JP2006306998A - Optical interference resin micro-particle and optical interference composite micro-particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical interference resin micro-particle having optical interference effects and excellent dispersibility in an organic solvent and a binder resin even when the micro-particle is not composed of a material with special properties of exhibiting liquid crystallinity, etc., and developing sufficient pearly color and to provide an optical interference composite micro-particle, a cosmetic, a coating, a coated article coated with the coating, ink and a print printed with the ink. <P>SOLUTION: The optical interference resin micro-particle of a flat shape has voids in the interior. Furthermore, the optical interference resin micro-particle has ≥50% void ratio and 0.1-100 μm volume-average particle diameter. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention is excellent in dispersibility in an organic solvent and a binder resin and exhibits a sufficient pearl color even if it is not made of a material having a light interference effect and having special properties such as liquid crystallinity. The present invention relates to a light interference resin fine particle and a light interference composite fine particle.

Conventionally, by including fine particles having a light interference effect in an organic solvent or a binder resin as a pearl pigment, a pearl color is developed in, for example, inks, paints, plastics, cosmetics, and the like.

This pearl pigment is a particle having a flake shape. By having a core / shell structure of at least two layers having different refractive indexes, the pearl color is changed by the mutual interference action of reflected light from both the particle surface and the layer interface. It expresses.
As a pearl pigment having such a light interference effect, conventionally, a transparent or translucent metal oxide having a high refractive index on a flaky inorganic compound base material having high smoothness such as mica, sericite, talc, etc. A material made of an inorganic material coated with has been used.

However, the pearl pigment made of such an inorganic material has a problem of high polarity and poor affinity for an organic solvent or a binder resin.

In order to solve such a problem, as a method for improving the affinity of particles having a light interference effect to an organic solvent or a binder resin, for example, a method using particles having a light interference effect made of an organic material can be considered.

For example, Patent Document 1 discloses that a light-interfering property is obtained by polymerizing a polymerizable liquid crystal having a polymerizable functional group and a mesogenic group in a molecule or a composition thereof dispersed in an incompatible solvent. A method for obtaining spherical resin particles is disclosed.

The spherical resin particles having the light interference effect are excellent in dispersibility in an organic solvent or a binder resin, but cannot exhibit a sufficient pearl color due to the light interference effect and can be used as a particle material. This is limited to some special materials that exhibit a cholesteric state in a solution state such as a cellulose derivative or a polymerizable liquid crystal.
JP 2003-26707 A

In view of the above situation, the present invention is excellent in dispersibility in an organic solvent and a binder resin even if it is not made of a material having a light interference effect and a special property such as liquid crystallinity. An object of the present invention is to provide a light interference resin fine particle and a light interference composite fine particle capable of exhibiting a simple pearl color.

The present invention is a light interference resin fine particle having a flat shape and having voids therein, having a porosity of 50% or more and a volume average particle diameter of 0.1 to 100 μm.
The present invention is described in detail below.

As a result of intensive studies, the inventors of the present invention have found that flat hollow resin fine particles having a predetermined particle diameter and having a porosity of a certain level or more are reflected light on the surface of the fine particles and the interface between the resin layer and the internal voids. It has been found that a sufficient pearl color can be expressed by the mutual interference effect with the reflected light, and the present invention has been completed.

The light interference resin fine particles of the present invention have voids inside, and the lower limit of the void ratio is 50%. If it is less than 50%, the optical interference resin fine particles of the present invention produced without using a special material exhibiting liquid crystallinity cannot be formed into a flat shape of a certain level or more, which will be described later. Further, the mutual interference effect between the reflected light on the surface of the fine particles and the reflected light at the interface between the resin layer and the internal void becomes insufficient, and a sufficient pearl color cannot be expressed. The preferable lower limit of the porosity is 70%, and the preferable upper limit is 99%.

Moreover, it is preferable that the light interference resin fine particles of the present invention have a single-hole structure having a single void inside. This is because the single-hole structure has a high mutual interference effect between the reflected light on the surface of the fine particles and the reflected light at the interface between the resin layer and the internal voids.

In the light interference resin fine particles of the present invention, the lower limit of the volume average particle diameter is 0.1 μm, and the upper limit is 100 μm. If it is less than 0.1 μm, no light reflection occurs at the particle surface and at the interface between the resin layer and the internal voids, and the light interference effect is not exhibited. If it exceeds 100 μm, the flickering of the powder or the feeling of roughness of the skin becomes a problem when the light interference resin fine particles of the present invention are used as cosmetics. A preferred lower limit is 0.2 μm and a preferred upper limit is 80 μm.

The light interference resin fine particles of the present invention have a flat shape. Such flat optical interference resin fine particles of the present invention can exhibit a suitable pearl color. In the present specification, the “flat shape” means that the shape is flattened to some extent without having a true spherical shape, and specifically, for example, a flat shape such as a disc shape or a meteorite shape, It means a flat shape like broad beans or red blood cells, or a flat shape like rugby balls.
Such a flat optical interference resin fine particle of the present invention may be bilaterally symmetric or bilaterally asymmetric.

