Composite particles and their applications

Abstract

The present invention aims to provide composite particles with high mechanical strength. [Solution] A composite particle comprising a thermoplastic resin (A) and inorganic particles (B), wherein the inorganic fixation rate is 50% or more. Preferably, the melting point of the thermoplastic resin (A) is 70 to 150°C. Preferably, the thermoplastic resin (A) comprises at least one selected from polyolefin resins, polyester resins, acrylic resins, and polyvinyl chloride resins. Preferably, the inorganic particles (B) comprises at least one selected from inorganic oxides, inorganic hydroxides, inorganic carbonates, clay minerals, inorganic chlorides, and inorganic phosphates. Preferably, the content of the inorganic particles (B) in the composite particle is 1 to 200 parts by weight per 100 parts by weight of the thermoplastic resin (A).

Description

[Technical Field]

[0001] This invention relates to composite particles and their applications. [Background technology]

[0002] Traditionally, organic microparticles have been used as compounding agents in various products such as cosmetics, paints, and plastic products to enhance the slipperiness and light scattering properties of the products. One proposed method for enhancing the functionality of organic microparticles is the composite formation of organic and inorganic particles. This method is expected to yield composite particles possessing the characteristics of both organic and inorganic particles, thereby improving various properties such as stability, heat resistance, flame retardancy, chemical resistance, thermal conductivity, and pressure resistance. Patent Document 1 describes composite particles obtained by coating magnetic resin particles with thermally conductive inorganic particles using a high-speed airflow impact method, a mechanofusion method, or a mechanochemical method. Patent Document 2 describes a method for producing composite particles, which includes the steps of preparing a liquid containing polymer particles, inorganic particles, and a water-soluble polymer, and insolubilizing the water-soluble polymer to attach the inorganic particles to the surface of the polymer particles. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2012-124449 [Patent Document 2] Japanese Patent Publication No. 2006-052332 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, conventional composite particles sometimes resulted in problems such as reduced slipperiness of the particle layer and susceptibility of the coating film containing the particles to scratches. Investigation into the causes of these problems revealed that the composite particles were prone to deformation and fracture when external forces were applied, indicating insufficient mechanical strength of the composite particles. Therefore, the present invention aims to provide composite particles with excellent mechanical strength. [Means for solving the problem]

[0005] As a result of diligent research to achieve the above objective, the inventors of the present invention have found that composite particles containing a specific resin and inorganic particles, with an inorganic fixation rate within a specific range, can be obtained, resulting in composite particles with excellent mechanical strength. In other words, the present invention is as follows <1> ~ <8> This includes the following aspects. <1> A composite particle comprising a thermoplastic resin (A) and inorganic particles (B), wherein the inorganic fixation rate is 50% or more. <2> The melting point of the thermoplastic resin (A) is 70 to 150°C. <1> The composite particles described above. <3> The thermoplastic resin (A) includes at least one selected from polyolefin resins, polyester resins, acrylic resins, and polyvinyl chloride resins. <1> or <2> The composite particles described above. <4> The inorganic particles (B) include at least one selected from inorganic oxides, inorganic hydroxides, inorganic carbonates, clay minerals, inorganic chlorides, and inorganic phosphates. <1> ~ <3> A composite particle as described in any of the following. <5> The amount of inorganic particles (B) in the composite particles is 1 to 200 parts by weight per 100 parts by weight of the thermoplastic resin (A). <1> ~ <4> A composite particle as described in any of the following. <6> The ash content of the composite particles is 1 to 60% by weight. <1> ~ <5> A composite particle as described in any of the following. <7> The volume-average particle diameter (D) of the inorganic particles (B) B50 ) is 10 μm or less. <1> ~ <6> A composite particle as described in any of the following. <8> The volume-average particle diameter (D) of the inorganic particles (B) B50 The volume-average particle diameter (D) of the composite particles relative to )50 ) ratio (D 50 / D B50 ) is 2 or more, the composite particle according to any one of <1> to <7>. <9> A composition containing the composite particle according to any one of <1> to <8>. <10> A cosmetic containing the composite particle according to any one of <1> to <8>.

Advantages of the Invention

[0006] The composite particle of the present invention is excellent in mechanical strength. Since the composition of the present invention contains composite particles excellent in mechanical strength, it is difficult to be damaged. Since the cosmetic of the present invention contains composite particles excellent in mechanical strength, it is excellent in slipperiness.

Brief Description of the Drawings

[0007] [Figure 1] Electron micrograph of composite particle 1 of Example 1

Modes for Carrying Out the Invention

[0008] The composite particle of the present invention is a composite particle containing a thermoplastic resin (A) and inorganic particles (B), and has an inorganic fixation rate of 50% or more. The reason why the composite particle of the present invention is excellent in mechanical strength is not particularly limited, but it is considered that at least a part of the inorganic particles (B) is incorporated into the thermoplastic resin (A). The composite particle of the present invention will be described below.

[0009] 〔Thermoplastic resin (A)〕 The composite particle of the present invention contains a thermoplastic resin (A). The thermoplastic resin (A) is not particularly limited, but examples include polyolefin resins, polyester resins, acrylic resins, polyvinyl chloride resins, polyurethane resins, polyether resins, polyamide resins, and cellulose resins. It is preferable that it contains at least one selected from polyolefin resins, polyester resins, acrylic resins, and polyvinyl chloride resins, is highly flexible, and is also preferable to contain at least one selected from polyolefin resins and polyester resins, and is particularly preferable to contain polyester resins.

[0010] Examples of polyolefin resins include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, low molecular weight polyolefin, and olefin elastomer, and one or more of these may be used in combination.

