Carboxyl-modified organopolysiloxane having (poly) glyceryl group or polyoxyalkylene group, and cosmetic

Abstract

Provided are an organopolysiloxane having excellent emulsion stability, and a cosmetic using the organopolysiloxane. [Formula 1] (R12SiO2 / 2) a (R1R2SiO2 / 2) b (R1R3SiO2 / 2) c (R1R4SiO2 / 2) d (R1SiO3 / 2) e (SiO4 / 2) f (R13SiO1 / 2) 2 + e + 2f (1) [in the formula, R1 is a monovalent hydrocarbon group, R2 is a (poly) glyceryl group or polyoxyalkylene group, R3 is a carboxyl group, 0 < = a < = 100, 1 < = b < = 10, 1 < = c < = 10, 0 < = d < = 10, e > = 0, and f > = 0. ] A carboxyl-modified organopolysiloxane having a (poly) glyceryl group or a polyoxyalkylene group represented by formula (1).

Description

Technical Field

[0001] The present invention relates to organopolysiloxane and a cosmetic using the same. Background Art

[0002] Silicone surfactants are widely used because they are refreshing, less sticky, and provide an excellent feel. For example, various emulsion compositions containing polyether-modified silicones and polyglycerol-modified silicones have been proposed (Patent Documents 1 and 2). However, when polar oils such as ester oils are used as lubricants, the emulsion stability is insufficient, and phase separation may occur over time.

[0003] Furthermore, Patent Document 3 proposes the use of carboxyl-modified silicone in an oil-in-water emulsion composition.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2021-075488

[0007] Patent Document 2: International Publication No. 2018 / 117172

[0008] Patent Document 3: Japanese Patent Application Laid-Open No. 2020-172481 Summary of the Invention

[0009] Problems to be solved by the invention

[0010] However, the combined use of fine-particle zinc oxide may deteriorate the emulsion stability, and thus there is room for further improvement in the emulsion stability performance of silicone surfactants.

[0011] Therefore, if the amount of the emulsifier or thickener added is increased in order to improve the emulsion stability, the stickiness will increase instead, which may lead to a problem that the feeling of use which is an advantage of the silicone surfactant is deteriorated.

[0012] The present invention has been made in view of the above-mentioned actual circumstances, and an object of the present invention is to provide an organopolysiloxane having excellent emulsion stability and a cosmetic using the organopolysiloxane.

[0013] Means for solving problems

[0014] The present inventors have conducted intensive studies to achieve the above-mentioned object and have found that the use of an organopolysiloxane having a (poly)glyceryl group or a polyoxyalkylene group in combination with a carboxyl group as an emulsifier provides an emulsion composition having extremely excellent storage stability, thereby completing the present invention.

[0015] Specifically, the present invention provides the following carboxyl-modified organopolysiloxane having a (poly)glyceryl group or a polyoxyalkylene group, the organopolysiloxane, and a cosmetic using the same.

[0016] [1] A carboxyl-modified organopolysiloxane represented by the following formula (1):

[0017] [Chemistry 1]

[0018] (R 1 2SiO 2 / 2 ) a (R 1 R 2 SiO 2 / 2 ) b (R 1 R 3 SiO 2 / 2 ) c (R 1 R 4 SiO 2 / 2 ) d (R 1 SiO 3 / 2 ) e (SiO 4 / 2 ) f (R 1 3SiO 1 / 2 ) 2+e+2f (1)

[0019] [Where R 1 are independently monovalent hydrocarbon groups selected from alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 15 carbon atoms, and aralkyl groups having 7 to 15 carbon atoms,

[0020] R 2 are independently a group represented by the following formula (2) or (3),

[0021] [Chemistry 2]

[0022] -C g H 2g -OR 5 (2)

[0023] (Where R 5 In the following formula (2-1)

[0024] [Chemistry 3]

[0025]

[0026] A group in which a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms is independently bonded to the oxygen atom terminal of a group represented by formula (2-1) or a group formed by connecting a plurality of groups represented by formula (2-1), wherein g in formula (2) is an integer satisfying 0≤g≤20, and R 5 The number h of the groups represented by formula (2-1) is an integer satisfying 1≤h≤10.

[0027] [Chemistry 4]

[0028]

[0029] (Where R 6 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, i is an integer satisfying 0≤i≤20, j1 and j2 are integers satisfying 2≤j1≤100 and 0≤j2≤100. The order of arrangement of the units enclosed by j1 and the units enclosed by j2 is arbitrary.