The light interference resin fine particles of the present invention preferably have a flat surface. By having the flat surface, the light interference resin fine particles of the present invention have a sufficient light interference effect. Here, the “flat surface” means a surface that is recognized as not a curved surface when the shape of the light interference resin fine particles of the present invention is observed.

More specifically, the flat optical interference resin fine particles of the present invention have a lower limit (1/50) of the ratio (a / b) of the minor axis (a) to the major axis (b) and an upper limit (1). / 1). When (a / b) is less than (1/50), the light interference resin fine particles of the present invention satisfying the above-mentioned volume average particle diameter are too small in short diameter, and the reflected light on the fine particle surface and the resin layer The mutual interference effect with the reflected light at the interface between the inner space and the inner space becomes insufficient, and a sufficient pearl color cannot be expressed. When (a / b) is (1/1), the optical interference resin fine particles of the present invention have the same short diameter and long diameter. The preferable lower limit of the above (a / b) is (1/10).

In the light interference resin fine particles of the present invention, the upper limit of the ratio (c / b) of the thickness (c) to the major axis (b) is preferably (1/2). If (1/2) is exceeded, the flatness of the fine particles is insufficient, and the interface between the resin layer and the internal voids is not smooth, and the reflected light on the surface of the fine particles and the interface between the resin layer and the internal voids are not smooth. The reflected light does not show a constant mutual interference and does not exhibit a sufficient interference color (pearl color). The preferable lower limit of the above (c / b) is (1/10).

In the present specification, the “major axis” means the longest diameter in the plane drawn by the maximum contour when the optical interference resin fine particles of the present invention are observed at a position where the contour is maximum. The “minor axis” means a diameter that is orthogonal to the midpoint of the major axis in the plane drawn by the maximum contour. Further, the “thickness” refers to a cross-section perpendicular to the plane drawn by the maximum contour and including the minor axis, or intersects the midpoint of the minor axis, or an extension line thereof This means the diameter that intersects the point. The minor axis of the light interference resin fine particles of the present invention is preferably larger than the thickness. Moreover, when the light interference resin fine particles of the present invention have the above-described flat surface, it is preferable that the flat surface and the surface drawn by the maximum contour have a parallel relationship.
In the present specification, the ratio (a / b) between the short diameter (a) and the long diameter (b) of the optical interference resin fine particles of the present invention, and the ratio between the thickness (c) and the long diameter (b) ( c / b) is an average value obtained by measuring at least 500 light interference resin fine particles of the present invention using an electron microscope.

The composition of the light interference resin fine particles of the present invention is not particularly limited as long as it can synthesize the hollow resin particles capable of taking the above-mentioned flat shape, but the air phase / fine particle surface and the resin layer / particle internal void layer are not limited. When the reflected light at the interface is sufficiently strong and the interference color is to be expressed strongly, it is preferable to use a high refractive index resin having a refractive index of 1.60 or more. In addition, when the reflected light at the air phase / resin particle surface and the resin layer / particle internal void layer interface is moderately suppressed and glare is desired to be suppressed, a low refractive index resin having a refractive index of 1.60 or less is used. It is preferable.

The resin having a high refractive index of 1.60 or more is not particularly limited. For example, polystyrene, polymethylstyrene, diphenylmethyl methacrylate, polybenzyl methacrylate, phenol formaldehyde resin, bisphenol A type epoxy resin, bisphenol F Type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, amine type epoxy resin, flexible epoxy resin, crystalline epoxy resin, biphenyl type epoxy resin, and other benzene ring-containing polymers; polynaphthyl methacrylate, polyvinyl naphthalene, Naphthalene skeleton-containing polymers such as naphthalene formaldehyde resin and naphthalene type epoxy resin; polyvinylidene chloride, polychlorostyrene, polybromophenyl methacrylate Over DOO, poly pentabromophenyl methacrylate, halogen-containing polymers such as brominated epoxy resins; polysulfone, polyvinyl thiophene, polysulfide, elemental sulfur-containing polymers such as polyvinyl phenyl sulfide and the like.

The resin having a low refractive index of 1.60 or less is not particularly limited, and examples thereof include alkyl (meth) acrylate monomers, hydrogenated epoxy resins, polydimethylsiloxane macromonomers, fluoroolefins (for example, fluoroethylene). , Vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.), trifluoroethyl methacrylate, perfluorooctylethyl (meth) acrylate, etc. ) Or partially fluorinated alkyl ester derivatives of methacrylic acid, fully or partially fluorinated vinyl ethers, partially fluorinated epoxy resins, and the like.

上記式（１）中、Ｒ^１は、水素原子、メチル基、又はフッ素原子を表し、ｎ、ｐは、自然数である。

In the above formula (1), R ¹ represents a hydrogen atom, a methyl group, or a fluorine atom, and n and p are natural numbers.