[0011] There are no particular limitations on the acrylic resin, but examples include (meth)acrylic acid esters and poly(meth)acrylic acid ester-(meth)acrylic acid copolymers. Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and 2-hydroxy (meth)acrylic acid ester, and one or more of these may be used in combination. Furthermore, nitrile monomers such as acrylonitrile, methacrylonitrile, fumaronitrile, and maleonitrile; vinyl halogenated monomers such as vinyl chloride; vinylidene halogenated monomers such as vinylidene chloride; vinyl ester monomers such as vinyl acetate, vinyl propionate, and vinyl butyrate; unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, and cinnamic acid; unsaturated dicarboxylic acids such as maleic acid, itaconic acid, fumaric acid, citraconic acid, and chloromaleic acid; anhydrides of unsaturated dicarboxylic acids; and unsaturated monocarboxylic acids such as monomethyl maleate, monoethyl maleate, monobutyl maleate, monomethyl fumarate, monoethyl fumarate, monomethyl itaconic acid, monoethyl itaconic acid, and monobutyl itaconic acid. Copolymers may be obtained by combining one or more of the following: carboxyl group-containing monomers such as Japanese dicarboxylic acid monoesters; (meth)acrylamide monomers such as acrylamide, substituted acrylamide, methacrylamide, and substituted methacrylamide; maleimide monomers such as N-phenylmaleimide and N-cyclohexylmaleimide; styrene monomers such as styrene and α-methylstyrene; ethylene unsaturated monoolefin monomers such as ethylene, propylene, and isobutylene; vinyl ether monomers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; vinyl ketone monomers such as vinyl methyl ketone; N-vinyl monomers such as N-vinylcarbazole and N-vinylpyrrolidone; and vinylnaphthalene salts. In this invention, (meth)acrylic means acrylic or methacrylic.

[0012] While there are no particular limitations on the polyester resin, it is preferable that it be at least one selected from aliphatic polyester resins and aliphatic-aromatic polyester resins, and more preferably an aliphatic polyester resin, due to its excellent flexibility.

[0013] As for the aliphatic polyester resin, there are no particular limitations as long as the constituent components of the polyester resin are an aliphatic polyhydric alcohol, an aliphatic polyhydric acid, and an aliphatic hydroxycarboxylic acid, respectively. However, aliphatic polyesters obtained from constituent components containing a polyhydric alcohol and a polyhydric acid are preferred because they are more likely to produce the effects of the present invention. Examples of aliphatic polyhydric alcohols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, propylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, neopentyl glycol (2,2-dimethylpropane-1,3-diol), 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,2-bis(4-hydroxycyclohexyl)propane, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, trimethylolpropane, glycerin, pentaerythritol, and the like. These aliphatic polyhydric alcohols may be used individually or in combination of two or more.

[0014] Examples of aliphatic polycarboxylic acids include succinic acid, adipic acid, suberic acid, sebacic acid, azelaic acid, octyl succinic acid, fumaric acid, maleic acid, itaconic acid, decamethylenedicarboxylic acid, and their anhydrides. These aliphatic polycarboxylic acids may be used individually or in combination of two or more types. Examples of aliphatic hydroxycarboxylic acids include lactic acid, glycolic acid, hydroxybutyric acid, hydroxycaproic acid, hydroxydimethylbutyric acid, and hydroxymethylbutyric acid. These aliphatic hydroxycarboxylic acids may be used individually or in combination of two or more.

[0015] Examples of aliphatic polyester resins include polycaprolactone butylene succinate, polybutylene succinate, polybutylene succinate adipate, polybutylene succinate carbonate, polybutylene adipate, polybutylene succinate tractate, polyethylene succinate, polyethylene adipate, polytetramethylene succinate, polyhydroxyalkanoate, polyhydroxybutyrate, and poly(3-hydroxybutyrate-c Examples include poly(3-hydroxyhexanoate), polyhydroxybutyrate valate, poly(3-hydroxybutyrate-co-3-hydroxyvalate), poly(3-hydroxybutyrate-co-3-hydroxypropionate), poly(3-hydroxybutyrate-co-4-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyacyl), polyhydroxyacyl, polylactic acid, etc., and one or more of these may be used in combination.

[0016] The aliphatic-aromatic polyester resin is not particularly limited as long as the polyhydric alcohol, polyhydric carboxylic acid, and hydroxycarboxylic acid that are components of the polyester resin each contain the aliphatic polyhydric alcohol, aliphatic polyhydric carboxylic acid, and aliphatic hydroxycarboxylic acid, and further contain an aromatic polycarboxylic acid or a derivative thereof. Examples of aromatic polycarboxylic acids include o-phthalic acid, terephthalic acid, isophthalic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, trimellitic acid, pyromellitic acid, etc., and one or more of these may be used in combination.

[0017] Examples of aliphatic-aromatic polyester resins include polybutylene succinate terephthalate, polybutylene adipate terephthalate, polytetramethylene adipate terephthalate, and polybutylene succinate adipate terephthalate.

[0018] There are no particular limitations on the polyether resin, but examples include polyphenylene ether, polysulfone, polyethersulfone, polyacetal, polyetherketone, polyetheretherketone, etc., and one or more of these may be used in combination.

[0019] There are no particular limitations on the polyamide resins, but for example, nylon 1, nylon 3, nylon 4, polycaproamide (nylon 6), poly-ω-aminoheptanoic acid (nylon 7), poly-9-aminononanoic acid (nylon 9), polyundecaneamide (nylon 11), polylaurin lactam (nylon 12), polyethylenediamine adipamide (nylon 2,6), polytetramethylene adipamide (nylon 4,6), polyhexamethylenediadipamide ( Examples include nylon 6,6), polyhexamethylene sevacamide (nylon 6,10), polyhexamethylene dodecamide (nylon 6,12), polyoctamethylene adipamide (nylon 8,6), polydecamethylene adipamide (nylon 10,6), polydecamethylene sevacamide (nylon 10,10), polydodecamethylene dodecamide (nylon 12,12), metaxylenediamine-6 ​​nylon (MXD6), etc., and one or more of these may be used in combination.

[0020] There are no particular limitations on the polyurethane resin, but examples include polyester-based polyurethane resin, polyether-based polyurethane resin, polycarbonate-based polyurethane resin, etc., and one or more types may be used in combination.

[0021] There are no particular limitations on the cellulose-based resin, but examples include cellulose acetate, ethylcellulose, cellulose ether derivatives, cellulose propionate acetate, cellulose butyrate acetate, etc., and one or more types may be used in combination.

