,000.
- Synthesis Example 2 of emulsion for seed particle formation Polymerization was carried out in the same manner as in Synthesis Example 1 of seed particle-forming emulsion except that n-dodecyl mercaptan was not used to obtain an emulsion.
- the obtained emulsion contained 14% by weight of a solid content (methyl methacrylate polymer), and the solid content was composed of true spherical fine particles having an average particle diameter of 0.43 ⁇ m and a weight average molecular weight of 850,000.
- a separable flask equipped with a stirrer, a thermometer, and a reflux condenser contains 550 g of water as an aqueous medium, 70 g of the emulsion obtained in Synthesis Example 1, and a halogenated alkyl group having 2 to 10 carbon atoms in the ester part.
- seed particle-containing emulsion an emulsion containing seed particles (hereinafter referred to as “seed particle-containing emulsion”) was obtained.
- the obtained seed particle-containing emulsion contained 14% by weight of a solid content, and the solid content consisted of true spherical particles (seed particles) having an average particle diameter of 1.0 ⁇ m and a weight average molecular weight of 620,000.
- the obtained seed particle-containing emulsion contained 14% by weight of a solid content, and the solid content consisted of true spherical fine particles having an average particle diameter of 1.1 ⁇ m and a weight average molecular weight of 820,000.
- Seed particles were polymerized in the same manner as in Seed Particle Production Example 1 except that 100 g of methyl methacrylate was used instead of 100 g of 2,2,2-trifluoroethyl methacrylate, and n-dodecyl mercaptan was not used. A containing emulsion was obtained.
- the obtained seed particle-containing emulsion contained 14% by weight of a solid content, and the solid content consisted of true spherical fine particles having an average particle diameter of 1.0 ⁇ m and a weight average molecular weight of 25,000.
- the obtained seed particle-containing emulsion contained 14% by weight of a solid content, and the solid content consisted of spherical particles having an average particle diameter of 0.95 ⁇ m and a weight average molecular weight of 590,000.
- the obtained dispersion was stirred with a high-speed emulsification / dispersing machine “TK homomixer” (manufactured by Primics Co., Ltd.) at a stirring speed of 3000 rpm for 10 minutes, and the droplet diameter of the mixed liquid was adjusted to about 20 ⁇ m. .
- TK homomixer manufactured by Primics Co., Ltd.
- the polymerization reactor was heated to 80 ° C. and subjected to suspension polymerization while stirring, and then cooled.
- the resulting suspension was filtered, washed, and dried to obtain methyl methacrylate-methacrylic acid 2,2,2-trifluoroethyl copolymer particles.
- the weight average molecular weight of the obtained particles was 350,000.
- the resulting mixture was mixed with 1 L of ion-exchanged water containing 10 g of sodium dioctylsulfosuccinate as an anionic surfactant, and a high-speed emulsifier / disperser “TK homomixer” (Primix Co., Ltd.) as a fine emulsifier.
- the product was stirred for 10 minutes at a stirring speed of 8000 rpm to obtain an aqueous emulsion.
- 360 g of seed particle-containing emulsion produced in Seed Particle Production Example 1 and having an average particle size of 1.0 ⁇ m was added while stirring with a stirrer.
- the obtained resin particles were imaged with a scanning electron microscope (SEM) to obtain the SEM image of FIG.
- the second resin component (the darker color portion having a darker color) derived from the seed particles was included, and the second resin component was unevenly distributed near the surface of the deformed resin particles.
- the obtained hemispherical irregular shaped resin particles have almost all the surface of the flat portion formed of the second resin component, and the remaining surface of the irregular shaped resin particles is the first.
- the resin component was formed.
- the black portions existing on the surface of the second resin component are encapsulated with the deformed resin particles. It is black due to the stain entering the boundary with the embedded resin, and does not indicate that components other than the first and second resin components are present in the deformed resin particles.
- Example 2 Resin particles were obtained in the same manner as in Example 1 except that the amount of the seed particle-containing emulsion produced in Seed Particle Production Example 1 was changed from 360 g to 180 g.
- the obtained resin particles were imaged with an SEM to obtain the SEM image of FIG.
- the obtained resin particles were irregular shaped resin particles having a horseshoe cross section as shown in FIG.
- A 3.45 ⁇ m.
- B 1.17 ⁇ m
- C 1.69 ⁇ m
- B / A 0.339
- C / A 0.490.
- the sphere conversion volume average particle diameter of the irregularly shaped resin particles measured by the above-described measuring method was 3.50 ⁇ m.
- the obtained cross-section horseshoe-shaped deformed resin particles include a first resin component derived from a monomer mixture containing a cross-linkable monomer (lighter and larger gray portion).
- the second resin component derived from the seed particles (the darker part of the color is darker), and the second resin component was unevenly distributed near the surface of the deformed resin particles. Further, as shown in FIG. 8, the obtained cross-section horseshoe-shaped deformed resin particles have more than half of the surface of the cut-out portion formed of the second resin component, and the rest of the deformed resin particles The surface was formed with the first resin component.
- Example 3 Resin particles were obtained in the same manner as in Example 1, except that 700 g of methyl methacrylate was used instead of 600 g of methyl methacrylate and 100 g of poly (ethylene glycol-propylene glycol) monomethacrylate.
- the obtained resin particles were imaged with an SEM, and the SEM image of FIG. 9 was obtained.
- the obtained resin particles were biconvex lens-shaped irregular resin particles.
- the particle diameter A of the obtained biconvex lens-shaped deformed resin particles, the height H of the larger plano-convex lens-shaped portion, and the height I of the smaller plano-convex lens-shaped portion were measured by the above-described measuring methods.
- A 2.7 ⁇ m
- H 1.23 ⁇ m
- I 0.58 ⁇ m
- H / A 0.456
- I / A 0.215.
- the spherical equivalent volume average particle diameter of the irregularly shaped resin particles measured by the above-described measuring method was 2.58 ⁇ m.
- the obtained biconvex lens-shaped deformed resin particles include a first resin component derived from a monomer mixture containing a crosslinkable monomer (a darker portion having a larger color).
- the second resin component derived from the seed particles (the lighter and smaller gray portion), and the second resin component was unevenly distributed near the surface of the deformed resin particles.
- the obtained biconvex lens-shaped deformed resin particles have almost all of the surface of the smaller plano-convex lens-shaped portion formed of the second resin component, and the rest of the deformed resin particles in the deformed resin particles. The surface of was formed with the 1st resin component.
- Example 4 Resin particles were obtained in the same manner as in Example 3 except that 360 g of the seed particle-containing emulsion produced in seed particle production example 2 was used instead of 360 g of the seed particle-containing emulsion produced in seed particle production example 1.
- the obtained resin particles were imaged with an SEM to obtain the SEM image of FIG.
- the second resin component (the darker color portion having a darker color) derived from the seed particles was included, and the second resin component was unevenly distributed near the surface of the deformed resin particles. Further, as shown in FIG. 12, the obtained mushroom-shaped deformed resin particles have more than half of the surface of the shaft portion formed of the second resin component, and the remaining surfaces of the deformed resin particles are The first resin component was formed.
- the black portions present on the first resin component surface and the second resin component surface are black due to the stain that has entered the boundary between the deformed resin particles and the embedding resin. It does not indicate that a component other than the first and second resin components is present in the deformed resin particles.
- Example 5 First, a single amount comprising 60 parts by weight of methyl methacrylate, 30 parts by weight of ethylene glycol dimethacrylate, and 10 parts by weight of poly (ethylene glycol-propylene glycol) monomethacrylate (product name “Blemmer (registered trademark) 50PEP-300”).