As a method for producing the optical interference resin fine particles of the present invention, for example, a method of obtaining flat particles by circulating heated heated particles described in JP-A-2002-229249 through a pressurized bottleneck is used. Using inorganic particles and / or organic particles having a predetermined flat shape satisfying the above-mentioned range as template particles, laminating and polymerizing a resin layer on the template particles, and then dissolving the laminated polymer resin layer A method of obtaining flat hollow particles using a solvent that dissolves the internal template particles without using a solvent; A method of flattening spherical hollow particles prepared by interfacial polymerization under pressure or shear force of a ball mill, mortar, etc .; Examples thereof include a method of producing hollow resin fine particles highly flattened by an interfacial polymerization method using a selected predetermined material. In particular, when a method of flattening spherical hollow particles produced by an interfacial polymerization method or a method of producing hollow resin fine particles flattened by an interfacial polymerization method using a predetermined material selected appropriately, a desired shape is obtained. The hollow resin fine particles can be obtained, which is preferable.

When the light interference resin fine particles of the present invention are produced by interfacial polymerization, specifically, the hydrophilic reaction component B is prepared by using a lipophilic reaction component A and a hydrophilic reaction component B that generate a resin by reaction. A step of preparing a dispersion in which polymerizable droplets containing the lipophilic reaction component A are dispersed in a polar medium, and a step of reacting the lipophilic reaction component A and the hydrophilic reaction component B. It can manufacture with the manufacturing method which has this. Further, it can also be produced by a production method having a step of flattening the obtained resin fine particles.

According to such a production method, the above-described light interference resin fine particles of the present invention having a high porosity and a single pore structure can be produced, and further, lipophilic reaction component A, hydrophilic reaction component B, and lipophilicity are produced. By selecting a lipophilic component other than the reactive component, the light interference resin fine particles of the present invention having the above-described flattened shape can be produced without using a material having special properties such as liquid crystallinity. be able to.

The lipophilic reaction component A is not particularly limited. For example, polyisocyanate, epoxy monomer, acid halide, and the like can be used. However, there is a wide selection of monomer species, and the resulting resin component is tough and highly sophisticated. Epoxy monomers are preferred because the particles are not crushed even during flattening and the internal voids are easily secured.

The epoxy monomer has lipophilic properties and reacts with amines, polycarboxylic acids, and acid anhydrides to give resins.
The epoxy monomer is not particularly limited, for example, glycidyl ether type, glycidyl ester type, glycidyl amine type, aliphatic type, alicyclic type, novolac type, aminophenol type, hydatoin type, isocyanurate type, biphenol type, Epoxy monomers having an epoxy equivalent of 500 or less that can be used in any of naphthalene type and their hydrogenated products, fluorinated products, etc., and the resulting resin component has a high cross-linking density and can easily secure internal voids even in high flattening. Is preferably an epoxy monomer having an epoxy equivalent of 200 or less.

The epoxy monomer having an epoxy equivalent of 200 or less is not particularly limited. For example, Epototo YD115, Epototo YD127, Epototo YD128 (trade name, manufactured by Toto Kasei Co., Ltd.), Epicoat 825, Epicoat 827, Epicoat 828 (trade name Japan Epoxy Resins) Bisphenol A type epoxy resins such as EPICLON 840, EPICLON 850 (trade name, manufactured by Dainippon Ink &Chemicals); Epototo YDF-170, Epototo YDF175S (trade name, manufactured by Toto Kasei), Epicoat 806, Epicoat 807 (trade name) Bisphenol F type epoxy resins such as Japan Epoxy Resin Co., Ltd., EPICLON 830, EPICLON 835 (trade name, Dainippon Ink Chemical Co., Ltd.); Epototo YDPN-638, Epotho YDCN-701, Epototo YDCN-702, Epotot YDCN-703, Epotot YDCN-704, Epotot YDCN-500 (trade name, manufactured by Tohto Kasei Co., Ltd.), Epicoat 152, Epicoat 154 (trade name, manufactured by Japan Epoxy Resin), EPICLON N- Novolak type epoxy resins such as 655, EPICLON N-740, EPICLONN-770, EPICLON N-775, EPICLON N-865 (trade name, manufactured by Dainippon Ink and Chemicals); Epototo YH-434, Epototo YH434-L Manufactured by Kasei Co., Ltd.), Epicoat 1031S, Epicoat 1032H60, Epicoat 604, Epicoat 630 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 430 (trade name, Dainippon Ink and Chemicals, Inc.) ), TETRAD-X, TETRAD-C (trade name: Mitsubishi Gas Chemical Co., Ltd.) and other special multifunctional types; Resin: Aliphatic polyglycidyl ether type epoxy resin such as Epototo YH-300, Epototo YH301, Epototo YH-315, Epototo YH-324, Epototo YH-325 (trade name, manufactured by Toto Kasei Co., Ltd.); Epototo YDC-1312, Epototo YSLV Crystalline epoxy resins such as -80XY (trade name manufactured by Toto Kasei Co., Ltd.); naphthalene type epoxy resins such as EPICLON HP-4032 and EPICLON EXA-4700 (trade names manufactured by Dainippon Ink and Chemicals); Special functional epoxy resins such as PICOAT 191P, Epicoat YX310 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON HP-820 (trade name, manufactured by Dainippon Ink and Chemicals); EPICLON 725 (trade name, manufactured by Dainippon Ink and Chemicals) Reactive diluents and the like.