[0022] The melting point of the thermoplastic resin (A) is not particularly limited, but 70 to 150°C is preferred because it improves stability when manufacturing composite particles and makes it easier to satisfy the inorganic fixation rate of the present invention. The upper limit of the melting point is more preferably 140°C, and even more preferably 120°C. On the other hand, the lower limit of the melting point is more preferably 80°C, and even more preferably 90°C. Also, for example, 80 to 140°C is more preferred, and even more preferably 90 to 120°C.

[0023] [Inorganic particles (B)] The composite particles of the present invention include inorganic particles (B). While there are no particular limitations on the inorganic particles (B), inorganic oxides, inorganic hydroxides, inorganic carbonates, clay minerals, inorganic chlorides, inorganic phosphates, etc. are preferred, and it is more preferable to include at least one selected from inorganic oxides and inorganic carbonates, and even more preferable to include at least one selected from titanium dioxide and calcium carbonate, as these have adsorption properties with thermoplastic resins and easily satisfy the inorganic fixation rate of the present invention.

[0024] While there are no particular limitations on the inorganic oxides, examples include silica, titania, alumina, silica-alumina, zirconia, zinc oxide, barium oxide, strontium oxide, titanium dioxide, and magnesium oxide. Titanium dioxide and zinc oxide are preferred due to their high stability in water.

[0025] While there are no particular limitations on the inorganic carbonate, examples include calcium carbonate, barium carbonate, magnesium carbonate, and strontium carbonate. Calcium carbonate and magnesium carbonate are preferred due to their high stability in water.

[0026] While there are no particular limitations on inorganic hydroxides, examples include barium hydroxide, aluminum hydroxide, and strontium hydroxide.

[0027] While there are no specific limitations on clay minerals, examples include smectite, kaolinite, and talc.

[0028] While there are no particular limitations on inorganic chlorides, examples include barium chloride and calcium chloride.

[0029] Examples of inorganic phosphates include aluminum phosphate, calcium phosphate, and titanium phosphate, although there are no particular limitations.

[0030] Volume-average particle size (D) of inorganic particles (B) B50 While there are no particular limitations, the particle size is preferably 0.001 μm to 20 μm, as this increases adsorption to thermoplastic resins and makes it easier to satisfy the inorganic fixation rate of the present invention. B50 The upper limit is more preferably 10 μm, and even more preferably 5 μm. On the other hand, the D B50 The lower limit is more preferably 0.01 μm, and even more preferably 0.1 μm. More preferably 0.01 μm to 10 μm, and even more preferably 0.1 μm to 5 μm. Furthermore, the volume-average particle diameter in this invention is determined by the method described in the examples.

[0031] [Composite particles] The composite particles of the present invention are composite particles comprising a thermoplastic resin (A) and inorganic particles (B), wherein the inorganic fixation rate is 50% or more. By having an inorganic fixation rate of 50% or more of the composite particles, composite particles with excellent mechanical strength can be obtained. The upper limit of the fixation rate is preferably 100%, more preferably 99%, and still preferably 95%. On the other hand, the lower limit of the fixation rate is preferably 60%, more preferably 70%, and still preferably 80%. Also, for example, 50-100% is preferred, 60-99% is more preferred, and 80-95% is still preferred. In this invention, the inorganic fixation rate is determined by the method described in the examples.

[0032] The proportion of thermoplastic resin (A) in the composite particles of the present invention is not particularly limited, but is preferably 35 to 99% by weight in terms of improving stability during manufacturing. The upper limit of this proportion is more preferably 90% by weight, and even more preferably 80% by weight. On the other hand, the lower limit of this proportion is more preferably 40% by weight, and even more preferably 60% by weight. For example, the proportion is more preferably 40 to 90% by weight, and even more preferably 60 to 80% by weight.

[0033] The proportion of at least one selected from polyolefin resins, polyester resins, acrylic resins, and polyvinyl chloride resins in the thermoplastic resin (A) of the present invention is not particularly limited, but is preferably 50% by weight or more in terms of improving stability during manufacturing. The upper limit of this proportion is more preferably 95% by weight, even more preferably 90% by weight, and particularly preferably 85% by weight. On the other hand, the lower limit of this proportion is more preferably 60% by weight, even more preferably 70% by weight, and particularly preferably 80% by weight. For example, the proportion is more preferably 60-95% by weight, even more preferably 70-90% by weight, and particularly preferably 80-85% by weight.

[0034] The proportion of inorganic particles (B) in the composite particles of the present invention is not particularly limited, but it is preferably 1 to 50% by weight in order to obtain composite particles with excellent mechanical strength. The upper limit of this proportion is more preferably 40% by weight, and even more preferably 30% by weight. On the other hand, the lower limit of this proportion is more preferably 10% by weight, and even more preferably 20% by weight. For example, the proportion is more preferably 10 to 40% by weight, and even more preferably 20 to 30% by weight.

[0035] The proportion of inorganic oxides and inorganic carbonates in the inorganic particles (B) of the present invention is not particularly limited, but it is preferably 50% by weight or more in terms of improving stability during manufacturing. The upper limit of this proportion is preferably 100% by weight, more preferably 95% by weight, even more preferably 90% by weight, and particularly preferably 85% by weight. On the other hand, the lower limit of this proportion is more preferably 60% by weight, even more preferably 70% by weight, and particularly preferably 80% by weight. For example, the proportion is more preferably 60-95% by weight, even more preferably 70-90% by weight, and particularly preferably 80-85% by weight.

[0036] The content of the inorganic particles (B) in the composite particles of the present invention is not particularly limited, but when it is 1 to 200 parts by weight with respect to 100 parts by weight of the content of the thermoplastic resin (A), it is preferable in terms of obtaining composite particles having excellent mechanical strength. The upper limit of the content is more preferably 100 parts by weight, and even more preferably 50 parts by weight. On the other hand, the lower limit of the content is more preferably 10 parts by weight, and even more preferably 20 parts by weight. Further, for example, the content is more preferably 10 to 100 parts by weight, and even more preferably 20 to 50 parts by weight.

