Surface-treated fine particle metal oxide

Abstract

To provide surface-treated solid particles which are excellent in handleability and impart a fresh feeling of use when blended in a cosmetic.SOLUTION: The surface-treated fine particle metal oxide is surface-treated with an amino-modified silicone represented by general formula (1). (R1 is a divalent hydrocarbyl group having C1 to 8 carbon atoms, n is a number of 1 to 5, R2 is a hydroxyl group and a divalent hydrocarbyl group having C1 to 20 carbon atoms, R3 is a divalent hydrocarbyl group having C1 to 8 carbon atoms, an alkoxyl group having C1 to 8 carbon atoms, a hydroxyl group, and a group R1 - NH (CH2) n -, a and b are each a number of 1 or more, a + b is 2 or more and less than 2000 as a number-average value, a plurality of the groups of,, and may be the same as or different from each other, and the () unit and the ((hepta-NH (hepta-n-dodecene) O) unit may be a block or random unit.) SiR2 NH2 NH2 R1 SiR22O R1 CH2 R3 R2. ) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a surface-treated particulate metal oxide. [Background technology]

[0002] Sunscreen cosmetics contain UV protection agents to impart a high SPF (Sun Protection Factor). For example, the use of organic UV absorbers, UV scattering agents, etc., can impair the feel of the cosmetics when applied. Furthermore, emulsion-type sunscreen cosmetics often contain surfactants, which can also impair the feel of the cosmetics when applied.

[0003] Therefore, in order to realize sunscreen cosmetics that have a high SPF and a refreshing feel when used, there is a demand for solid particles that can be "Pickering emulsified" without the addition of surfactants and that have a high SPF function.

[0004] In order to realize such particles, it is conceivable to modify the solid particles by subjecting them to a surface treatment.

[0005] Regarding the modification of solid particles, for example, Patent Document 1 describes a surface-treated powder in which the surface of spherical glass beads is treated with amino-modified silicone, and explains that cosmetics containing this surface-treated powder provide a feeling of softness, moisture, and adhesion when applied to the skin.

[0006] Furthermore, Patent Document 2 describes treating the surface of a base powder made of sericite, talc, titanium oxide, or the like with amino-modified silicone, and explains that cosmetics containing the resulting surface-treated powder have excellent spreadability, adhesion, and moisturizing properties. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2020-203842 [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-182729 Summary of the Invention [Problem to be solved by the invention]

[0008] The Pickering emulsifiers used in the prior art did not have SPF functionality themselves and had to be combined with other UV protection agents.

[0009] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide surface-treated solid particles that have a high SPF function and are capable of undergoing Pickering emulsification when incorporated into cosmetics. [Means for solving the problem]

[0010] The present invention is as follows.

[0011] <Embodiment 1> A surface-treated fine particle metal oxide that has been surface-treated with a hydrophobic treatment agent, The hydrophobic treatment agent contains an amino-modified silicone represented by the following general formula (1): Surface treated fine particle metal oxide. [ka] (In formula (1), R 1 is selected from divalent hydrocarbon groups having 1 to 8 carbon atoms; n is a number from 1 to 5, R 2 is selected from a hydroxyl group and a divalent hydrocarbon group having 1 to 20 carbon atoms, R 3 represents a divalent hydrocarbon group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a hydroxyl group, and a group R 1 -NH(CH2) n -NH2, a and b are each a number of 1 or more, and a+b is a number average value of 2 or more and less than 2,000, Multiple Rs 1 , R 2 , and R 3 may be the same or different groups, (SiR 2 2O) units and (SiR 2 (R 1 -NH(CH2) n The —NH2)O) units may be in block or random arrangement. Aspect 2: The surface-treated fine metal oxide particles according to Aspect 1, wherein the amino-modified silicone is an aminoethylaminopropylmethylsiloxanedimethylsiloxane copolymer. Aspect 3: The surface-treated fine particle metal oxide according to Aspect 1, wherein the surface-treated fine particle metal oxide is surface-treated fine particle zinc oxide. Aspect 4: The surface-treated fine particle metal oxide according to Aspect 2, wherein the surface-treated fine particle metal oxide is surface-treated fine particle zinc oxide. Aspect 5: The surface-treated fine metal oxide particles according to any one of Aspects 1 to 4, having an average primary particle size of less than 80 nm. <Embodiment 6> Further, the film is treated with a hydrophilic treatment agent, The hydrophilic treatment agent contains hydrated silica. 5. The surface-treated fine metal oxide particles according to any one of aspects 1 to 4. Aspect 7: The amount of substance of the hydrophilic treatment agent (M WAT (mol)) of the substance amount of the hydrophobic treatment agent (M OIL (mol)) ratio ((M OIL ) / M WAT 7. The surface-treated particulate metal oxide according to embodiment 6, wherein the value of (R) is 0.090 or less. Aspect 8: The ratio (M OIL / M WAT 4. The surface-treated fine metal oxide particle according to any one of aspects 1 to 3, wherein ) is 0.0001 or more. Aspect 9: The surface-treated fine metal oxide particle according to aspect 6, wherein the hydrophobic treatment agent further contains a fatty acid. Aspect 10: The surface-treated fine metal oxide particles according to any one of Aspects 1 to 4, which have Pickering emulsification ability. Aspect 11: The surface-treated fine metal oxide particles according to Aspect 6, which have Pickering emulsification ability. Aspect 12: An oil-in-water cosmetic comprising the surface-treated fine metal oxide particles according to any one of Aspects 1 to 4. [Effects of the Invention]