Epoxy monomer having an epoxy equivalent of more than 200 and less than 500 is not particularly limited. For example, Epototo YD134, Epototo YD011 (trade name, manufactured by Toto Kasei), Epicoat 801, Epicoat 1001 (trade name, manufactured by Japan Epoxy Resin), Bisphenol A type epoxy resin such as EPICLON 860, EPICLON 1050, EPICLON 1055 (trade name manufactured by Dainippon Ink and Chemicals); Bisphenol F type epoxy resin such as Epototo YDF-2001 (trade name manufactured by Tohto Kasei Co., Ltd.); EPICLON N-660, EPICLON N -665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-695 (trade name, manufactured by Dainippon Ink and Chemicals), etc. Special multi-functional types such as Epicoat 157S70 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 5500 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.); Brominated epoxy resins such as EPICLON152, EPICLON153 (trade name, manufactured by Dainippon Ink &Chemicals); Epototo YD-171 (trade name, manufactured by Tohto Kasei Co., Ltd.), Epicoat 871 (trade name, manufactured by Japan Epoxy Resin), EPICLON Flexible epoxy resins such as TSR-960 and EPICLON TSR-601 (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.); Epotot ST-3000 (trade name, manufactured by Toto Kasei), Epicoat YX8000, Epicoat YX8034 (trade name) Hydrogenated epoxy resins such as Japan Epoxy Resin Co .; and dicyclopentadiene epoxy resins such as EPICLON HP-7200 (trade name Dainippon Ink and Chemicals).

Among them, when one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, flexible epoxy resin, and hydrogenated products thereof, which have high toughness and can be highly deformed, are obtained, an interface is obtained. Hollow particles having a shape flattened by a polymerization method are easily obtained and are suitable.
These epoxy monomers may be used alone or in combination of two or more.

Further, for example, when an epoxy monomer is used as the lipophilic reaction component A, amine and / or polycarboxylic acid, acid anhydride, etc. can be used as the hydrophilic reaction component B. Among them, amine-based curing agents are used. It is suitable in terms of reaction temperature and cured properties.

The amine is not particularly limited. For example, ethylenediamine, 1,4-diaminobutane, 1,5-diaminoheptane, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane. 1,10-diaminodecane, tetramethylenediamine, bishexamethylenetriamine, phenylenediamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenepentamine, norbornanediamine, isophoronediamine, xylylenediamine, etc .; 2- Methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2- Enyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4 -Methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl -S-triazine, 2,4-diamino-6- [2'-methyl-4'-methyl Imidazolyl- (1 ′)]-ethyl-s-triazine, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, etc .; piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, etc. Piperazine compounds; amino group-containing prepolymers such as amino adducts of epoxy resins.
In particular, when a curing agent system having at least one alkylene diamine having an active hydrogen equivalent of 50 or less and having 4 or more and less than 10 carbon atoms is used, the light interference of the present invention is highly flattened due to the flexibility of the alkylene moiety. Resin fine particles are easily obtained.

The polycarboxylic acid is not particularly limited. For example, oxalic acid, adipic acid, azelaic acid, sebacic acid, malonic acid, succinic acid, 1,4-cyclohexyldicarboxylic acid, (o-, m-, p-) benzene Examples thereof include a polymer copolymer containing 10% by weight or more of any of dicarboxylic acid, maleic acid, itaconic acid, acrylic acid, methyl methacrylic acid and the like.

The acid anhydride is not particularly limited. For example, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride and a mixture thereof, cyclopentane / tetracarboxylic dianhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride Acid, tetramethylene maleic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydroxyfuryl) -3 Examples include acid anhydrides such as -methyl-3-cyclohexene-1,2'-dicarboxylic anhydride and methyl nadic anhydride, and modified products thereof.

In the above production method, a non-polymerizable compound may be added to the lipophilic reaction component A. In addition to the role of forming a stable polymerizable droplet in a polar medium and controlling the reaction rate between the lipophilic reaction component A and the hydrophilic reaction component B, the non-polymerizable compound is added by a process described later. When resin fine particles encapsulating unreacted lipophilic reaction component A are prepared, non-polymerizable compounds are also encapsulated in the resin fine particles, and the non-polymerizable compound and unreacted lipophilic reaction components A and By removing the non-polymerizable compound and the unreacted lipophilic reaction component A from the resin fine particles encapsulating the resin, the resin fine particles have a role of making it hollow.