[0030] R 3 are independently a group represented by the following formula (4),

[0031] [Chemistry 5]

[0032] -L 1 -((OR 7 ) k -L 2 ) z -COOH (4)

[0033] (Where, L 1 and L 2 Each is a divalent linking group having 2 to 20 carbon atoms, R 7 is a divalent alkylene group having 2 to 4 carbon atoms, k is an integer satisfying 0≤k≤100, and l is 0 or 1.

[0034] R 4 are independently a group represented by the following formula (5), (6), (7), or (8),

[0035] [Chemistry 6]

[0036] -(CH2)2-C n H 2n -(SiR 1 2O) m -SiR 1 3 (5)

[0037] -(CH2)2-C n H 2n -SiR 1 m1 -(OSiR 1 3)3-m1 (6)

[0038] -(CH2)2-C n H 2n -SiR 1 m1 -(OSiR 1 m2 (OSiR 1 3) 3-m2 ) 3-m1 (7)

[0039] -(CH2)2-C n H 2n -SiR 1 m1 -(OSiR 1 m2 (OSiR 1 m3 (OSiR 1 3) 3-m3 ) 3-m2 ) 3-m1 (8)

[0040] (Where R 1 As defined above, n and m are integers satisfying 0≤n≤5, 0≤m≤100, and m1, m2, and m3 are integers satisfying 0≤m1≤2, 0≤m2≤2, and 0≤m3≤2.

[0041] a, b, c, d, e, and f each satisfy

[0042] 0≤a≤100,

[0043] 1≤b≤10,

[0044] 1≤c≤10,

[0045] 0≤d≤10,

[0046] An integer where e≥0 and f≥0.

[0047] The order of arrangement of the structural units enclosed by a to f is arbitrary.]

[0048] [2] The carboxyl-modified organopolysiloxane according to [1], wherein the organopolysiloxane is represented by the following formula (1-1):

[0049] [Chemistry 7]

[0050]

[0051] (Where R 1 、R 2 、R 3 、R4 , a, b, c, and d have the same meanings as above.)

[0052] [3] A cosmetic material comprising:

[0053] (A) the carboxyl-modified organopolysiloxane represented by formula (1) according to [1] or [2],

[0054] (B) oil, and

[0055] (C) Water.

[0056] [4] The cosmetic according to [3], wherein the oil (B) is at least one selected from silicone oil, hydrocarbon oil, and fatty acid ester.

[0057] [5] The cosmetic according to [3] or [4], which is an oil-in-water emulsified cosmetic.

[0058] Effects of the Invention

[0059] The emulsified composition containing the carboxy-modified organopolysiloxane having a (poly)glyceryl group or a polyoxyalkylene group of the present invention has little change in viscosity and particle size over time, and a cosmetic obtained using the emulsified composition has excellent stability. DETAILED DESCRIPTION

[0060] The present invention will be described in detail below.

[0061] [Carboxyl-modified organopolysiloxane]

[0062] The organopolysiloxane of the present invention is a carboxyl-modified organopolysiloxane having a (poly)glyceryl group or a polyoxyalkylene group and represented by the following formula (1).

[0063] [Chemistry 8]

[0064] (R 1 2SiO 2 / 2 ) a (R 1 R 2 SiO 2 / 2 ) b (R 1 R 3 SiO 2 / 2 ) c (R 1 R 4 SiO 2 / 2 ) d (R 1 SiO 3 / 2 ) e (SiO 4 / 2 ) f (R 1 3SiO 1 / 2) 2+e+2f (1)

[0065] [Where R 1 are independently monovalent hydrocarbon groups selected from alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 15 carbon atoms, and aralkyl groups having 7 to 15 carbon atoms,

[0066] R 2 are independently a group represented by the following formula (2) or (3),

[0067] [Chemistry 9]

[0068] -C g H 2g -OR 5 (2)

[0069] (Where R 5 In the following formula (2-1)

[0070] [Chemistry 10]

[0071]

[0072] A group in which a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms is independently bonded to the oxygen atom terminal of a group represented by formula (2-1) or a group formed by connecting a plurality of groups represented by formula (2-1), wherein g in formula (2) is an integer satisfying 0≤g≤20, and R 5 The number h of the groups represented by formula (2-1) is an integer satisfying 1≤h≤10.

[0073] [Chemistry 11]

[0074]

[0075] (Where R 6 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, i is an integer satisfying 0≤i≤20, j1 and j2 are integers satisfying 2≤j1≤100 and 0≤j2≤100. The order of arrangement of the units enclosed by j1 and the units enclosed by j2 is arbitrary.

[0076] R 3 are independently a group represented by the following formula (4),

[0077] [Chemistry 12]

[0078] -L 1 -((OR 7 ) k -L 2 ) z -COOH (4)

[0079] (Where, L1 and L 2 Each is a divalent linking group having 2 to 20 carbon atoms, R 7 is a divalent alkylene group having 2 to 4 carbon atoms, k is an integer satisfying 0≤k≤100, and z is 0 or 1.