- the obtained cross-section horseshoe-shaped deformed resin particles include a first resin component derived from a monomer mixture containing a crosslinkable monomer (a darker gray portion having a larger color).
- a second resin component derived from a 2,2,2-trifluoroethyl methacrylate-methyl methacrylate copolymer (light gray, smaller gray portion), and the second resin component is an odd-shaped resin It was unevenly distributed near the surface of the particles.
- the obtained cross-section horseshoe-shaped deformed resin particles have a portion more than half of the surface of the notch portion formed of the second resin component, and the rest of the deformed resin particles in the deformed resin particles The surface was formed with the first resin component.
- the black portion present on the surface of the first resin component is black due to the staining agent that has entered the boundary between the deformed resin particles and the embedding resin, It does not indicate that components other than the first and second resin components are present in the deformed resin particles.
- Example 6 Resin particles were obtained in the same manner as in Example 3 except that 360 g of the seed particle-containing emulsion produced in seed particle production example 4 was used instead of 360 g of the seed particle-containing emulsion produced in seed particle production example 1.
- the obtained resin particles were imaged with an SEM to obtain the SEM image of FIG.
- the obtained resin particles were biconvex lens-shaped irregular resin particles as shown in FIG. Further, the particle diameter A of the obtained biconvex lens-shaped deformed resin particles, the height H of the larger plano-convex lens-shaped portion, and the height I of the smaller plano-convex lens-shaped portion were measured by the above-described measuring methods.
- A 2.90 ⁇ m
- H 1.13 ⁇ m
- I 0.80 ⁇ m
- H / A 0.390
- I / A 0.276.
- the obtained biconvex lens-shaped deformed resin particles are composed of a first resin component derived from a monomer mixture containing a crosslinkable monomer (a lighter gray portion having a lighter color).
- the second resin component derived from the seed particles (the darker part of the color is darker), and the second resin component was unevenly distributed near the surface of the deformed resin particles.
- the obtained biconvex lens-shaped deformed resin particles have almost the entire surface of the smaller plano-convex lens-shaped portion formed of the second resin component, and the rest of the deformed resin particles in the deformed resin particles. The surface of was formed with the 1st resin component.
- the obtained resin particles were imaged with an SEM to obtain the SEM image of FIG.
- the second resin component (the darker color portion having a darker color) derived from the seed particles was included, and the second resin component was unevenly distributed near the surface of the deformed resin particles.
- the obtained hemispherical deformed resin particles have almost the entire surface of the planar portion formed of the second resin component, and the remaining surfaces of the deformed resin particles are the first.
- the resin component was formed.
- the obtained resin particles were observed with an SEM, they were spherical resin particles. Moreover, the average particle diameter of the obtained resin particles was 2.54 ⁇ m.
- Example 8 Production example of external preparation
- aqueous phase component 50 parts by weight of purified water, 1.0 part by weight of triethanolamine as a pH adjuster, and 0.5 part by weight of VEEGUM (registered trademark, manufactured by Vanderbilt) as clay minerals Were added and dissolved by heating.
- the powder part prepared previously was added to the solution thus obtained, and the powder part was uniformly dispersed in the solution with a homomixer, and then kept at 70 ° C. to obtain an aqueous phase component.
- aqueous phase component 2.0 parts by weight of stearic acid, 0.3 parts by weight of cetyl alcohol, 20.0 parts by weight of liquid paraffin, fragrance (appropriate amount), and preservative (appropriate amount) are added. After mixing and dissolution by heating, the mixture was kept at 70 ° C. to obtain an oil phase component.
- the aqueous phase component is added to the obtained oil phase component, pre-emulsified, and uniformly emulsified and dispersed with a homomixer, and then cooled while stirring to emulsify the oil phase component dispersed in the aqueous phase component.
- a mold foundation emulsion cosmetic
- FIG. 19 shows a photograph obtained by imaging the obtained emulsified foundation with an optical microscope at a magnification of 1000 times. From the photograph, it was confirmed that the irregular shaped resin particles were present on the surface of the droplet.
- Comparative Example 2 Comparative production example of external preparation
- the emulsified foundation obtained in Comparative Example 2 had no emulsion stability, and separation of the oil phase component and the water phase component was observed. In contrast, the emulsified foundation obtained in Example 8 had a stable emulsified state. Further, the emulsified foundation obtained in Example 8 was superior to the emulsion foundation obtained in Comparative Example 2 in terms of slippage when applied to the skin, and was smooth and excellent in usability. . In addition, the emulsified foundation obtained in Example 8 was able to correct skin defects (make spots, freckles, pores, etc. inconspicuous) when applied to the skin.
- Example 9 Production example of optical member
- 5 parts by weight of the hemispherical irregular shaped resin particles obtained in Example 1 were mixed with 10 parts by weight of isopropanol and stirred for 3 minutes with a centrifugal stirrer to obtain a dispersion.
- This dispersion was gently spread using a dropper on the water surface of a beaker containing distilled water.
- a PET film as a transparent film base material is put on the water surface, the developed dispersion is transferred onto the PET film, and dried in an oven kept at 70 ° C. for 1 hour to form a light diffusing member (one form of optical member).
- the light-diffusion film as one form of was obtained.
- Such an array state was obtained because the hemispherical irregular shaped resin particles obtained in Example 1 were the hydrophobic second resin component in which almost all of the surface of the flat surface portion was derived from seed particles.
- the remaining surface is formed of a hydrophilic first resin component derived from a monomer mixture containing a crosslinkable monomer, an isopropanol dispersion is formed on the surface of distilled water. It is considered that, by developing, at the interface between distilled water and isopropanol, a state is formed in which a hydrophilic first resin component is arranged on the water surface side and a hydrophobic second resin component is arranged on the isopropanol side. It is done.
- the light diffusing film obtained in this example has the plurality of deformed resin particles arranged on the PET film so that the flat portions of the plurality of deformed resin particles face the PET film.