The non-polymerizable compound is liquid at the reaction temperature of the lipophilic reaction component A and the hydrophilic reaction component B, can be mixed with the lipophilic reaction component A, does not react with the lipophilic reaction component A, and There is no particular limitation as long as it can be easily evaporated by heating, for example, butane, pentane, hexane, cyclohexane, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl pentyl ketone, ethyl acetate, Organic solvents such as butyl acetate, methyl chloride, methylene chloride, chloroform, and carbon tetrachloride can be used. Of these, the use of an organic solvent having a lower SP value of 16.0 MPa ^1/2 and an upper limit of 18.0 MPa ^1/2 is preferable because the light interference resin fine particles of the present invention that are highly flattened can be easily obtained. Such organic solvent is not particularly limited, for example, butyl ether, diisobutyl ketone, methylcyclohexane, methylnonyl ketone, dioctyl phthalate, propyl ether, dodecane, diethylamine, dihexyl ether, diisopropyl ketone, methyl amyl acetate, butyl chloride, Dibutylamine, lauryl alcohol, propyl chloride, butyl acetate, cyclohexane, ethyl amyl ketone, ethylene glycol diethyl ether, methyl butyl ketone, methyl hexyl ketone, anisole, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, methyl amyl ketone , Methyl isopropyl ketone, cyclopentane, diethylene glycol monolaurate Methyl propyl ketone, chlorotoluene, dimethyl ether, xylene.

The blending amount of the non-polymerizable compound is not particularly limited, but a preferable lower limit is 50 parts by weight and a preferable upper limit is 1000 parts by weight with respect to 50 parts by weight of the lipophilic reaction component. When the amount is less than 50 parts by weight, the porosity of the obtained light interference resin fine particles of the present invention may be low, and flattened particles are difficult to obtain. When the amount exceeds 1000 parts by weight, the light interference resin of the present invention obtained is obtained. Since the resin layer of the fine particles becomes too thin, the internal voids may be crushed when flattened.

The polar medium is not particularly limited, and is usually water, glycine-HCl buffer, citric acid-sodium citrate buffer, acetic acid-sodium acetate buffer, phosphate buffer, ethanol, methanol, isopropyl alcohol, or the like. Any polar medium can be used as long as it does not mix with the lipophilic reaction component A and can prepare a dispersion of the lipophilic reaction component A.

The method for preparing the dispersion is not particularly limited. For example, a dispersion of flat polymerizable droplets can be suitably prepared by using an emulsifying device having a high shearing force. Examples of such high shearing emulsifiers include homomixers, biomixers, omni mixers, ultrasonic homogenizers, and microfluidizers.

When preparing the dispersion, various additives may be added to the polar medium, such as sodium lauryl sulfate, higher alcohol sodium sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, polyoxyethylene lauryl ether. Sodium sulfate, sodium polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether sulfate triethanolamine, sodium dodecylbenzene sulfonate, sodium alkyl naphthalene sulfonate, sodium dialkyl sulfosuccinate, sodium alkyl diphenyl ether disulfonate, polyoxyethylene alkyl ether phosphorus Anionic emulsifiers such as potassium acid, dipotassium alkenyl succinate and sodium alkanesulfonate, polyoxyethylene Uryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene myristyl ether, polyoxyethylene alkyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene Distyrenated phenyl ether, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan laurate, Polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate Nonionic emulsifiers such as polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, glycerol monostearate, glycerol monostearate, glycerol monooleate, lauryltrimethylammonium chloride , Cationic emulsifiers such as stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, alkylbenzylmethylammonium chloride, laurylbetaine, stearylbetaine, 2-alkyl-N-carboxymethyl-N- Hydroxyethyl imidazolinium betaine, lauryl dimethyla Polymer dispersions such as amphoteric emulsifiers such as minoxide, partially saponified polyvinyl acetate, cellulose derivatives, poly (meth) acrylic acid, poly (meth) acrylic acid copolymer, polyvinylpyrrolidone, polyacrylamide, marialim, polystyrene sulfonic acid, etc. And dispersion aids such as cetyl alcohol.

The method for producing the light interference resin fine particles of the present invention described above includes a step of obtaining resin fine particles by reacting the lipophilic reaction component A and the hydrophilic reaction component B.
For example, by heating the dispersion to a reaction temperature between the lipophilic reaction component A and the hydrophilic reaction component B, the lipophilic reaction component A and the hydrophilic reaction component B react to produce a resin. At this time, since the polymerizable droplet containing the lipophilic reaction component A and the polar medium containing the hydrophilic reaction component B are phase-separated, the reaction is performed only near the interface between the polymerizable droplet and the polar medium. Occurring and forming resin fine particles having a shell made of the generated resin and encapsulating the unreacted lipophilic reaction component A (and the non-polymerizable compound).