[0012] The surface-treated fine metal oxide particles of the present invention have excellent handleability and impart a fresh feeling to cosmetics when blended therein. Furthermore, the surface-treated fine metal oxide particles of the present invention have Pickering emulsifying ability and can be used as a Pickering emulsifier. DETAILED DESCRIPTION OF THE INVENTION

[0013] The surface-treated fine particle metal oxide of the present invention is A surface-treated fine particle metal oxide that has been surface-treated with a hydrophobic treatment agent, The hydrophobic treatment agent contains an amino-modified silicone represented by the following general formula (1): It is a surface-treated fine particle metal oxide. [ka] (In formula (1), R 1 is selected from divalent hydrocarbon groups having 1 to 8 carbon atoms; n is a number from 1 to 5, R 2 is selected from a hydroxyl group and a divalent hydrocarbon group having 1 to 20 carbon atoms, R 3 represents a divalent hydrocarbon group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a hydroxyl group, and a group R 1 -NH(CH2) n -NH2, a and b are each a number of 1 or more, and a+b is a number average value of 2 or more and less than 2,000, Multiple Rs 1 , R 2 , and R3 may be the same or different groups, (SiR 2 2O) units and (SiR 2 (R 1 -NH(CH2) n The —NH2)O) units may be in block or random arrangement.

[0014] The surface-treated fine particle metal oxide of the present invention may be treated with a hydrophilic treatment agent in addition to a hydrophobic treatment agent, and is preferably a fine particle metal oxide treated with both a hydrophobic treatment agent and a hydrophilic treatment agent.

[0015] The surface-treated fine particle metal oxide of the present invention has Pickering emulsification ability, and a composition containing the surface-treated fine particle metal oxide of the present invention, water, and an oil component exhibits an oil-in-water emulsion state. This emulsion composition can be used, for example, as a cosmetic.

[0016] <Hydrophobic treatment agent> The hydrophobic treatment agent contains a predetermined amino-modified silicone and may further contain a fatty acid. The hydrophobic treatment agent may or may not contain treatment agents other than the amino-modified silicone and the fatty acid.

[0017] <Amino-modified silicone> The amino-modified silicone used in the surface treatment of the fine particle metal oxide of the present invention is a compound represented by the following general formula (1).

[0018] [ka]

[0019] (In formula (1), R 1 is selected from divalent hydrocarbon groups having 1 to 8 carbon atoms; n is a number from 1 to 5, R 2 is selected from a hydroxyl group and a monovalent hydrocarbon group having 1 to 20 carbon atoms, R 3 represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a hydroxyl group, and a group R 1 -NH(CH2) n -NH2, a and b are each a number of 1 or more, and a+b is a number average value of 2 or more and less than 2,000, Multiple Rs 1 , R 2 , and R 3 may be the same or different groups, (SiR 2 2O) units and (SiR 2 (R 1 -NH(CH2) n The —NH2)O) units may be in block or random arrangement.