- an optical device for example, a liquid crystal display device
Abstract
Description
本発明の異形樹脂粒子は、前記課題を解決するために、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、非真球形状を有する異形樹脂粒子であって、第1の樹脂成分と、前記第1の樹脂成分と異なる第2の樹脂成分とを含み、前記異形樹脂粒子の表面近傍に前記第2の樹脂成分が偏在していることを特徴としている。
以上のように、上記方法によれば、重合性ビニル系単量体が重合する過程で重合性ビニル系単量体が樹脂から相分離して異形樹脂粒子の表面近傍に偏在し易く、かつ、重合性ビニル系単量体が樹脂からなる粒子に十分に吸収されるか、あるいは樹脂を十分に溶解する。これらの相乗効果により、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、非真球形状の異形樹脂粒子であって、第1の樹脂成分と、前記第1の樹脂成分と異なる第2の樹脂成分とを含み、前記異形樹脂粒子の表面近傍に前記第2の樹脂成分が偏在している本発明の異形樹脂粒子を製造することができる。
〔異形樹脂粒子〕
本発明の異形樹脂粒子は、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、非真球形状を有する異形樹脂粒子であって、第1の樹脂成分と、前記第1の樹脂成分と異なる種類の樹脂である第2の樹脂成分とを含み、前記異形樹脂粒子の表面近傍に前記第2の樹脂成分が偏在している。
〔断面馬蹄形状の異形樹脂粒子〕
本発明の一例に係る断面馬蹄形状の異形樹脂粒子は、図1(a)(b)に示すように、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馬蹄形状(後述する切り欠き部3の投影図に対応する凹部と、扇形とからなる形状)である。上記異形樹脂粒子は、図1(c)に示すように、互いに異なる第1の樹脂成分1および第2の樹脂成分2を含み、前記異形樹脂粒子の表面近傍に第2の樹脂成分2が偏在している。
〔マッシュルーム形状の異形樹脂粒子〕
本発明の一例に係るマッシュルーム形状の異形樹脂粒子は、図2(a)(b)に示すように、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。上記異形樹脂粒子は、図2(c)に示すように、互いに異なる第1の樹脂成分4および第2の樹脂成分5を含み、前記異形樹脂粒子の表面近傍に第2の樹脂成分5が偏在している。
軸部7の軸長方向の高さEは、異形樹脂粒子の粒子径Aの0.2~1.5倍の範囲内であることが好ましく、粒子径Aの0.2~0.7倍の範囲内であることがより好ましく、粒子径Aの0.2~0.6倍の範囲内であることがさらに好ましい。軸部7の軸長方向の高さEが粒子径Aの0.2倍より小さい場合、異形樹脂粒子の形状が半球形状に近くなるので、マッシュルーム形状に特有の効果が僅かしか得られなくなる。一方、軸部7の軸長方向の高さEが粒子径Aの1.5倍より大きい場合、製造が困難となる。
〔半球形状の異形樹脂粒子〕
本発明の一例に係る半球形状の異形樹脂粒子は、図3(a)(b)に示すように、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、半円形である。上記異形樹脂粒子は、図3(c)に示すように、互いに異なる第1の樹脂成分11および第2の樹脂成分12を含み、前記異形樹脂粒子の表面近傍に第2の樹脂成分12が偏在している。
〔両凸レンズ形状の異形樹脂粒子〕
本発明の一例に係る両凸レンズ形状の異形樹脂粒子は、図4(a)(b)に示すように、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。上記異形樹脂粒子は、図4(c)に示すように、互いに異なる第1の樹脂成分14および第2の樹脂成分15を含み、前記異形樹脂粒子の表面近傍に第2の樹脂成分15が偏在している。
本発明の異形樹脂粒子は、球換算体積平均粒子径が0.5~50μmの範囲内であることが好ましい。これにより、各種用途に適した粒子となる。本発明の異形樹脂粒子は、防眩フィルムの構成要素(光拡散剤)として用いる場合、球換算体積平均粒子径が1.5~8μmの範囲内であることがより好ましい。これにより、良好な防眩性を有する防眩フィルムを実現できる。また、本発明の異形樹脂粒子は、光拡散部材の構成要素(光拡散剤)として用いる場合、球換算体積平均粒子径が1~50μmの範囲内であることがより好ましく、球換算体積平均粒子径が1~10μmの範囲内であることがさらに好ましい。これにより、良好な光拡散性を有する光拡散部材を実現できる。また、本発明の異形樹脂粒子は、外用剤の原料として用いる場合、球換算体積平均粒子径が1~50μmの範囲内であることが好ましい。これにより、良好な外用剤を実現できる。また、本発明の異形樹脂粒子は、紙用コーティング剤として用いる場合、球換算体積平均粒子径が0.5~10μmの範囲内であることが好ましい。これにより、良好な紙用コーティング剤を実現できる。また、上記構成の異形樹脂粒子は、球換算体積平均粒子径が1~10μmの範囲内である場合に、異形樹脂粒子の形状を所望の異形形状に制御することが容易となり、異形樹脂粒子の製造が容易となる。
本発明の異形樹脂粒子において、前記第1の樹脂成分は、親水性樹脂であることが好ましい。前記親水性樹脂としては、水酸基、カルボキシル基、スルホ基、およびアミノ基からなる群より選ばれる少なくとも1種の親水性置換基を有する樹脂が好ましい。親水性置換基を有する樹脂は、例えば、水酸基、カルボキシル基、スルホ基、およびアミノ基からなる群より選ばれる少なくとも1種の親水性置換基を有する重合性ビニル系単量体を単独重合または共重合することにより得られる。重合性ビニル系単量体は、重合可能なアルケニル基(広義のビニル基)を1分子中に少なくとも1つ有する化合物である。親水性置換基を有する重合性ビニル系単量体としては、例えば、(メタ)アクリル酸、(メタ)アクリルアミド、(メタ)アクリル酸2-ヒドロキシルエチル、水酸基を含む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等の(メタ)アクリル酸誘導体が挙げられる。
一般式(1)の単量体において、mが50より大きい場合およびnが50より大きい場合には、重合時に重合安定性が低下し、合着粒子が発生することがある。mおよびnは、0~30の範囲内であることが好ましく、0~15の範囲内であることがより好ましい。
前記一般式(1)で表される化合物としては、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、ポリプロピレングリコールモノメタクリレート、メトキシポリエチレングリコールモノメタクリレート等が好適である。
本発明の異形樹脂粒子において、前記第2の樹脂成分は、疎水性樹脂であることが好ましい。前記疎水性樹脂としては、フッ化アルキル、塩化アルキル、臭化アルキル、ヨウ化アルキル基等のハロゲン化アルキル基を有する樹脂、シクロヘキシル基等の脂環式炭化水素基を有する樹脂が好ましい。ハロゲン化アルキル基を有する樹脂は、ハロゲン化アルキル基を有する重合性ビニル系単量体を単独重合または共重合することにより得られる。このようなハロゲン化アルキル基を有する重合性ビニル系単量体としては、メタクリル酸トリフルオロメチル、アクリル酸2,2,2-トリフルオロエチル、メタクリル酸2,2,2-トリフルオロエチル、アクリル酸2,2,3,3-テトラフルオロプロピル、メタクリル酸2,2,3,3-テトラフルオロプロピル、メタクリル酸2,2,3,4,4,4-ヘキサフルオロブチル、アクリル酸1H,1H,5H-オクタフルオロペンチル、メタクリル酸1H,1H,5H-オクタフルオロペンチル、メタクリル酸パーフルオロオクチルエチル、アクリル酸パーフルオロオクチルエチル等のような、炭素数2~10のフッ化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が挙げられる。脂環式炭化水素基を有する樹脂は、脂環式炭化水素基を有する重合性ビニル系単量体を単独重合または共重合することにより得られる。脂環式炭化水素基を有する重合性ビニル系単量体としては、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸イソボルニル等のような、脂環式炭化水素基をエステル部に含む(メタ)アクリル酸エステルが挙げられる。これら重合性ビニル系単量体は、1種のみを用いてもよく、2種以上を混合して用いてもよい。