The resin fine particles produced in the above process may encapsulate the unreacted lipophilic reaction component A. In this case, the method for producing the optical interference resin particles of the present invention preferably further includes a step of removing the unreacted lipophilic reaction component A encapsulated from the resin fine particles.
The method for removing the remaining lipophilic reaction component A in the obtained resin fine particles is not particularly limited. For example, a method of blowing a gas such as nitrogen or air into the dispersion of the obtained resin fine particles; A method of extracting and removing the lipophilic reaction component A in a solvent that can be mixed with the remaining lipophilic component.
Furthermore, the remaining lipophilic reaction component A can be removed from the resin fine particles encapsulating the remaining lipophilic reaction component A by setting the temperature condition to be equal to or higher than the boiling point of the internal unreacted lipophilic reaction component A.

The resin fine particles formed by the above-described production method are constant like the above-described light interference resin fine particles of the present invention by selecting the lipophilic reaction component A, the hydrophilic reaction component B, the non-polymerizable compound, and the like. It is flattened as described above.
In addition, the light interference resin fine particles of the present invention can be suitably obtained by producing true spherical hollow resin fine particles having a desired particle diameter and a desired porosity by the above-described method and performing a flattening step. Can be manufactured. The step for flattening is not particularly limited, and flattening can be performed by the method described above.

By such a method for producing the optical interference resin fine particles of the present invention, the optical interference resin fine particles of the present invention having a porosity of 50% or more and a volume average particle diameter of 0.1 to 100 μm can be produced. .

Further, by coating the surface of the light interference resin fine particles of the present invention with the coating fine particles, gloss control of the light interference resin fine particles of the present invention, improvement of skin feel, etc. can be suitably performed.
A light interference composite fine particle comprising such a light interference resin fine particle of the present invention and coating fine particles for coating the surface of the light interference resin fine particle is also one aspect of the present invention.

The coating fine particles are not particularly limited, and examples thereof include inorganic fine particles such as zinc oxide, titanium oxide, silica, and alumina, and organic fine particles such as acrylic resin, Nylon resin, styrene resin, and silicon resin.

The size of the coating fine particles is not particularly limited as long as the particle size of the light interference resin fine particles of the present invention is small and can be coated, but the light interference resin fine particles of the present invention from the viewpoint of easy coating. It is preferable that the upper limit of the particle diameter is 1/2 with respect to the major axis. If it exceeds 1/2, the surface of the light interference resin fine particles of the present invention may not be coated.

The covering ratio of the coating resin fine particles to the light interference resin fine particles of the present invention is not particularly limited, but a preferred lower limit is 1% by weight and a preferred upper limit is 20% by weight. If it is less than 1% by weight, the effects of gloss control and skin feel improvement of the light interference resin fine particles of the present invention may not be sufficiently obtained. If it exceeds 20% by weight, the surface of the light interference resin fine particles of the present invention The expression of the pearl color due to the mutual interference effect between the reflected light at and the reflected light at the interface between the resin layer and the internal gap may be insufficient.

In the light interference composite fine particles of the present invention, the coating fine particles are preferably hollow fine particles. By using hollow particles as the coating fine particles, for example, when the light interference composite fine particles of the present invention are used as a powder blending component of a makeup cosmetic, a natural finish with a transparent feeling can be realized.

When the coating fine particles are hollow fine particles, the porosity is not particularly limited, but the preferred lower limit is 10% and the preferred upper limit is 90%. If it is less than 10%, the above-mentioned effects as hollow fine particles may not be sufficiently obtained. If it exceeds 90%, the strength may be reduced and the voids may be crushed.

The coating fine particles that are hollow fine particles are not particularly limited. For example, hollow silica particles, hollow acrylic resin particles, hollow styrene-acrylic copolymer resin particles, hollow nylon resin particles, hollow silicone resin particles, hollow fluororesin particles. , Hollow silicone resin particles, hollow epoxy resin particles, and the like.

The light interference resin fine particles of the present invention and / or the light interference composite particles of the present invention can be used in various applications. For example, the light interference resin fine particles of the present invention and / or the light interference composite particles of the present invention are fine particles. It can be used in cosmetics, paints, and inks for the purpose of imparting gloss due to mutual interference between reflected light on the surface and reflected light at the interface between the resin layer and the internal voids.
Cosmetics, paints and inks containing the light interference resin fine particles of the present invention and / or the light interference composite particles of the present invention are also one aspect of the present invention.