[0020] R in formula (1) 1 is a divalent hydrocarbon group having 1 to 8 carbon atoms. 1 The carbon number of the hydrocarbon group may be 2 to 6, and particularly 3 or 4. Specifically, R 1 may be, for example, a divalent group selected from a 1,2-propylene group, a 1,3-propylene group, an isobutylene group, a 2-methyl-1,3-propylene group, and the like.

[0021] R 2 R is a monovalent group selected from a hydroxyl group and a monovalent hydrocarbon group having 1 to 20 carbon atoms. 2 When R is a hydrocarbon group, the number of carbon atoms may be 1 to 12, 1 to 6, or 1 to 4. Specifically, R 2 may be, for example, a group selected from a methyl group and an ethyl group.

[0022] R 3 represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a hydroxyl group, and a group R 1 -NH(CH2) n R is a monovalent group selected from —NH 2When is a hydrocarbon group or an alkoxyl group, the number of carbon atoms may be 1 to 12, 1 to 6, or 1 to 4. The hydrocarbon group may specifically be, for example, a group selected from a methyl group and an ethyl group, and the alkoxyl group may specifically be, for example, a group selected from a methoxyl group and an ethoxyl group.

[0023] In formula (1), a+b may be 20 or more, or 30 or more, and may be less than 1,000.

[0024] The amino equivalent of the amino-modified silicone may be 200 g / mol or more, 500 g / mol or more, or 600 g / mol or more, and may be 30,000 g / mol or less, 20,000 g / mol or less, 15,000 g / mol or less, 10,000 g / mol or less, or 5,000 g / mol or less. This amino equivalent is a value defined as the mass of the siloxane skeleton per amino group or ammonium group.

[0025] The viscosity of amino-modified silicone is the kinematic viscosity at 25°C, measured at 100 mm 2 / s or more, 200mm 2 / s or more, 300mm 2 / s or more, 500mm 2 / s or more, or 700 mm 2 / s or more, 3,000 mm 2 / s or less, 2,500mm 2 / s or less, 2,000mm 2 / s or less, 1,800mm 2 / s or less, 1,500mm 2 / s or less, or 1,300 mm 2 / s or less.

[0026] The amino-modified silicone in the present invention may be an aminoethylaminopropylmethylsiloxane-dimethylsiloxane copolymer, known by the INCI (International Nomenclature of Cosmetic Ingredients) name "amodimethicone."

[0027] <fatty acid> The fatty acid optionally used in the surface treatment of the surface-treated fine particle metal oxide of the present invention may be, for example, a higher fatty acid, particularly a saturated higher fatty acid, and the hydrocarbon group portion of the fatty acid may be linear or branched.

[0028] The fatty acid may be a saturated fatty acid having 12 to 28 carbon atoms, and specifically may be, for example, lauric acid, myristic acid, palmitic acid, isopalmitic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, isobehenic acid, lignoceric acid, cerotic acid, montanic acid, etc., and may be one or more selected from these.

[0029] <Hydrophilic treatment agent> The hydrophilic treatment agent optionally used in the surface treatment of the surface-treated fine particle metal oxide of the present invention contains hydrated silica. The hydrophilic treatment agent may or may not contain a treatment agent other than hydrated silica.

[0030] Hydrous silica is a hydrate of silica that normally adsorbs 5 to 8% water by mass, and is known in the industry as having the chemical formula "SiO2·nH2O" or "SiO2·xH2O" (n and x vary depending on the manufacturing method).

[0031] 《Ratio((M OIL ) / M WAT )》 When the surface-treated fine particle metal oxide of the present invention is surface-treated with both a hydrophobic treatment agent and a hydrophilic treatment agent, the amount of the hydrophilic treatment agent (M WAT (mol)) to the amount of hydrophobic treatment agent (M OIL (mol)) ratio ((M OIL ) / M WATFrom the viewpoint of imparting good Pickering emulsification ability to the obtained surface-treated fine particle metal oxide, the ratio ((M OIL ) / M WAT ) may be 0.0001 or more, 0.0005 or more, 0.001 or more, 0.005 or more, or 0.010 or more.