[0037] The volume average particle diameter (D 50 ) of the composite particles of the present invention is not particularly limited, but is preferably 1 to 100 μm in terms of obtaining composite particles having excellent mechanical strength. The upper limit of the D 50 is more preferably 50 μm, and even more preferably 30 μm. On the other hand, the lower limit of the D 50 is more preferably 2 μm, and even more preferably 4 μm. Further, for example, the D 50 is more preferably 2 to 50 μm, and even more preferably 4 to 30 μm. The volume average particle diameter of the composite particles is measured by the method measured in the examples.

[0038] The coefficient of variation CV of the particle size distribution of the composite particles of the present invention is not particularly limited, but is preferably 2 to 70% in terms of excellent dispersibility in a coating film or the like. The upper limit of the coefficient of variation CV is preferably 65% or less, more preferably 60% or less, even more preferably 55% or less, and particularly preferably 50% or less. The lower limit of the coefficient of variation CV is preferably 3%, more preferably 5%, and particularly preferably 7%. Further, for example, 3 to 65% is more preferably, and 5 to 60% is even more preferably. The coefficient of variation CV refers to the value calculated by the following calculation formulas (l) and (2).

[0039]

Equation

[0040] Volume-average particle size (D) of inorganic particles (B) B50 The volume-average particle diameter (D) of the composite particles relative to ) 50 ) ratio (D 50 / D B50 ) is not particularly limited, but it is preferable that it is 2 or more in that it readily adsorbs with thermoplastic resins and yields composite particles with excellent mechanical strength. 50 / D B50 The upper limit is more preferably 10000, even more preferably 1000, and particularly preferably 100. 50 / D B50 The lower limit is more preferably 3, even more preferably 5, and particularly preferably 10. Also, for example, 3 to 10000 is more preferable, 5 to 1000 is even more preferable, and 10 to 100 is particularly preferable.

[0041] The ash content of the composite particles of the present invention is not particularly limited, but is preferably 1 to 60% by weight in order to obtain composite particles with excellent mechanical strength. The upper limit of the ash content is more preferably 50% by weight, and even more preferably 45% by weight. On the other hand, the lower limit of the ash content is more preferably 10% by weight, and even more preferably 20% by weight. The ash content is more preferably 10 to 50% by weight, and even more preferably 20 to 45% by weight.

[0042] The inorganic fixation rate of the composite particles of the present invention is 50% or more. While there are no particular limitations on the inorganic fixation rate as long as it is 50% or more, the upper limit of the inorganic fixation rate is more preferably 95%, even more preferably 90%, and particularly preferably 85%, in order to obtain composite particles with excellent mechanical strength. The lower limit of the inorganic fixation rate is more preferably 60%, even more preferably 70%, and particularly preferably 80%. Furthermore, for example, the ratio is more preferably 60-95%, even more preferably 70-90%, and particularly preferably 80-85%.

[0043] The compression recovery rate of the composite particles of the present invention is preferably 70% or higher, in that it is possible to obtain composite particles with excellent mechanical strength. The upper limit of the compression recovery rate is more preferably 98%, even more preferably 95%, and particularly preferably 90%. The lower limit of the compression recovery rate is more preferably 75%, even more preferably 80%, and particularly preferably 85%. For example, the ratio is more preferably 75-98%, even more preferably 80-95%, and particularly preferably 85-90%.

[0044] The true specific gravity of the composite particles of the present invention is preferably 2.0 or less, in terms of excellent dispersibility in coatings and the like. The lower limit of the true specific gravity is more preferably 0.85, even more preferably 0.90, and particularly preferably 0.95. On the other hand, the upper limit of the true specific gravity is more preferably 1.8, even more preferably 1.6, and particularly preferably 1.4. Furthermore, for example, 0.85 to 1.8 is more preferably, and 0.95 to 1.4 is even more preferably. The true specific gravity of the particles described in the present invention is determined by the method described in the examples.

[0045] [Other ingredients] The composite particles of the present invention may contain other components besides the thermoplastic resin (A) and inorganic particles (B). Examples of other components include thermosetting resins, cellulose, other organic polymers, surfactants, and organic substances other than organic polymers.

[0046] There are no particular limitations on the thermosetting resin, but examples include polyurethane resins, silicone resins, phenolic resins, unsaturated polyester resins, epoxy resins, melamine resins, and rubber, and one or more types may be used in combination.

[0047] There are no particular limitations on organic polymers other than thermoplastic resins, thermosetting resins, and cellulose, but examples include paraffins such as liquid paraffin; silicone oils such as dimethyl silicone; polyalkylene oxides such as polyethylene oxide and polypropylene oxide; water-soluble polymers such as sodium polyacrylate, polyvinylpyrrolidone, polyvinyl alcohol, dextrin, sodium alginate, potassium alginate, gum arabic, tamarind gum, pectin, pullulan, casein, xanthan gum, carrageenan, tragacanth gum, gelatin, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, carboxymethylcellulose, and carboxyethylcellulose, and one or more of these may be used in combination.

[0048] There are no particular limitations on the surfactants, but examples include anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and silicone-based surfactants. Specifically, these include anionic surfactants such as alkyl sulfate salts, alkyl ether carboxylate salts, alkyl ether sulfate salts, alkyl phosphate salts, polyoxyalkylene alkyl ether acetate salts, alkyl sulfonates, alkylbenzene sulfonates, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkyl ether phosphate salts, higher fatty acid amide sulfonates, fatty acid alkali metal salts (e.g., potassium laurate, sodium myristic acid, sodium stearate), alkyl sulfosuccinate salts, and N-acyl amino acid salts; cationic surfactants such as quaternary ammonium salts and alkylamine salts; and polyoxyalkylene oxide-based surfactants. Nonionic surfactants such as alkyl ethers, polyoxyalkylene styrene phenyl ethers, ester compounds of polyhydric alcohols and monohydric fatty acids, polyoxyalkylene alkylphenyl ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, glycerin fatty acid esters, polyoxyalkylene castor oil, polyoxyalkylene hydrogenated castor oil, higher fatty acid PEG glyceryls, higher fatty acid sorbitans, polyoxyalkylene sorbitol fatty acid esters, polyglycerin fatty acid esters, alkylglycerin ethers, polyoxyalkylene cholesteryl ethers, alkyl polyglucosides, sucrose fatty acid esters, and polysorbates; amphoteric surfactants such as amino acid-based, betaine-type, hydrogenated lecithin, and lecithin; and silicone-based surfactants such as modified silicones are examples, and one or more of them may be used in combination.