The cosmetic amount of the present invention containing the light interference resin fine particles and / or light interference composite particles of the present invention is the same as in the conventional method for producing cosmetics, and the light interference resin fine particles and / or light interference composite particles of the present invention are used. In addition, the components blended in ordinary cosmetics are blended.
These components include, for example, petrolatum, lanolin, ceresin, microcrystalline wax, carnauba wax, candelilla wax, higher fatty acids, higher alcohols and other solid, semi-solid oils, squalane, liquid paraffin, ester oil, diglyceride, triglyceride, silicon Fluid oils such as oil, fluorine-based oils such as perfluoropolyether, perfluorodecalin and perfluorooctane, water-soluble and oil-soluble polymers, surfactants, inorganic and organic pigments, inorganics treated with silicon or fluorine compounds, and Coloring agents such as organic pigments and organic dyes, ethanol, preservatives, antioxidants, pigments, thickeners, pH adjusters, fragrances, UV absorbers, moisturizers, blood circulation promoters, cooling sensates, antiperspirants, A bactericidal agent, a skin activator, etc. are mentioned.
The blending amount of these components is not particularly limited, and can be appropriately blended within a range that does not impair the effects of the light interference resin fine particles and / or the light interference composite particles of the present invention described above.

The paint or ink of the present invention containing the light interference resin fine particles and / or light interference composite particles of the present invention is the same as the conventional paint or ink production method, and the light interference resin fine particles and / or light interference of the present invention. It can be produced by kneading composite particles, a binder resin, a solvent, and additives as required.
Examples of the binder resin for ink include conventionally used coating resins such as rosin-modified phenol resin, rosin alkyd resin, rosin ester resin, acrylic resin, and oil-modified alkyd resin.
For kneading, a ball mill, dynole mill, sand grind mill, paint conditioner, two rolls, three rolls, heating kneader, ultrasonic disperser, or the like can be used.

According to the present invention, even if it does not consist of a material having a light interference effect and special properties such as liquid crystallinity, it has excellent dispersibility in an organic solvent and a binder resin, and has a sufficient pearl color. The light interference resin fine particles and the light interference composite fine particles that can be expressed can be provided.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
30 parts by weight of Epicoat 834 (epoxy equivalent 230-270 manufactured by Japan Epoxy Resin Co., Ltd.) as an epoxy monomer component and 10 parts by weight of Epicoat 871 (epoxy equivalent 390-470 manufactured by Japan Epoxy Resin Co., Ltd.) and diisobutylketone 60 as a non-polymerizable compound The total amount of the mixed solution obtained by mixing and stirring parts by weight is added to 400 parts by weight of ion-exchanged water containing 5 parts by weight of hexamethylenediamine as a curing agent component, 5 parts by weight of diaminoheptane, and 2 parts by weight of polyvinyl alcohol as a water-soluble dispersant. The mixture was added and stirred and emulsified with a homogenizer to prepare a dispersion in which droplets having an average particle diameter of 8 μm were dispersed.
After using a 20 L polymerization vessel equipped with a stirrer, jacket, reflux condenser and thermometer, the inside of the polymerization vessel was depressurized and deoxygenated in the vessel, and then replaced with nitrogen to make the inside nitrogen atmosphere Then, the obtained dispersion was charged, and the polymerization vessel was heated to 80 ° C. to initiate polymerization. Polymerization was performed for 4 hours, and after a aging period of 1 hour, the polymerization vessel was cooled to room temperature.
The obtained slurry was dehydrated with a centle, and then the remaining lipophilic component was removed by vacuum drying to obtain optical interference resin fine particles.

(Example 2)
30 parts by weight of Epicoat 834 (epoxy equivalent 230-270 manufactured by Japan Epoxy Resin Co., Ltd.) as an epoxy monomer component and 10 parts by weight of Epicoat 871 (epoxy equivalent 390-470 manufactured by Japan Epoxy Resin Co., Ltd.) and diisobutylketone 60 as a non-polymerizable compound The total amount of the mixed solution obtained by mixing and stirring parts by weight is added to 400 parts by weight of ion-exchanged water containing 5 parts by weight of hexamethylenediamine as a curing agent component, 5 parts by weight of diaminoheptane, and 2 parts by weight of polyvinyl alcohol as a water-soluble dispersant. The mixture was added and stirred and emulsified with a homogenizer to prepare a dispersion in which droplets having an average particle diameter of 8 μm were dispersed.
After using a 20 L polymerization vessel equipped with a stirrer, jacket, reflux condenser and thermometer, the inside of the polymerization vessel was depressurized and deoxygenated in the vessel, and then replaced with nitrogen to make the inside nitrogen atmosphere Then, the obtained dispersion was charged, and the polymerization vessel was heated to 80 ° C. to initiate polymerization. Polymerization was performed for 4 hours, and after a aging period of 1 hour, the polymerization vessel was cooled to room temperature.
After adding 3 g of acrylic resin fine particles with an average particle diameter of 80 nm to the obtained slurry and stirring for 1 hour, the slurry was dehydrated with a centle, and then the remaining lipophilic components were removed by vacuum drying to obtain a hollow flat optical interference A light interference composite fine particle having the resin fine particle surface coated with acrylic resin fine particles was obtained.