[0032] Here, when the hydrophobic treatment agent is composed only of the amino-modified silicone represented by the general formula (1), the amount of substance (M OIL When the hydrophobic treatment agent is composed of the amino-modified silicone represented by the general formula (1) and a fatty acid, the amount of the hydrophobic treatment agent (M OIL (mol)) is equal to the sum of the amount of substance of the amino-modified silicone and the amount of substance of the fatty acid.

[0033] In addition, when the hydrophilic treatment agent is composed only of hydrated silica, the substance amount of the hydrophilic treatment agent (M WAT (mol)) is equal to the amount of hydrous silica.

[0034] 《Fine particle metal oxide》 The fine particle metal oxide in the surface-treated fine particle metal oxide of the present invention may be, for example, fine particle zinc oxide, fine particle iron oxide, fine particle titanium oxide, fine particle alumina, fine particle tin oxide, fine particle cerium oxide, etc., and may be one or more types selected from these.

[0035] The particulate metal oxide in the surface-treated particulate metal oxide of the present invention may typically be particulate zinc oxide.

[0036] From the viewpoint of allowing the surface-treated fine particle metal oxide to exhibit good Pickering emulsifying ability and imparting a fresh feel to cosmetics containing the surface-treated fine particle metal oxide, the average primary particle diameter of the surface-treated fine particle metal oxide of the present invention may be less than 80 nm. The average primary particle diameter of the surface-treated fine particle metal oxide may be 60 nm or less, 50 nm or less, 40 nm or less, or 30 nm or less. On the other hand, from the viewpoint of ensuring the handleability of the surface-treated fine particle metal oxide, the average primary particle diameter may be 5 nm or more, 10 nm or more, 15 nm or more, or 20 nm or more.

[0037] <Oil-in-water cosmetics> According to another aspect of the present invention, there is provided an oil-in-water cosmetic comprising the surface-treated fine particle metal oxide of the present invention.

[0038] As explained above, the surface-treated fine particle metal oxide of the present invention has Pickering emulsification ability, and therefore, the oil-in-water cosmetic of the present invention containing the surface-treated fine particle metal oxide does not need to contain an emulsifier that is contained in ordinary cosmetics.

[0039] The oil-in-water cosmetic of the present invention contains the surface-treated fine particle metal oxide of the present invention, and may also contain water and oil together with this, and may further contain a functional component that enables the oil-in-water cosmetic of the present invention to function as a cosmetic.

[0040] Examples of oils contained in the oil-in-water cosmetic of the present invention include diisopropyl sebacate, isopropyl myristate, glyceryl tri-2-ethylhexanoate, cetyl 2-ethylhexanoate, tripropylene glycol dineopentanoate, isononyl isononanoate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, and stearic acid. Isocetyl phosphate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentaerythrityl tetra-2-ethylhexanoate, triethylhexyl Sanoin (Glyceryl tri-2-ethylhexanoate), Glyceryl trioctanoate, Glyceryl triisopalmitate, Trimethylolpropane triisostearate, Cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, Glyceryl trimyristate, Tri-2-heptylundecanoic acid glyceride, Castor oil fatty acid methyl ester, Oleyl oleate, Acetoglyceride, 2-heptylundecyl palmitate, Diisobutyl adipate, N-octyldodecyl lauroyl-L-glutamate esters, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, 2-ethylhexyl succinate, triethyl citrate, diisopropyl sebacate, olive oil, sunflower oil, camellia oil, soybean oil, jojoba oil, macadamia nut oil, meadowfoam oil, alkyl benzoate, dimethicone, caprylyl methicone, etc., and one or more selected from these may be used.

[0041] Since the surface-treated metal oxide fine particles of the present invention have a sunscreen effect, it is conceivable that the oil-in-water cosmetic composition of the present invention can be used as a sunscreen cosmetic composition. In this case, the functional ingredients in the oil-in-water cosmetic composition of the present invention include, for example, an ultraviolet protection agent, and may further include a moisturizer, a thickener, a pH adjuster, an active agent, a preservative, etc.