[0049] Other organic substances besides organic polymers are not particularly limited, but examples include waxes, oils, fatty acid metal salts and amino acid compounds, specifically waxes such as carnauba wax, candelilla wax, beeswax, and higher alcohols; oils such as almond oil, olive oil, rice bran oil, squalane, alkanes, and alkyl benzoates; fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, and cerotic acid; calcium laurate, zinc laurate, zinc myristic acid, zinc palmitate, magnesium stearate, zinc stearate, calcium stearate, aluminum stearate, calcium 12-hydroxystearate, 1 Examples include fatty acid metal salts such as zinc 2-hydroxystearate, magnesium 12-hydroxystearate, aluminum 12-hydroxystearate, calcium behenate, zinc behenate, magnesium behenate, calcium montana, zinc montana, magnesium montana, and aluminum montana; and amino acid compounds such as N-lauroyl-L-arginine, N-lauroyl-L-lysine, N-hexanoyl-L-lysine, N-oleyl-L-lysine, N-palmitoyl-L-lysine, N-stearoyl-L-lysine, N-hexanoyl-L-lysine, N-myristoyl-L-lysine, N-capryloyl-L-lysine, and N-decanoyl-L-lysine. One or more of these may be used in combination.

[0050] The composite particles of the present invention may be hollow, solid, porous, or encapsulated, but solid particles are preferred in that they provide composite particles with excellent mechanical strength.

[0051] The composite particles of the present invention may contain an encapsulating agent. Examples of encapsulating agents include cosmetic oils such as squalane, liquid paraffin, silicone oil, and ester oil; linear hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, nonane, decane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, and nanodecane; isobutane, isopentane, isohexane, isoheptane, isooctane, isononane, isodecane, isododecane, 3-methylundecane, isotridecane, 4-methyldodecane, isotetradecane, isopentadecane, isohexadecane, 2,2,4,4,6,8,8-heptamethylnonane, and isoheptadecane. Examples of encapsulating agents include branched hydrocarbons such as can, isooctadecane, isonanodecane, and 2,6,10,14-tetramethylpentadecane; hydrocarbons such as cyclododecane, cyclotridecane, hexylcyclohexane, heptylcyclohexane, n-octylcyclohexane, cyclopentadecane, nonylcyclohexane, decylcyclohexane, pentadecylcyclohexane, hexadecylcyclohexane, heptadecylcyclohexane, and octadecylcyclohexane; petroleum ethers, their halides, fluorine-containing compounds such as hydrofluoroethers; tetraalkylsilanes; and compounds that decompose thermally upon heating to produce gas. In addition, one or more of these encapsulating agents may be used in combination.

[0052] The shape of the composite particles of the present invention may be spherical, granular, bowl-shaped, needle-shaped, rice grain-shaped, or flake-shaped, but a spherical shape is preferred in that it can be obtained as composite particles with excellent mechanical strength.

[0053] [Method for manufacturing composite particles] The composite particles of the present invention can be manufactured, for example, by a method comprising: step 1, mixing the components constituting the thermoplastic resin (A) described above, the components constituting the inorganic particles (B), a surfactant, a water-soluble polymer, and water to obtain a preliminary mixture; step 2, heating and stirring the preliminary mixture obtained in step 1 to obtain a heated dispersion; and step 3, cooling the heated dispersion obtained in step 2.

[0054] In the composite particles of the present invention, it is preferable to manufacture them without using organic solvents, as this makes it easier to satisfy the inorganic fixation rate of the present invention. When organic solvents are used, inorganic components tend to be removed when the organic solvent is removed from the composite particles, resulting in a decrease in the inorganic fixation rate.

[0055] The surfactant is not particularly limited, but can be appropriately selected according to the components constituting the composite particles so as to achieve the effects of the present invention. The surfactants described above can be used. The surfactant is not particularly limited, but it is preferable to use at least one selected from anionic surfactants and nonionic surfactants because it provides good stability in the dispersion of the components constituting the thermoplastic resin (A) in water, and it is preferable to use a nonionic surfactant because it can produce composite particles with high dispersibility. There are no particular limitations on the nonionic surfactant, but it is preferably an ester compound of a polyhydric alcohol and a monohydric fatty acid, and more preferably at least one selected from glycerol fatty acid esters and higher fatty acid sorbitans. While there are no particular limitations on the nonionic surfactant, it is preferable to use a nonionic surfactant with an HLB value of 1 to 13, as this allows for the creation of highly dispersible composite particles. Furthermore, using ester-type or ester salt-type surfactants is preferable because it allows for the creation of highly dispersible composite particles. HLB values ​​can be calculated, for example, using the following formula (3) based on the Griffin method. HLB = 20 × (Molecular weight of hydrophilic group / Total molecular weight) (3)

[0056] The surfactant may ultimately be contained within the particles. It is thought that the presence of the surfactant near the particle surface will have a greater influence on the surface structure. The weight percentage of the surfactant in the particles is not particularly limited, but is preferably 0.001 to 10% by weight, with an upper limit of 7% by weight, and even more preferably 5% by weight. On the other hand, the lower limit of the weight percentage is more preferably 0.005% by weight, and even more preferably 0.01% by weight. Furthermore, for example, 0.001 to 7% by weight is more preferably, and even more preferably 0.001 to 5% by weight.

[0057] The water-soluble polymer can be any of the above-mentioned types, and it is preferable that the water-soluble polymer has a viscosity of 2 to 200,000 mPa·s in a 4% aqueous solution at 20°C, as this makes it easier to obtain the composite particles of the present invention stably. The water-soluble polymer is preferably at least one selected from polyvinylpyrrolidone, polyvinyl alcohol, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, and carboxymethylcellulose, and more preferably polyvinyl alcohol. The water-soluble polymer may ultimately be contained in the particles. The weight percentage of the water-soluble polymer in the particles is not particularly limited, but is preferably 0.001 to 10% by weight, with an upper limit of 8% by weight, and even more preferably 5% by weight. On the other hand, the lower limit of the weight percentage is more preferably 0.002% by weight, and even more preferably 0.005% by weight. Furthermore, for example, 0.001 to 8% by weight is more preferably, and even more preferably 0.001 to 5% by weight.