[0080] R 4 are independently a group represented by the following formula (5), (6), (7), or (8),

[0081] [Chemistry 13]

[0082] -(CH2)2-C n H 2n -(SiR 1 2O) m -SiR 1 3 (5)

[0083] -(CH2)2-C n H 2n -SiR 1 m1 -(OSiR 1 3) 3-m1 (6)

[0084] -(CH2)2-C n H 2n -SiR 1 m1 -(OSiR 1 m2 (OSiR 1 3) 3-m2 ) 3-m1 (7)

[0085] -(CH2)2-C n H 2n -SiR 1 m1 -(OSiR 1 m2 (OSiR 1 m3 (OSiR 1 3) 3-m3 ) 3-m2 ) 3-m1 (8)

[0086] (Where R 1 As defined above, n and m are integers satisfying 0≤n≤5, 0≤m≤100, and m1, m2, and m3 are integers satisfying 0≤m1≤2, 0≤m2≤2, and 0≤m3≤2.

[0087] a, b, c, d, e, and f each satisfy

[0088] 0≤a≤100,

[0089] 1≤b≤10,

[0090] 1≤c≤10,

[0091] 0≤d≤10,

[0092] An integer where e≥0 and f≥0.

[0093] The order of arrangement of the structural units enclosed by a to f is arbitrary.]

[0094] In formula (1), the order of arrangement of the structural units enclosed by a to f is arbitrary. The structural unit group enclosed by a, the structural unit group enclosed by b, the structural unit group enclosed by c, the structural unit group enclosed by d, the structural unit group enclosed by e, and the structural unit group enclosed by f can be arranged in any order within each structural unit group, and the structural units enclosed by a, the structural units enclosed by b, the structural units enclosed by c, the structural units enclosed by d, the structural units enclosed by e, and the structural units enclosed by f can be arranged in any order for each of these structural units.

[0095] In formula (1), R 1 are independently monovalent hydrocarbon groups selected from alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 15 carbon atoms, and aralkyl groups having 7 to 15 carbon atoms. The alkyl group may be linear, branched, or cyclic. 1 Specifically, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, and hexadecyl; cycloalkyl groups such as cyclopentyl; aryl groups such as phenyl and tolyl; and aralkyl groups such as benzyl and phenethyl. Different R groups may be contained in one molecule. 1 As R 1 , preferably methyl. In addition, the organopolysiloxane of formula (1) has an alkyl group having 6 or more carbon atoms as R 1 In this case, the alkyl group having 6 or more carbon atoms is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, based on the total mass of the organopolysiloxane of formula (1).

[0096] In formula (1), R 2 Each of the following groups is independently represented by the following formula (2) or (3), and may contain different R 2 .

[0097] [Chemistry 14]

[0098] -C g H2g -OR 5 (2)

[0099] [Chemistry 15]

[0100]

[0101] In the group represented by formula (2), R 5 In the following formula (2-1)

[0102] [Chemistry 16]

[0103]

[0104] A group in which a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms is independently bonded to the oxygen atom terminal of a group represented by formula (2-1) or a group formed by linking a plurality of groups represented by formula (2-1).

[0105] When a plurality of groups represented by formula (2-1) are linked, examples of the linked structure include a linear structure in which the 1-position or 3-position of glycerol is linked to each other, and a branched structure in which the 2-position of glycerol is linked to the 1-position or 3-position of glycerol. In the case of a branched structure, the number of branch points is not particularly limited, but is preferably 2 or less, more preferably 1 or less.

[0106] Examples of the hydrocarbon group in the hydrogen atom or monovalent hydrocarbon group having 1 to 30 carbon atoms bonded to the terminal of the oxygen atom include alkyl groups having 1 to 30 carbon atoms, preferably 1 to 16 carbon atoms, aryl groups having 6 to 30 carbon atoms, preferably 6 to 15 carbon atoms, and aralkyl groups having 7 to 30 carbon atoms, preferably 7 to 15 carbon atoms. Specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, neopentyl, decyl, lauryl, stearyl, and oleyl; aryl groups such as phenyl and naphthyl; and aralkyl groups such as benzyl and 2-phenylethyl.

[0107] In formula (2), g is an integer satisfying 0≤g≤20, and g may be 2 or more, or 3 or more. g H 2g -, specifically, -(CH2)2-, -(CH2)3-, -CH2CH(CH3)CH2-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -(CH2)2-CH(CH2CH2CH3)-, -CH2-CH(CH2CH3)-, etc. can be exemplified.