ハロゲン化アルキル基を有する重合性ビニル系単量体としては、フッ化アルキル基を有する重合性ビニル系単量体が好ましい。これにより、屈折率が低く、透明性の高い異形樹脂粒子が得られ易くなる。また、ハロゲン化アルキル基を有する重合性ビニル系単量体としては、炭素数2~10のハロゲン化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が好ましく、炭素数2~10のフッ化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がより好ましい。これにより、単量体混合物が重合する過程で単量体混合物の重合体が樹脂粒子から相分離し易くなり、本発明に特有の異形形状および偏在構造が得られ易くなる。ハロゲン化アルキル基に含まれるハロゲン原子の個数は、対応するアルキル基の全水素原子数に対して、40%以上であることが好ましく、50%以上であることがより好ましい。これにより、単量体混合物が重合する過程で単量体混合物の重合体が樹脂粒子から相分離し易くなり、本発明に特有の異形形状および偏在構造が得られ易くなる。例えば、2,2,2-トリフルオロエチル基の場合、対応するアルキル基の全水素原子数が5個であり、ハロゲン原子の数が3個であるから、60%の割合で対応するアルキル基の水素がハロゲン原子で置換されていることになる。
本発明に係る異形樹脂粒子の製造方法は、樹脂からなる粒子(以下「樹脂粒子」と呼ぶ)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こと、または、樹脂を重合性ビニル系単量体に溶解させ、得られた溶液を水性媒体中で重合させることにより、異形樹脂粒子を得る異形樹脂粒子の製造方法であって、前記樹脂が、炭素数2~10のハロゲン化アルキル基または脂環式炭化水素基をエステル部に含む(メタ)アクリル酸エステルに由来する部位を含み、かつ15万~100万の範囲内の重量平均分子量(ゲルパーミエーションクロマトグラフィーによって測定された値)を有する樹脂であり、前記重合性ビニル系単量体が、前記重合性ビニル系単量体の全量に対して5~50重量%の架橋性単量体を含んでいる。この方法により、本発明の異形樹脂粒子を高い確実性で製造することができる。
まず、本発明に係る異形樹脂粒子の製造方法のうち、樹脂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ことにより、異形樹脂粒子を得る方法、すなわち、シード重合を用いた異形樹脂粒子の製造方法について説明する。
樹脂粒子製造工程では、炭素数2~10のハロゲン化アルキル基または脂環式炭化水素基をエステル部に含む(メタ)アクリル酸エステルを含む疎水性単量体を重合して樹脂粒子を得る。
次に、樹脂粒子製造工程において必要に応じて用いられる(メタ)アクリル酸エステル重合体粒子の製造方法について説明する。
シード重合工程では、樹脂粒子製造工程で得られた樹脂粒子に、単量体混合物の全量に対して5~50重量%の架橋性単量体を含む水性乳化液中の単量体混合物を吸収させ、吸収させた単量体混合物を重合させる。
前記架橋性単量体は、重合可能なアルケニル基(広義のビニル基)を1分子中に2つ以上有する化合物である。前記架橋性単量体としては、特に限定されず公知の単量体を何れも使用できるが、例えば、エチレングリコールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ジビニルベンゼン等が挙げられる。前記架橋性単量体の使用量は、前記単量体混合物の全量に対して5~50重量%の範囲内であるが、前記単量体混合物の全量に対して10~40重量%の範囲内であることがより好ましい。架橋性単量体の使用量が5重量%より小さい場合および架橋性単量体の使用量が50重量%より大きい場合には、単量体混合物が重合する過程で前記単量体混合物の重合体と樹脂粒子との相分離が起こり難くなって、本発明に特有の異形形状および偏在構造が得られ難くなる。
前記単量体混合物は、水酸基、カルボキシル基、スルホ基、およびアミノ基からなる群より選ばれる少なくとも1種の親水性置換基を有する重合性ビニル系単量体、および20℃における水に対する溶解度が1重量%以上の重合性ビニル系単量体の少なくとも一方でない他の重合性ビニル系単量体を含んでいてもよい。前記他の重合性ビニル系単量体としては、(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tert-ブチル等の(メタ)アクリル酸誘導体等が挙げられる。前記他の重合性ビニル系単量体としては、(メタ)アクリル酸エステルが好ましく、直鎖アルキル(メタ)アクリレートがより好ましい。これら化合物は、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。他の重合性ビニル系単量体の使用量は、前記単量体混合物の全量に対して、20重量%以下であることが好ましく、10重量%以下であることがより好ましい。
次に、本発明に係る異形樹脂粒子の製造方法のうち、樹脂を単量体混合物に溶解させ、得られた溶液を水性媒体中で重合させることにより、異形樹脂粒子を得る方法について説明する。
樹脂溶液を用いた製造方法における樹脂製造工程は、前述したシード重合を用いた製造方法における樹脂粒子製造工程と同様にして行うことができるが、前記樹脂製造工程の重合法としては、乳化重合を用いるよりも懸濁重合を用いることが好ましい。また、前記樹脂製造工程の重合法としては、溶液重合、塊状重合等を用いることも可能である。以下に懸濁重合を用いて粒子状の樹脂(樹脂からなる粒子)を得る方法について述べるが、この方法に限定されるものではない。
油相と水性媒体とを調製した後、水性媒体に油相を添加し、混合攪拌し懸濁液を得る。このとき、油相は、油滴を形成する。このとき、攪拌手段としてホモジナイザーを用いることで攪拌時間、回転数等の攪拌条件を変化させて油滴サイズ、他の攪拌手段を用いた場合に比べて容易に調整できる。油滴サイズを調整できることは、油滴から得られる粒子のサイズを調整できることを意味する。
次に、水系重合工程では、樹脂製造工程で得られた樹脂を、前記シード重合工程の項で説明した前記単量体混合物に溶解させ、得られた溶液を水性媒体中で重合させる。樹脂を前記単量体混合物に溶解させるには、樹脂を前記単量体混合物と混合すればよい。樹脂1重量部と混合する前記単量体混合物の量は、1~125重量部の範囲内であることが好ましく、5~50重量部の範囲内であることがより好ましく、10~30重量部の範囲内であることがさらに好ましい。樹脂1重量部と混合する前記単量体混合物の量が1重量部未満である場合、樹脂を十分に溶解させることができないことがある。樹脂粒子1重量部と混合する前記単量体混合物の量が125重量部より多い場合、得られる異形樹脂粒子における第2の樹脂成分の割合が小さくなり過ぎて、第2の樹脂成分の偏在による効果が僅かしか得られない可能性がある。
以上のようにして、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、非真球形状を有する異形樹脂粒子であって、架橋性単量体を含む単量体混合物に由来する第1の樹脂成分と、樹脂(疎水性単量体の重合体)に由来する第2の樹脂成分とを含み、前記異形樹脂粒子の表面近傍に前記第2の樹脂成分が偏在している本発明の異形樹脂粒子を製造することができる。