[0058] The composite particles of the present invention are preferable in that they have a high affinity for solvents such as water if they contain at least one selected from surfactants and water-soluble polymers. The total weight percentage of surfactants and water-soluble polymers in the particles is not particularly limited, but is preferably 0.001 to 10% by weight. The lower limit of this weight percentage is preferred in the following order: (1) 0.002% by weight, (2) 0.005% by weight, (3) 0.01% by weight, (4) 0.02% by weight, (5) 0.05% by weight, and (6) 0.1% by weight (the higher the number in parentheses, the more preferable it is). On the other hand, the upper limit of this weight percentage is preferred in the following order: (1) 7% by weight, (2) 6% by weight, (3) 5% by weight, (4) 4% by weight, and (5) 3% by weight (the higher the number in parentheses, the more preferable it is). Furthermore, for example, 0.001 to 7% by weight is more preferable, and 0.001 to 5% by weight is even more preferable.

[0059] In the present invention, when a surfactant and a water-soluble polymer are mixed during manufacturing, the water-soluble polymer improves the viscosity of the liquid during manufacturing, the surfactant improves the uniformity efficiency of the particles, and the dispersibility of the resin components is improved, resulting in stable composite particles. Therefore, it is even more preferable that the weight ratios of the surfactant and the water-soluble polymer are within the aforementioned ranges.

[0060] (Process 1) Step 1 is a step of mixing the components constituting the thermoplastic resin (A), the components constituting the inorganic particles (B), a surfactant, a water-soluble polymer, and water to obtain a preliminary mixture. By creating this preliminary mixture, the inorganic particles (B) are more easily incorporated into the thermoplastic resin (A), thus easily satisfying the inorganic fixation rate of the present invention. If the composite particles contain components other than those constituting the thermoplastic resin (A), the components constituting the inorganic particles (B), the surfactant, and the water-soluble polymer, it is preferable to add and mix the other components in this step.

[0061] In step 1, the components constituting the thermoplastic resin (A) are not particularly limited, but are preferably 1 to 200 parts by weight per 100 parts by weight of water. When the ratio is within the above range, composite particles with a more uniform shape tend to be obtained, which is preferable in that it is easier to satisfy the inorganic fixation rate of the present invention. The lower limit of the mixing ratio is more preferably 3 parts by weight, even more preferably 5 parts by weight, and most preferably 10 parts by weight. On the other hand, the upper limit of the mixing ratio is more preferably 180 parts by weight, even more preferably 160 parts by weight, and most preferably 150 parts by weight. Furthermore, for example, 5 to 200 parts by weight is more preferable, and 10 to 180 parts by weight is even more preferable.

[0062] In step 1, the components constituting the inorganic particles (B) are not particularly limited, but are preferably 1 to 100 parts by weight per 100 parts by weight of water. When this ratio is within the above range, the inorganic fixation rate of the present invention is easily satisfied. The lower limit of the mixing ratio is more preferably 3 parts by weight, even more preferably 5 parts by weight, and most preferably 10 parts by weight. On the other hand, the upper limit of the mixing ratio is more preferably 90 parts by weight, even more preferably 80 parts by weight, and most preferably 10 parts by weight. Furthermore, for example, 5 to 100 parts by weight is more preferable, and 10 to 90 parts by weight is even more preferable.

[0063] In step 1, the mixing ratio of the surfactant is not particularly limited, but is preferably 0.001 to 10 parts by weight per 100 parts by weight of the component constituting the thermoplastic resin (A), in that it is easier to obtain the particle size of the present invention. When the ratio is within the above range, it is preferable in that the mechanical strength of the resulting composite particles tends to improve. The lower limit of the mixing ratio is preferably 0.01 parts by weight, more preferably 0.05 parts by weight, and particularly preferably 0.1 parts by weight. The upper limit of the mixing ratio is more preferably 7 parts by weight, even more preferably 5 parts by weight, and particularly preferably 3 parts by weight. Furthermore, for example, 0.001 to 7 parts by weight is more preferable, and 0.01 to 7 parts by weight is even more preferable.

[0064] In step 1, the mixing ratio of the water-soluble polymer to water is not particularly limited, but is preferably 0.1 to 100 parts by weight per 100 parts by weight of water, as this makes it easier to obtain the composite particles of the present invention stably. This ratio is preferable because it tends to improve the dispersibility of the obtained composite particles. The lower limit of this ratio is more preferably 0.5 parts by weight, even more preferably 1 part by weight, and particularly preferably 2 parts by weight. On the other hand, the upper limit of this ratio is more preferably 80 parts by weight, even more preferably 70 parts by weight, and particularly preferably 60 parts by weight. Also, for example, 0.5 to 100 parts by weight is more preferable, and 1 to 100 parts by weight is even more preferable.

[0065] When the composite particles of the present invention contain an encapsulating agent, it is preferable in step 1 to further use a mixed solution containing the encapsulating agent, as this can increase the encapsulation rate of the encapsulating agent. In step 1, when a mixed liquid containing the encapsulating agent is used, the mixing ratio is not particularly limited, but is preferably 0.1 to 100 parts by weight, more preferably 1 to 50 parts by weight, and more preferably 10 to 30 parts by weight, per 100 parts by weight of the component constituting the thermoplastic resin (A).

[0066] (Process 2) Step 2 involves heating and stirring the pre-mixed liquid obtained in Step 1 to obtain a heated dispersion. The pressure during heating and stirring in step 2 is not particularly limited, but is preferably 0.1 to 10 MPa. It is preferable that this pressure is equal to or greater than the saturated vapor pressure of water at the heating temperature. The heating temperature is not particularly limited, but is preferably 80 to 200°C. A temperature within this range is preferable because it tends to result in a more uniform shape of the resulting composite particles. The temperature is preferably above the softening point or melting point of the components constituting the thermoplastic resin (A), more preferably 10°C or more above the softening point or melting point of the components constituting the thermoplastic resin (A), even more preferably 20°C or more above, and particularly preferably 30°C or more above. Furthermore, in step 2, heating the thermoplastic resin (A) to a temperature above its softening point or melting point, and stirring under a pressure of 0.1 MPa or higher, makes it easier to satisfy the inorganic fixation rate of the present invention.