[0042] The types and amounts of functional ingredients contained in the oil-in-water cosmetic of the present invention may be determined appropriately by those skilled in the art depending on the specific use of the cosmetic. [Example]

[0043] Examples 1 to 5 and Comparative Examples 1 and 2 Cosmetic compositions containing water and oil were prepared by blending the components shown in Table 1. In Table 1, the blending amount of each component is expressed in mass % based on the total mass of the cosmetic composition.

[0044] Specifically, (A) a mixture of surface-treated fine particle metal oxide and, if blended, (A') other fine particle metal oxide, and (C) oil, and (B) a mixture of other ingredients in water were prepared separately, then mixed and shaken well to obtain a cosmetic composition.

[0045] The (A) surface-treated fine particle metal oxide and (A') other fine particle metal oxide listed in Table 1 are both fine particles with an average primary particle diameter of 25 nm.

[0046] The obtained cosmetic composition was sampled in a test tube and visually inspected for emulsification. The results are shown in Table 1.

[0047] [Table 1]

[0048] The cosmetic compositions obtained in Comparative Examples 1 and 2 had separated oil and were not emulsified. In contrast, the cosmetic compositions obtained in Examples 1 to 5 were in a stable emulsified state. The emulsions of the cosmetic compositions obtained in Examples 1 to 5 were oil-in-water type.

Claims

1. A surface-treated fine particle metal oxide that has been surface-treated with a hydrophobic treatment agent, The hydrophobic treatment agent contains an amino-modified silicone represented by the following general formula (1): Surface treated fine particle metal oxide. 【Chemistry 1】 (In formula (1), R １ is selected from divalent hydrocarbon groups having 1 to 8 carbon atoms; n is a number from 1 to 5, R ２ is selected from a hydroxyl group and a divalent hydrocarbon group having 1 to 20 carbon atoms; R ３ represents a divalent hydrocarbon group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a hydroxyl group, and a group R １ -NH(CH ２ ) ｎ -NH ２ is selected from a and b are each a number of 1 or more, and a+b is a number average value of 2 or more and less than 2,000, Multiple Rs １ , R ２ , and R ３ may be the same or different groups, (SiR ２ ２ O) unit and (SiR ２ (R １ -NH(CH ２ ) ｎ -NH ２ 0) Units may be block or random.

2. 2. The surface-treated fine particle metal oxide according to claim 1, wherein the amino-modified silicone is an aminoethylaminopropylmethylsiloxanedimethylsiloxane copolymer.

3. 2. The surface-treated particulate metal oxide of claim 1, wherein said surface-treated particulate metal oxide is surface-treated particulate zinc oxide.

4. 3. The surface-treated particulate metal oxide of claim 2, wherein the surface-treated particulate metal oxide is surface-treated particulate zinc oxide.

5. 5. The surface-treated fine metal oxide particle according to claim 1, wherein the average primary particle size is less than 80 nm.

6. Furthermore, it has been treated with a hydrophilic treatment agent, The hydrophilic treatment agent contains hydrated silica. The surface-treated fine metal oxide particles according to any one of claims 1 to 4.

7. The amount of the hydrophilic treatment agent (M ＷＡＴ (mol)) of the hydrophobic treatment agent (M ＯＩＬ (mol)) ratio ((M ＯＩＬ ) / M ＷＡＴ 7. The surface-treated fine particle metal oxide according to claim 6, wherein the value of (a) is 0.090 or less.

8. Said ratio (M ＯＩＬ / M ＷＡＴ 4. The surface-treated fine metal oxide particle according to claim 1, wherein the value of (a) is 0.0001 or more.

9. 7. The surface-treated fine particle metal oxide according to claim 6, wherein the hydrophobic treatment agent further contains a fatty acid.

10. The surface-treated fine particle metal oxide according to any one of claims 1 to 4, which has Pickering emulsification ability.

11. The surface-treated fine particle metal oxide according to claim 6, which has Pickering emulsification ability.

12. An oil-in-water cosmetic comprising the surface-treated fine particle metal oxide according to any one of claims 1 to 4.

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