本発明の異形樹脂粒子は、塗料、紙用コーティング剤、情報記録紙用コーティング剤、光拡散フィルム(光学シート)用等の光拡散部材用コーティング剤等として用いられるコーティング剤(塗布用組成物)の添加剤;光拡散板製造用の光拡散性樹脂組成物を構成する光拡散剤;化粧品等の外用剤の添加剤;界面活性剤等として有用である。
本発明の異形樹脂粒子は、塗膜軟質化剤、塗料用艶消し剤、光拡散剤等としてコーティング剤に含有させることが可能である。本発明のコーティング剤は、本発明の異形樹脂粒子を含んでいる。
前記コーティング剤は、必要に応じて、媒体を含んでいる。前記媒体として、バインダー樹脂を溶解できる溶剤(溶媒)、またはバインダー樹脂を分散できる分散媒を使用することが好ましい。分散媒または溶媒としては、水性の媒体および油性の媒体がいずれも使用できる。油性の媒体としては、トルエン、キシレン等の炭化水素系溶剤;メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤;酢酸エチル、酢酸ブチル等のエステル系溶剤;ジオキサン、エチレングリコールジエチルエーテル、エチレングリコールモノブチルエーテル等のエーテル系溶剤等が挙げられる。水性の媒体としては、水、アルコール類(例えばイソプロパノール)等が挙げられる。これら溶剤は、1種のみを使用してもよく、2種以上を混合して使用してもよい。コーティング剤中における媒体の含有量は、コーティング剤全量に対し、通常、20~60重量%の範囲内である。
コーティング剤を使用した塗膜の形成方法は、特に限定されず、公知の方法をいずれも使用できる。塗膜の形成方法としては、例えば、スプレー塗装法、ロール塗装法、ハケ塗り法等の方法が挙げられる。コーティング剤は、必要に応じて粘度を調整するために、希釈剤を加えて希釈してもよい。希釈剤としては、トルエン、キシレン等の炭化水素系溶剤;メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤;酢酸エチル、酢酸ブチル等のエステル系溶剤;ジオキサン、エチレングリコールジエチルエーテル等のエーテル系溶剤;水;アルコール系溶剤等が挙げられる。これら希釈剤は、単独で使用してもよく、2種以上を混合して使用してもよい。光拡散部材を製造する場合には、塗膜の形成方法としては、異形樹脂粒子に由来する凹凸が塗膜表面に形成されるような方法を使用することが好ましい。
本発明の異形樹脂粒子を光拡散剤として、透明基材樹脂(透明性樹脂)中に分散させることで、光拡散性樹脂組成物として使用できる。すなわち、前記光拡散性樹脂組成物は、本発明の異形樹脂粒子と、透明基材樹脂とを含んでいる。前記光拡散性樹脂組成物は、照明カバー(発光ダイオード(LED)照明用照明カバー、蛍光灯照明用照明カバー等)、光拡散部材(光拡散シートあるいは光拡散フィルム、光拡散板等)の原料として使用できる。
本発明の異形樹脂粒子は、外用剤の原料として、例えば外用剤の滑り性向上剤として、使用できる。本発明の外用剤は、本発明の異形樹脂粒子を含んでいる。前記外用剤としては、例えば化粧料(化粧品)、外用医薬品等が挙げられる。
これらの外用剤には、本発明の効果を損なわない範囲で、一般に用いられている主剤または添加物を目的に応じて配合できる。そのような主剤または添加物としては、例えば、粘土鉱物類(光沢向上および触感向上などの数種の機能を兼ね備えた成分;マイカ、タルク等)、着色用顔料(赤色酸化鉄、黄色酸化鉄、酸化チタン、群青、紺青、カーボンブラック等)、アゾ系染料等の合成染料、水、低級アルコール(炭素数5以下のアルコール)、高級アルコール(セチルアルコール等の炭素数6以上のアルコール)、炭化水素(ワセリン、流動パラフィン等)、シリコーンオイル、植物性油脂、動物性油脂、ロウ類、高級脂肪酸(ステアリン酸等の炭素数12以上の脂肪酸)、ステロール、脂肪酸エステル(ミリスチン酸オクチルドデシル、オレイン酸エステル等)、金属石鹸、保湿剤、抗炎症剤、美白剤、UVケア剤、殺菌剤、制汗剤、清涼剤、香料、界面活性剤(ポリエチレングリコール等)、高分子化合物、防腐・殺菌剤、酸化防止剤、紫外線吸収剤、アクリル樹脂粒子(ポリ(メタ)アクリル酸エステル粒子)、シリコーン系粒子、ポリスチレン粒子等の樹脂粒子、本発明の異形樹脂粒子以外の異形樹脂粒子、pH調整剤(トリエタノールアミン等)、特殊配合添加物、医薬品活性成分等が挙げられる。
本発明の異形樹脂粒子は、表面の一部が、親水性樹脂からなる第1の樹脂成分で形成され、残りの表面が、疎水性樹脂からなる第2の樹脂成分で形成された構成である場合、親水性表面と疎水性表面とを有するので、界面活性剤としての機能を有している。したがって、本発明の異形樹脂粒子は、油等の油性媒体(または油相成分)を水性媒体(または水相成分)中に分散させて乳化させるか、あるいは水性媒体(または水相成分)を油性媒体(または油相成分)中に分散させて乳化させるための乳化剤、洗剤、帯電防止剤、潤滑剤、柔軟剤、防曇・展着剤、媒染剤等として利用できると考えられる。
本発明のエマルジョンは、本発明の異形樹脂粒子を含んでいる。本発明のエマルジョンでは、本発明の異形樹脂粒子が乳化剤として機能する。本発明のエマルジョンは、水相成分および油相成分を含むものであり、油性成分の液滴が水性成分中に分散する水中油滴型エマルジョンと、水性成分の液滴が油性成分中に分散する油中水滴型エマルジョンとのいずれであってもよい。
本発明の光学部材は、基材と、複数個の本発明の異形樹脂粒子とを含む光学部材であって、前記複数個の異形樹脂粒子の各々は、半球面部と平面部とを有する半球形状であり、前記複数個の異形樹脂粒子は、それらの平面部が前記基材に対向するように前記基材上に配列されている。
重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)を用いて測定した。測定した重量平均分子量は、ポリスチレン(PS)換算重量平均分子量である。その測定方法は、次の通りである。まず、試料50mgをテトラヒドロフラン(THF)10mlに溶解させた。得られた溶液を0.45μmの非水系クロマトディスクを用いて濾過した。得られた濾液をGPCにより分析し、PS換算重量平均分子量を測定した。GPCの測定条件は、下記の通りとした。
カラム:東ソー株式会社製の商品名「TSKgel GMH XL-L」(直径7.8mm×長さ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:1mL/分
注入・ポンプ温度:35℃
検出:RI(示差屈折率検出器)
注入量:100μL
PS換算重量平均分子量を算出するための検量線用標準ポリスチレン:昭和電工株式会社製の商品名「shodex」(重量平均分子量:1030000)および東ソー株式会社製の検量線用標準ポリスチレン(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、レーザー回折散乱粒度分布測定装置(ベックマン・コールター株式会社製、LS230型)で測定した。具体的には、試験管に、種粒子0.1gおよび0.1重量%ノニオン性界面活性剤溶液10mlを投入し、タッチミキサー(ヤマト科学株式会社製、「TOUCHMIXER MT-31」)で2秒間混合した。この後、試験管内の種粒子を市販の超音波洗浄器(株式会社ヴェルヴォクリーア製、「ULTRASONIC CLEARNER VS-150」)を用いて10分間かけて分散させて、分散液を得た。分散液に超音波を照射しながら、分散液中の種粒子の平均粒子径をレーザー回折散乱粒度分布測定装置(ベックマン・コールター株式会社製、LS230型)にて測定した。その測定のときの光学モデルは、作製した種粒子の屈折率に合わせた。種粒子の製造に1種類の単量体を用いた場合には、種粒子の屈折率としてその単量体の単独重合体の屈折率を用いた。種粒子の製造に複数種類の単量体を用いた場合には、種粒子の屈折率として、各単量体の単独重合体の屈折率を各単量体の使用量で加重平均した平均値を用いた。
異形樹脂粒子の長さA~Iは、以下のようにして測定した。走査型電子顕微鏡「JSM-6360LV」(日本電子株式会社製)を用いて5,000~10,000倍の倍率で任意の30個の異形樹脂粒子を観察し、各異形樹脂粒子の各部位(A~Iに相当する部位)の長さを測定し、30個の測定値の平均値を長さA~Iとした。