(Example 3)
30 parts by weight of Epicoat 834 (epoxy equivalent 230-270 manufactured by Japan Epoxy Resin Co., Ltd.) as an epoxy monomer component, 10 parts by weight of Epicoat 871 (manufactured by Japan Epoxy Resin Co., Ltd. 390-470), and 60 wt. The total amount of the mixed solution obtained by mixing and stirring the parts was added to 400 parts by weight of ion-exchanged water containing 5 parts by weight of hexamethylenediamine as a curing agent component, 5 parts by weight of diaminoheptane, and 2 parts by weight of polyvinyl alcohol as a water-soluble dispersant. Then, the mixture was stirred and emulsified with a homogenizer to prepare a dispersion in which droplets having an average particle diameter of 8 μm were dispersed.
After using a 20 L polymerization vessel equipped with a stirrer, jacket, reflux condenser and thermometer, the inside of the polymerization vessel was depressurized and deoxygenated in the vessel, and then replaced with nitrogen to make the inside nitrogen atmosphere Then, the obtained dispersion was charged, and the polymerization vessel was heated to 80 ° C. to initiate polymerization. Polymerization was performed for 4 hours, and after a aging period of 1 hour, the polymerization vessel was cooled to room temperature.
After adding 3 g of epoxy hollow resin fine particles with an average particle diameter of 102 nm to the obtained slurry and stirring for 1 hour, the slurry was dehydrated with a centle, and then the remaining lipophilic component was removed by vacuum drying to obtain a hollow flat light. A light interference composite fine particle in which the surface of the interference resin fine particle was coated with the epoxy hollow resin fine particle was obtained.

(Comparative Example 1)
A pearl pigment (Merck, Iriodin 201) having an average particle size of 12 μm was used as the inorganic luster pigment.

(Comparative Example 2)
As the non-flat hollow particles, hollow porous spherical particles (M-610, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) having an average particle diameter of 15 μm were used.

(Comparative Example 3)
As non-hollow flat resin particles, 10 parts by weight of spherical nylon (manufactured by Toray Industries Inc., average particle size 4 μm), 0.2 part by weight of sodium polyoxyethylene lauryl ether phosphate (Nikko Chemicals, Nikkor DLP10), 40 parts by weight of water After putting it in a magnetic pot with a capacity of 200 mL containing 200 g of magnetic balls and rotating for 36 hours, it was filtered and dried to obtain flat non-hollow flat resin particles.

(Evaluation)
The fine particles obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were evaluated by the following methods. The results are shown in Table 1.

(1) Measurement of volume average particle diameter The volume average particle diameter was measured using a laser diffraction particle size distribution analyzer (Horiba, Ltd., "LA-910"). Three places were sampled from arbitrary places of the powder, and the average value was used.

(2) Measurement of major axis, minor axis and thickness Using an electron microscope (manufactured by Hitachi High-Technologies Corporation, "S-3500N"), 500 or more randomly selected particles were observed, and the average major axis, minor axis, The thickness was measured.

(3) Measurement of porosity The true specific gravity of particles including voids inside the particles was measured using a densitometer (manufactured by Shimadzu Corporation, “Acpic 1330”), and the porosity was calculated.

(4) Evaluation of dispersibility in organic solvent The fine particles in Examples 1 to 3 and Comparative Examples 1 to 3 were added to water, isopropyl alcohol, and cyclohexanone solvent, respectively, and the dispersibility was evaluated visually by the following criteria. Judged by.
○: Dispersibility good △: Slightly aggregated ×: Aggregated

(5) Coating property evaluation An ink was prepared with a composition of 20 g of CCST medium (produced by Toyo Ink) and 20 g of cyclohexanone with respect to 10 g of the fine particles obtained in Examples 1 to 3 and Comparative Examples 1 to 3, and K-Plin. Gravure printing was performed on black-and-white concealment paper using a Tingpur fur printing press (manufactured by RK Print-Coat Instruments). The color tone and gloss of the printed surface were visually judged in three stages according to the following criteria.
1: Low 2: Normal 3: High

According to the present invention, even if it does not consist of a material having a light interference effect and special properties such as liquid crystallinity, it has excellent dispersibility in an organic solvent and a binder resin, and has a sufficient pearl color. The light interference resin fine particles and the light interference composite fine particles that can be expressed can be provided.

Claims (8)

An optical interference resin fine particle having a flat shape and having voids therein, a porosity of 50% or more, and a volume average particle diameter of 0.1 to 100 μm. A light interference composite fine particle comprising the light interference resin fine particle according to claim 1 and a coating fine particle covering a surface of the light interference resin fine particle. 3. The optical interference composite fine particle according to claim 2, wherein the coating fine particle is a hollow fine particle. A cosmetic comprising the light interference resin fine particles according to claim 1 and / or the light interference composite fine particles according to claim 2 or 3. A paint comprising the light interference resin fine particles according to claim 1 and / or the light interference composite fine particles according to claim 2 or 3. A painted product, which is coated with the paint according to claim 5. An ink comprising the light interference resin fine particles according to claim 1 and / or the light interference composite fine particles according to claim 2 or 3. A printed matter printed with the ink according to claim 7.