[0067] The stirring method is not particularly limited, but it is sufficient if the mixture is stirred to a degree that it is well combined. The heating time is not particularly limited, but is preferably 1 to 30 hours. A heating time of 1 hour or more is preferable as it allows for more uniform dispersion and makes it easier to obtain the particle size of the present invention. A heating time of 30 hours or less tends to improve production efficiency. The lower limit of the heating time is more preferably 2 hours, even more preferably 3 hours, and most preferably 5 hours. The upper limit of the heating time is more preferably 25 hours, even more preferably 20 hours, and most preferably 15 hours.

[0068] (Step 3) Step 3 is a step of cooling the heated dispersion obtained in Step 2. By cooling the heated dispersion from Step 2, a dispersion of composite particles can be obtained. The cooling method is not particularly limited, but it is preferable to cool the heated dispersion obtained in step 2 to 5-50°C. The cooling rate is not particularly limited, but it may be rapidly cooled or naturally cooled by air cooling or the like. In step 3, stirring may be carried out at the stirring speed of step 2, or stirring may be stopped. The cooled dispersion is an aqueous dispersion containing composite particles.

[0069] The composite particles of the present invention may be used in the form of a dispersion, a wet powder, or a dry powder. The wet powder can be obtained by dehydrating the dispersion from step 3 using, for example, a centrifuge, a pressure press, or a vacuum dehydrator. The dispersion in step 3 may be dehydrated after measures are taken to reduce its viscosity. There are no particular limitations on the methods for reducing viscosity, but examples include diluting by adding water, salting out water-soluble components, and decomposing water-soluble components with oxidizing agents or enzymes. The viscosity of the liquid is not particularly limited as long as dehydration treatment can be carried out, but it is preferably 1,000 mPa·s or less, more preferably 500 mPa·s or less, and especially preferably 100 mPa·s or less, in order to suppress the aggregation of composite particles in the subsequent drying process. The dried powder can be obtained by drying the wet powder using a shelf dryer, indirect heating dryer, fluidized bed dryer, vacuum dryer, vibrating dryer, airflow dryer, etc. Alternatively, the dispersion obtained in step 3 can be dried using a spray dryer, fluidized bed dryer, etc. to obtain the dried powder. The dried powder may be classified by methods such as air classification or screen classification.

[0070] The method for producing the composite particles of the present invention is not particularly limited, but it may include a washing step in which the obtained particles are redispersed in a solvent such as water, dehydrated, and then the surfactants and water-soluble polymers contained therein are removed. The temperature of the solvent used for redispersion is not particularly limited, but a temperature of 50°C to 150°C is effective in removing contained surfactants, water-soluble polymers, etc. Preferably, this temperature is below the softening point or melting point of the components constituting the thermoplastic resin (A), more preferably 10°C or more lower than the softening point or melting point of the components constituting the thermoplastic resin (A), even more preferably 20°C or more lower, and particularly preferably 30°C or more lower.

[0071] [Applications of composite particles] The composite particles of the present invention can be used in cosmetics, paints, optical applications, resins, building materials, and the like. In particular, because the composite particles of the present invention have excellent mechanical strength, they can be suitably used in cosmetics and coating compositions.

[0072] When the composite particles of the present invention are incorporated into a cosmetic composition, the composite particles exhibit excellent mechanical strength, resulting in a cosmetic composition with high slipperiness. When used in cosmetics, it can be used in combination with known cosmetic ingredients. Examples of cosmetic ingredients include oils, surfactants, alcohols, water, humectants, gelling agents, thickeners, powders other than the composite particles of the present invention, UV absorbers, preservatives, antibacterial agents, antioxidants, and functional ingredients. Cosmetics containing the composite particles of the present invention can take the form of powder, solid, cream, gel, liquid, mousse, spray, etc. The weight percentage of composite particles in the total cosmetic composition is not particularly limited, but is preferably 0.1 to 50% by weight, more preferably 0.5 to 30% by weight, and even more preferably 1 to 20% by weight.

[0073] When the composite particles of the present invention are incorporated into a coating composition, the composite particles exhibit excellent mechanical strength, making them resistant to deformation, breakage, and scratching when external forces are applied. When used in coating compositions, it can be used in combination with known coating components. The weight percentage of composite particles in the overall coating composition is not particularly limited, but is preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, and even more preferably 1 to 10% by weight. [Examples]

[0074] Examples of the composite particles of the present invention will be described in detail below. However, the present invention is not limited to these examples. Furthermore, the physical properties of the particles listed in the examples and comparative examples were measured and further evaluated in the manner described below.

[0075] (Measurement of volume-average particle diameter) A laser diffraction scattering particle size distribution analyzer (Microtrac particle size distribution analyzer (model 9320-HRA), manufactured by Nikkiso Co., Ltd.) was used, and measurements were performed by irradiating with ultrasound for 120 seconds using a wet measurement method. For the volume-average particle size, the value at which the cumulative frequency of volume-based measurements reached 50% was adopted.