異形樹脂粒子の球換算体積平均粒子径は、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解質溶液の導電率変化から体積を求めることによって、計算した。具体的には、異形樹脂粒子の球換算体積平均粒子径は、コールター方式精密粒度分布測定装置マルチサイザーII(ベックマン・コールター株式会社製)を用いてコールター方式にて測定した体積平均粒子径(体積基準の粒度分布における算術平均径)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マルチサイザーIIのキャリブレーションを行い、測定を行った。
攪拌機、温度計および還流コンデンサーを備えたセパラブルフラスコに、水性媒体としての水600gと、(メタ)アクリル酸エステルとしてのメタクリル酸メチル100gと、連鎖移動剤としてのn-ドデシルメルカプタン0.5gとを仕込み、セパラブルフラスコの内容物を攪拌機で攪拌しながらセパラブルフラスコ内の空間を窒素置換し、セパラブルフラスコの内温を70℃に昇温した。セパラブルフラスコの内温を70℃に保ちながら、重合開始剤として過硫酸カリウム0.5gをセパラブルフラスコの内容物に添加した後、セパラブルフラスコの内温を70℃に保ったまま8時間かけて重合反応させ、エマルジョン(水性乳化液)を得た。得られたエマルジョンは、固形分(メタクリル酸メチル重合体)を14重量%含有し、その固形分は、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。
n-ドデシルメルカプタンを使用しないこと以外は種粒子形成用エマルジョンの合成例1と同様にして重合を行い、エマルジョンを得た。得られたエマルジョンは固形分(メタクリル酸メチル重合体)を14重量%含有し、その固形分は、平均粒子径0.43μm、重量平均分子量85万の真球状微粒子からなっていた。
攪拌機、温度計、および還流コンデンサーを備えたセパラブルフラスコに、水性媒体としての水550gと、合成例1で得られたエマルジョン70gと、炭素数2~10のハロゲン化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としてのメタクリル酸2,2,2-トリフルオロエチル100gと、連鎖移動剤としてのn-ドデシルメルカプタン0.3gとを仕込み、セパラブルフラスコの内容物を攪拌機で攪拌しながらセパラブルフラスコ内の空間を窒素置換し、セパラブルフラスコの内温を70℃に昇温した。セパラブルフラスコの内温を70℃に保ちながら、重合開始剤としての過硫酸カリウム0.5gを添加した後、セパラブルフラスコの内温を70℃に保ったまま8時間かけて重合反応させた。これにより、種粒子を含有するエマルジョン(以下「種粒子含有エマルジョン」と呼ぶ)が得られた。
合成例1で得られたエマルジョン70gに代えて合成例2で得られたエマルジョン70gを用いること、およびn-ドデシルメルカプタンを使用しないことを除いて種粒子製造例1と同様にして重合を行い、種粒子含有エマルジョンを得た。
メタクリル酸2,2,2-トリフルオロエチル100gに代えてメタクリル酸メチル100gを用いること、およびn-ドデシルメルカプタンを使用しないことを除いて種粒子製造例1と同様にして重合を行い、種粒子含有エマルジョンを得た。
メタクリル酸2,2,2-トリフルオロエチル100gに代えてメタクリル酸シクロヘキシル100gを用いる以外は種粒子製造例1と同様にして重合を行い、種粒子含有エマルジョンを得た。
まず、炭素数2~10のハロゲン化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としてのメタクリル酸2,2,2-トリフルオロエチル85重量部およびメタクリル酸メチル15重量部からなる重合性ビニル系単量体(疎水性単量体)に、重合開始剤としての過酸化ベンゾイル0.5重量部と、連鎖移動剤としてのn-ドデシルメルカプタン3重量部とを溶解させて、混合液を調製した。
攪拌機および温度計を備えた5Lの反応器に、単量体混合物としての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(架橋性単量体;重合性ビニル系単量体の全量に対して30重量%)、およびポリ(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、前記一般式(1)で表される複数の化合物からなる混合物であって、R1=CH3、R2=C2H5、R3=C3H6、R4=Hであり、mが平均して3.5であり、nが平均して2.5であるもの)100gと、重合開始剤としての2,2’-アゾビスイソブチロニトリル6gとを入れ、攪拌機で攪拌することにより混合した。得られた混合物を、アニオン系界面活性剤としてのジオクチルスルホコハク酸ナトリウム10gが含まれたイオン交換水1Lと混合し、微細乳化機としての高速乳化・分散機「T.Kホモミキサー」(プライミクス株式会社製)にて8000rpmの攪拌速度で10分間かけて攪拌することにより、水性乳化液を得た。この水性乳化液に、種粒子製造例1で製造した平均粒子径が1.0μmの種粒子含有エマルジョン360gを攪拌機で攪拌しながら加えた。
また、得られた半球形状の異形樹脂粒子を包埋樹脂(エポキシ樹脂)に包埋した後、包埋樹脂で包埋された異形樹脂粒子から異形樹脂粒子の中心を含む薄切片を切り出し、薄切片を染色剤(四酸化ルテニウム)により染色して透過型電子顕微鏡(TEM)で撮像し、図6のTEM画像を得た。得られた半球形状の異形樹脂粒子は、図6に示すように、架橋性単量体を含む単量体混合物に由来する第1の樹脂成分(色が薄く、大きい方の灰色部分)と、種粒子に由来する第2の樹脂成分(色が濃く、小さい方の灰色部分)とを含み、第2の樹脂成分が異形樹脂粒子の表面近傍に偏在していた。また、得られた半球形状の異形樹脂粒子は、図6に示すように、平面部の表面のほぼ全てが第2の樹脂成分で形成されており、異形樹脂粒子における残りの表面が、第1の樹脂成分で形成されていた。なお、図6のTEM画像、並びに、後段の実施例に関する図8、図10、図16、および図18のTEM画像において、第2の樹脂成分表面に存在する黒色部分は、異形樹脂粒子と包埋樹脂との境界部に入り込んだ染色剤に起因して黒くなっているものであり、第1および第2の樹脂成分以外の成分が異形樹脂粒子中に存在することを示すものではない。
種粒子製造例1で製造した種粒子含有エマルジョンの使用量を360gから180gに変更したこと以外は実施例1と同様にして樹脂粒子を得た。
また、得られた断面馬蹄形状の異形樹脂粒子を包埋樹脂(エポキシ樹脂)に包埋した後、包埋樹脂で包埋された異形樹脂粒子から異形樹脂粒子の中心を含む薄切片を切り出し、薄切片を染色剤(四酸化ルテニウム)により染色してTEMで撮像し、図8のTEM画像を得た。得られた断面馬蹄形状の異形樹脂粒子は、図8に示すように、架橋性単量体を含む単量体混合物に由来する第1の樹脂成分(色が薄く、大きい方の灰色部分)と、種粒子に由来する第2の樹脂成分(色が濃く、小さい方の灰色部分)とを含み、第2の樹脂成分が異形樹脂粒子の表面近傍に偏在していた。また、得られた断面馬蹄形状の異形樹脂粒子は、図8に示すように、切り欠き部の表面の半分より多くの部分が第2の樹脂成分で形成されており、異形樹脂粒子における残りの表面が、第1の樹脂成分で形成されていた。
メタクリル酸メチル600gおよびポリ(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100gに代えてメタクリル酸メチル700gを用いたこと以外は実施例1と同様にして樹脂粒子を得た。
また、得られた両凸レンズ形状の異形樹脂粒子を包埋樹脂(エポキシ樹脂)に包埋した後、包埋樹脂で包埋された異形樹脂粒子から異形樹脂粒子の中心を含む薄切片を切り出し、薄切片を染色剤(四酸化ルテニウム)により染色してTEMで撮像し、図10のTEM画像を得た。得られた両凸レンズ形状の異形樹脂粒子は、図10に示すように、架橋性単量体を含む単量体混合物に由来する第1の樹脂成分(色が濃く、大きい方の灰色部分)と、種粒子に由来する第2の樹脂成分(色が薄く、小さい方の灰色部分)とを含み、第2の樹脂成分が異形樹脂粒子の表面近傍に偏在していた。また、得られた両凸レンズ形状の異形樹脂粒子は、図10に示すように、小さい方の平凸レンズ形状部の表面のほぼ全てが第2の樹脂成分で形成されており、異形樹脂粒子における残りの表面が、第1の樹脂成分で形成されていた。
種粒子製造例1で製造した種粒子含有エマルジョン360gに代えて種粒子製造例2で製造した種粒子含有エマルジョン360gを用いたこと以外は実施例3と同様にして樹脂粒子を得た。
また、得られたマッシュルーム形状の異形樹脂粒子を包埋樹脂(エポキシ樹脂)に包埋した後、包埋樹脂で包埋された異形樹脂粒子から異形樹脂粒子の中心を含む薄切片を切り出し、薄切片を染色剤(四酸化ルテニウム)により染色してTEMで撮像し、図12のTEM画像を得た。得られたマッシュルーム形状の異形樹脂粒子は、図12に示すように、架橋性単量体を含む単量体混合物に由来する第1の樹脂成分(色が薄く、大きい方の灰色部分)と、種粒子に由来する第2の樹脂成分(色が濃く、小さい方の灰色部分)とを含み、第2の樹脂成分が異形樹脂粒子の表面近傍に偏在していた。また、得られたマッシュルーム形状の異形樹脂粒子は、図12に示すように、軸部の表面の半分より多くの部分が第2の樹脂成分で形成されており、異形樹脂粒子における残りの表面が、第1の樹脂成分で形成されていた。なお、図12のTEM画像において、第1の樹脂成分表面および第2の樹脂成分表面に存在する黒色部分は、異形樹脂粒子と包埋樹脂との境界部に入り込んだ染色剤に起因して黒くなっているものであり、第1および第2の樹脂成分以外の成分が異形樹脂粒子中に存在することを示すものではない。
まず、メタクリル酸メチル60重量部、ジメタクリル酸エチレングリコール30重量部、およびポリ(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」)10重量部からなる単量体混合物に、メタクリル酸2,2,2-トリフルオロエチル-メタクリル酸メチル共重合体の製造例1で製造したメタクリル酸2,2,2-トリフルオロエチル-メタクリル酸メチル共重合体(樹脂からなる粒子)5重量部と、重合開始剤としての過酸化ベンゾイル0.5重量部およびアゾビスイソブチロニトリル0.5重量部とを溶解させて、混合溶液を調製した。
また、得られた断面馬蹄形状の異形樹脂粒子を包埋樹脂(エポキシ樹脂)に包埋した後、包埋樹脂で包埋された異形樹脂粒子から異形樹脂粒子の中心を含む薄切片を切り出し、薄切片を染色剤(四酸化ルテニウム)により染色してTEMで撮像し、図14のTEM画像を得た。得られた断面馬蹄形状の異形樹脂粒子は、図14に示すように、架橋性単量体を含む単量体混合物に由来する第1の樹脂成分(色が濃く、大きい方の灰色部分)と、メタクリル酸2,2,2-トリフルオロエチル-メタクリル酸メチル共重合体に由来する第2の樹脂成分(色が薄く、小さい方の灰色部分)とを含み、第2の樹脂成分が異形樹脂粒子の表面近傍に偏在していた。また、得られた断面馬蹄形状の異形樹脂粒子は、図14に示すように、切り欠き部の表面の半分より多くの部分が第2の樹脂成分で形成されており、異形樹脂粒子における残りの表面が、第1の樹脂成分で形成されていた。なお、図14のTEM画像において、第1の樹脂成分表面に存在する黒色部分は、異形樹脂粒子と包埋樹脂との境界部に入り込んだ染色剤に起因して黒くなっているものであり、第1および第2の樹脂成分以外の成分が異形樹脂粒子中に存在することを示すものではない。
種粒子製造例1で製造した種粒子含有エマルジョン360gに代えて種粒子製造例4で製造した種粒子含有エマルジョン360gを用いたこと以外は実施例3と同様にして樹脂粒子を得た。
また、得られた両凸レンズ形状の異形樹脂粒子を包埋樹脂(エポキシ樹脂)に包埋した後、包埋樹脂で包埋された異形樹脂粒子から異形樹脂粒子の中心を含む薄切片を切り出し、薄切片を染色剤(四酸化ルテニウム)により染色してTEMで撮像し、図16のTEM画像を得た。得られた両凸レンズ形状の異形樹脂粒子は、図16に示すように、架橋性単量体を含む単量体混合物に由来する第1の樹脂成分(色が薄く、大きい方の灰色部分)と、種粒子に由来する第2の樹脂成分(色が濃く、小さい方の灰色部分)とを含み、第2の樹脂成分が異形樹脂粒子の表面近傍に偏在していた。また、得られた両凸レンズ形状の異形樹脂粒子は、図16に示すように、小さい方の平凸レンズ形状部の表面のほぼ全てが第2の樹脂成分で形成されており、異形樹脂粒子における残りの表面が、第1の樹脂成分で形成されていた。
〔実施例7〕
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100gに代えてメトキシポリエチ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)PME-400」、日油株式会社製、前記一般式(1)で表される複数の化合物からなる混合物であって、R1=CH3、R2=C2H5、R4=CH3であり、mが平均して9であり、nが0であるもの)を用いたこと、および、種粒子製造例1で製造した種粒子含有エマルジョン360gに代えて種粒子製造例4で製造した種粒子含有エマルジョン360gを用いたことを除いて実施例1と同様にして、樹脂粒子を得た。
また、得られた半球形状の異形樹脂粒子を包埋樹脂(エポキシ樹脂)に包埋した後、包埋樹脂で包埋された異形樹脂粒子から異形樹脂粒子の中心を含む薄切片を切り出し、薄切片を染色剤(四酸化ルテニウム)により染色して透過型電子顕微鏡(TEM)で撮像し、図18のTEM画像を得た。得られた半球形状の異形樹脂粒子は、図18に示すように、架橋性単量体を含む単量体混合物に由来する第1の樹脂成分(色が薄く、大きい方の灰色部分)と、種粒子に由来する第2の樹脂成分(色が濃く、小さい方の灰色部分)とを含み、第2の樹脂成分が異形樹脂粒子の表面近傍に偏在していた。また、得られた半球形状の異形樹脂粒子は、図18に示すように、平面部の表面のほぼ全てが第2の樹脂成分で形成されており、異形樹脂粒子における残りの表面が、第1の樹脂成分で形成されていた。
〔比較例1〕
種粒子製造例1で製造した種粒子含有エマルジョン360gに代えて種粒子製造例3で製造した種粒子含有エマルジョン360gを用いたことを除いて実施例1と同様にして、樹脂粒子を得た。
実施例1で得られた半球形状の異形樹脂粒子20.0重量部と、粘土鉱物類としてのセリサイト6.0重量部と、二酸化チタン3.0重量部と、顔料(適量)とを混合し、粉末部を調製した。
写真より、異形樹脂粒子が液滴表面に存在していることが確認できた。
実施例1で得られた半球形状の異形樹脂粒子に代えて比較例1で得られた真球状の樹脂粒子を用いたこと以外は実施例と同様にして、比較用の乳化型ファンデーション(エマルジョン化粧料)を得た。
実施例1で得られた半球形状の異形樹脂粒子5重量部をイソプロパノール10重量部と混合し、遠心攪拌機にて3分間攪拌し、分散液を得た。この分散液を、蒸留水を入れたビーカーの水面上に、スポイトを用いて静かに展開した。展開後、透明フィルム基材としてのPETフィルムを水面に入れ、展開した分散液をPETフィルム上に移しとり、70℃に保ったオーブンで1時間乾燥し、光拡散部材(光学部材の一形態)の一形態としての光拡散フィルムを得た。
2,5,12 第2の樹脂成分
3 切り欠き部
6 傘部
7 軸部
13 平面部
16,17 平凸レンズ形状部
Claims (16)
- [規則91に基づく訂正 15.01.2013]
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、非真球形状を有する異形樹脂粒子であって、
第1の樹脂成分と、
前記第1の樹脂成分と異なる第2の樹脂成分とを含み、
前記異形樹脂粒子の表面近傍に前記第2の樹脂成分が偏在していることを特徴とする異形樹脂粒子。 - 請求項1に記載の異形樹脂粒子であって、
前記非真球形状が、球の一部が欠けた形状であり、