[0076] (Ash content measurement) The composite particles Wp (g), which had been dried in a 60°C oven for one day to remove moisture, were placed in a crucible and heated with an electric heater to 700°C for 30 minutes to induce ashing. The resulting ash Wq (g) was then measured by weight. The ash content CA (weight %) of the sample was calculated from Wp (g) and Wq (g) using the following formula. CA(weight%)=(Wq / Wp)×100

[0077] (Measurement of inorganic fixation rate) The composite particles were classified for 15 minutes using an ultrasonic sieve (SW-20AT, manufactured by Tsutsui Rikagakukikai Co., Ltd.). The sieved material was collected, and the ash content CB (weight %) was measured using the method described above. The inorganic fixation rate was calculated using the following formula. The sieve opening was set to be larger than the volume-average particle diameter of the inorganic particles and smaller than the volume-average particle diameter of the composite particles divided by 2. If the volume-average particle diameter of the inorganic particles was larger than the volume-average particle diameter of the composite particles divided by 2, the sieve opening closest to the value of the volume-average particle diameter of the composite particles divided by 2 was used. Inorganic fixation rate (%)=CB / CA×100

[0078] (Measurement of compression recovery rate) A sample was prepared by placing 10 mg of composite particles in an aluminum cup with a diameter of 6 mm (inner diameter 5.65 mm) and a depth of 4.8 mm, and placing an aluminum lid with a diameter of 5.6 mm and a thickness of 0.1 mm on top of the composite particle layer. Next, using a DMA (DMAQ800 model, TAinstruments), the height L1 of the composite particle layer was measured when a force of 2.5 N was applied to the sample from the top of the aluminum lid using a pressure bar at a 30°C environment. Subsequently, the composite particle layer was pressurized from 2.5 N to 18 N at a rate of 10 N / min, and then depressurized from 18 N to 2.5 N at a rate of 10 N / min, repeating this operation eight times. After that, the height L2 was measured when a force of 2.5 N was applied to the top of the aluminum lid using a pressure bar. The ratio of the measured L1 to L2, as shown in the formula below, was defined as the compression recovery rate of the composite particles. A compression recovery rate of 70% or higher was judged to indicate superior mechanical strength of the composite particles. Compression recovery rate (%) = (L2 / L1) × 100

[0079] (Measurement of true specific gravity) The weight a of a 100 mL volumetric flask was weighed, and then 1 g of composite particles were added to the volumetric flask as a sample, and the weight b was weighed. Isopropyl alcohol was then added to this to the 100 mL mark, and the total weight c was weighed. Separately, the empty weight x of the volumetric flask was weighed, and isopropyl alcohol was added to this to the mark, and the total weight y was weighed. From these weighed values, the true specific gravity was calculated using the following formula (4). True specific gravity=(ba)×(yx) / {100×(yx)-(cb)}(4) The true specific gravity of the composite particles was measured using this method.

[0080] [Example 1] 300 parts by weight of deionized water, 70 parts by weight of polybutylene succinate adipate (PBSA), 30 parts by weight of calcium carbonate, 0.5 parts by weight of sorbitan monolaurate, and 20 parts by weight of polyvinyl alcohol were mixed and placed in a 1 L pressure-resistant container and sealed. The internal temperature of the container was raised to 140°C, the initial pressure was set to 0.2 MPa, and the mixture was stirred at 300 rpm for 5 hours. After that, it was cooled to 50°C to obtain an aqueous dispersion of particles. The obtained aqueous dispersion was filtered, dried, and then classified by passing it through a sieve to obtain particle 1. The evaluation results for particle 1 are shown in Table 1. An electron microscope image of particle 1 is shown in Figure 1.

[0081] <Example 2> In Example 2, particle 2 was obtained in the same manner as in Example 1, except that the manufacturing conditions were changed as shown in Table 1, and after filtration, the particles were redispersed in a large amount of 90°C hot water and filtered again. The results are shown in Table 1.

[0082] <Examples 3-12 and Comparative Examples 1-3> Examples 3-12 and Comparative Examples 1-3 were obtained in the same manner as in Example 1, except that the manufacturing conditions were changed as shown in Table 1, to obtain particles 2-12 and comparative particles 1-2. In Comparative Example 3, composite particles could not be obtained. The results are shown in Table 1. [Table 1]

[0083] The types of raw materials used in Table 1 are shown below. Calcium carbonate 1: Manufactured by Bihoku Powdering Industry Co., Ltd., Softon 3200 (volume average particle size 0.7 μm) Calcium carbonate 2: Manufactured by Bihoku Powdering Industry Co., Ltd., Softon 1000 (volume average particle size 2.2 μm) Magnesium carbonate: Volume-average particle size 8 μm Titanium dioxide: STR-100N (volume average particle size 15 nm), manufactured by Sakai Chemical Co., Ltd. Zinc oxide: Volume-average particle size 0.75 μm

[0084] The particles in Examples 1 to 12 contained thermoplastic resin (A) and inorganic particles (B), and because the inorganic fixation rate was 50% or more, the particles had high mechanical strength. On the other hand, the particles in Comparative Examples 1 and 2 were not the particles of the present invention, and therefore were prone to deformation and fracture when external force was applied. [Industrial applicability]

[0085] Because the composite particles of the present invention have high mechanical strength, they can be suitably used in a variety of fields, such as cosmetics, paints, optical applications, resins, and building materials.< / x>

Claims

1. A composite particle comprising a thermoplastic resin (A) and inorganic particles (B), wherein the inorganic fixation rate is 50% or more.

2. The composite particle according to claim 1, wherein the melting point of the thermoplastic resin (A) is 70 to 150°C.

3. The composite particle according to claim 1 or 2, wherein the thermoplastic resin (A) comprises at least one selected from polyolefin resins, polyester resins, acrylic resins, and polyvinyl chloride resins.

4. The composite particle according to claim 1 or 2, wherein the inorganic particle (B) comprises at least one selected from inorganic oxides, inorganic hydroxides, inorganic carbonates, clay minerals, inorganic chlorides, and inorganic phosphates.

5. The composite particle according to claim 1 or 2, wherein the content of the inorganic particles (B) in the composite particle is 1 to 200 parts by weight per 100 parts by weight of the thermoplastic resin (A).

6. The composite particle according to claim 1 or 2, wherein the ash content of the composite particle is 1 to 60% by weight.

7. The volume-average particle diameter (D) of the inorganic particles (B) Ｂ５０ The composite particle according to claim 1 or 2, wherein the diameter is 10 μm or less.

8. The volume-average particle diameter (D) of the inorganic particles (B) Ｂ５０ The volume-average particle diameter (D) of the composite particles relative to ) ５０ ) ratio (D ５０ / D Ｂ５０ The composite particle according to claim 1 or 2, wherein ) is 2 or more.

9. A composition comprising the composite particles described in claim 1 or 2.

10. A cosmetic composition comprising the composite particles described in claim 1 or 2.

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