前記異形樹脂粒子における欠けた部分の表面の少なくとも一部が第2の樹脂成分で形成されており、前記異形樹脂粒子における残りの表面が第1の樹脂成分で形成されていることを特徴とする異形樹脂粒子。 - 請求項1または2に記載の異形樹脂粒子であって、
前記非真球形状が、半球形状であることを特徴とする異形樹脂粒子。 - 請求項1または2に記載の異形樹脂粒子であって、
前記非真球形状が、両凸レンズ形状であることを特徴とする異形樹脂粒子。 - 請求項1または2に記載の異形樹脂粒子であって、
前記非真球形状が、マッシュルーム形状であることを特徴とする異形樹脂粒子。 - 請求項1または2に記載の異形樹脂粒子であって、
前記非真球形状が、断面馬蹄形状であることを特徴とする異形樹脂粒子。 - 請求項1~6の何れか1項に記載の異形樹脂粒子であって、
前記第1の樹脂成分が、親水性樹脂であり、
前記第2の樹脂成分が、疎水性樹脂であることを特徴とする異形樹脂粒子。 - 樹脂からなる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こと、または、樹脂を重合性ビニル系単量体に溶解させ、得られた溶液を水性媒体中で重合させることにより、異形樹脂粒子を得る異形樹脂粒子の製造方法であって、
前記樹脂が、炭素数2~10のハロゲン化アルキル基または脂環式炭化水素基をエステル部に含む(メタ)アクリル酸エステルに由来する部位を含み、かつ15万~100万の範囲内の重量平均分子量(ゲルパーミエーションクロマトグラフィーによって測定された値)を有する樹脂であり、
前記重合性ビニル系単量体が、前記重合性ビニル系単量体の全量に対して5~50重量%の架橋性単量体を含むことを特徴とする異形樹脂粒子の製造方法。 - 請求項1~7のいずれか1項に記載の異形樹脂粒子を含むことを特徴とする乳化剤。
- 請求項1~7のいずれか1項に記載の異形樹脂粒子を含むことを特徴とする外用剤。
- 請求項1~7のいずれか1項に記載の異形樹脂粒子を含むことを特徴とするエマルジョン。
- 請求項1~7のいずれか1項に記載の異形樹脂粒子を含むことを特徴とするコーティング剤。
- 請求項1~7のいずれか1項に記載の異形樹脂粒子を含むことを特徴とする光拡散部材。
- 基材と、請求項1~7のいずれか1項に記載の複数の異形樹脂粒子とを含む光学部材であって、
前記複数の異形樹脂粒子は、半球形状であり、
前記複数の異形樹脂粒子は、それらの平面部が前記基材に対向するように前記基材上に配列されていることを特徴とする光学部材。 - 光拡散フィルムである請求項15の光学部材であって、
前記基材が、透明フィルム基材であることを特徴とする光学部材。
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CN201280041434.5A CN103764687B (zh) | 2011-08-25 | 2012-08-27 | 异形树脂粒子及其制造方法与其用途 |
EP12825843.1A EP2754676B1 (en) | 2011-08-25 | 2012-08-27 | Non-spherical resin particles, manufacturing method thereof, and use thereof |
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KR101689620B1 (ko) | 2012-01-31 | 2016-12-26 | 세키스이가세이힝코교가부시키가이샤 | 다공질 수지 입자, 그 제조 방법, 분산액 및 그 용도 |
JP6401992B2 (ja) * | 2014-09-30 | 2018-10-10 | 日本乳化剤株式会社 | 塗料用エマルジョン組成物 |
CN104945647B (zh) * | 2015-04-14 | 2018-06-26 | 常州大学 | 一种增透pet薄膜的制备方法 |
US9957468B2 (en) | 2015-11-06 | 2018-05-01 | The Procter & Gamble Company | Shaped particles |
EP3438169A4 (en) * | 2016-03-31 | 2020-04-01 | Sekisui Plastics Co., Ltd. | METAL-COVERED IRREGULAR-SHAPED RESIN PARTICLES AND METHOD FOR THE PRODUCTION THEREOF, ORIENTED FILM OF METAL-COVERED IRON-SHAPED RESIN PARTICLES AND METHOD FOR THE PRODUCTION THEREOF, PARTICLES AND METHOD FOR THE PRODUCTION THEREOF |
KR102095003B1 (ko) | 2017-01-03 | 2020-03-30 | 주식회사 엘지화학 | 수지 입자의 제조 방법 |
KR102234168B1 (ko) * | 2019-05-30 | 2021-03-31 | 주식회사 넥센 | 골프공용 코팅 조성물 |
US11186745B2 (en) | 2019-05-30 | 2021-11-30 | Nexen Corporation | Coating composition for golf balls |
CN110615875B (zh) * | 2019-10-16 | 2022-10-25 | 佛山市顺德区巴德富实业有限公司 | 一种速干型抗起鼓外墙涂料用羟基乳液及其制备方法 |
CN110927847A (zh) * | 2019-12-23 | 2020-03-27 | 宁波长阳科技股份有限公司 | 反射膜及其制备方法 |
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JP3700997B2 (ja) | 1997-11-07 | 2005-09-28 | ガンツ化成株式会社 | 表面にシワ状構造を有する球状ポリマー微粒子およびその製造法 |
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CN103459471B (zh) * | 2011-03-31 | 2016-04-27 | 积水化成品工业株式会社 | 着色树脂粒子、其制造方法及其用途 |
US9527969B2 (en) * | 2011-06-30 | 2016-12-27 | Sekisui Plastics Co., Ltd. | Non-spherical resin particles, manufacturing method thereof, and use thereof |
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US20140194565A1 (en) | 2014-07-10 |
EP2754676A4 (en) | 2015-04-15 |
KR101954111B1 (ko) | 2019-03-05 |
TWI586688B (zh) | 2017-06-11 |
EP2754676A1 (en) | 2014-07-16 |
CN103764687B (zh) | 2016-05-04 |
JP5972880B2 (ja) | 2016-08-17 |
TW201313754A (zh) | 2013-04-01 |
US9187632B2 (en) | 2015-11-17 |
CN103764687A (zh) | 2014-04-30 |
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WO2013027849A1 (ja) | 2013-02-28 |
EP2754676B1 (en) | 2020-01-22 |
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