[0108] R 5The number h of the groups represented by formula (2-1) is an integer satisfying 1≤h≤10, preferably 2≤h≤5, more preferably 2≤h≤3. If h exceeds 10, the viscosity of the organopolysiloxane itself increases, deteriorating the feel and usability.

[0109] Furthermore, (poly)glyceryl includes monoglyceryl and polyglyceryl, and also includes isomers. 2 Examples include groups derived from monoglycerol of the following general formula (9), diglycerol of the general formulas (10) and (11), and triglycerol of the general formulas (12) to (15), wherein g = 3 and h = 1 to 3 in formula (2).

[0110] [Chemistry 17]

[0111]

[0112] In the group represented by formula (3), R 6 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms. Examples of the hydrocarbon group include alkyl groups having 1 to 30 carbon atoms, preferably 1 to 16 carbon atoms, aryl groups having 6 to 30 carbon atoms, preferably 6 to 15 carbon atoms, and aralkyl groups having 7 to 30 carbon atoms, preferably 7 to 15 carbon atoms. Specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, neopentyl, decyl, lauryl, stearyl, and oleyl; aryl groups such as phenyl and naphthyl; and aralkyl groups such as benzyl and 2-phenylethyl.

[0113] In formula (3), i is an integer satisfying 0≤i≤20, and i may be 2 or more, or 3 or more. i H 2i -, specifically, -(CH2)2-, -(CH2)3-, -CH2CH(CH3)CH2-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -(CH2)2-CH(CH2CH2CH3)-, -CH2-CH(CH2CH3)-, etc. can be exemplified.

[0114] j1 in formula (3) is an integer satisfying 2≤j1≤100, preferably 2≤j1≤50, more preferably 2≤j1≤15. j2 is an integer satisfying 0≤j2≤100, preferably 0≤j2≤50, more preferably 0≤j2≤5.

[0115] Furthermore, regarding the bonding of the oxyalkylene units enclosed by j1 and j2 in the above formula (3), the order of arrangement is arbitrary and may be block or random.

[0116] When the organopolysiloxane of the present invention is used as an emulsifier, R 2The content is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, based on the total mass of the organopolysiloxane.

[0117] In formula (1), R 3 Each of the groups is independently represented by the following formula (4), and different groups may be contained in one molecule.

[0118] [Chemistry 18]

[0119] -L 1 -((OR 7 ) k -L 2 ) z -COOH (4)

[0120] (Where, L 1 and L 2 Each is a divalent linking group having 2 to 20 carbon atoms, R 7 is a divalent alkylene group having 2 to 4 carbon atoms, k is an integer satisfying 0≤k≤100, and z is 0 or 1.

[0121] Among them, L 1 and L 2 Each is a divalent linking group having 2 to 20 carbon atoms. Examples of the divalent linking group include alkylene groups having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms. Specific examples include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene, and octadecamethylene.

[0122] R 7 It is a divalent alkylene group having 2 to 4 carbon atoms. Examples of the divalent alkylene group include ethylene, trimethylene, and tetramethylene.

[0123] k is an integer satisfying 0≤k≤100, preferably 0≤k≤50, and more preferably 0≤k≤5.

[0124] When the organopolysiloxane of the present invention is used as an emulsifier, R 3 The content of R is preferably 1 to 50% by mass, more preferably 1 to 25% by mass, of the total mass of the organopolysiloxane. 3 , groups derived from carboxylic acids of the following general formulae (16) to (18) can be exemplified.

[0125] [Chemistry 19]

[0126] -C 10 H 20 -COOH (16)

[0127] -C3H6-COOH (17)

[0128]

[0129] In formula (1), R 4 Each of the following groups is independently represented by the general formula (5), (6), (7), or (8), and may contain different R 4 .

[0130] [Chemistry 20]

[0131] -(CH2)2-C n H 2n -(SiR 1 2O) m -SiR 1 3 (5)

[0132] -(CH2)2-C n H 2n -SiR 1 m1 -(OSiR 1 3) 3-m1 (6)

[0133] -(CH2)2-C n H 2n -SiR 1 m1 -(OSiR 1 m2 (OSiR 1 3) 3-m2 ) 3-m1 (7)

[0134] -(CH2)2-C n H 2n -SiR 1 m1 -(OSiR 1 m2 (OSiR 1 m3 (OSiR 1 3) 3-m3 ) 3-m2 ) 3-m1 (8)

[0135] (Where R 1 As defined above, n and m are integers satisfying 0≤n≤5, 0≤m≤100, and m1, m2, and m3 are integers satisfying 0≤m1≤2, 0≤m2≤2, and 0≤m3≤2.

[0136] n is an integer satisfying 0 ≤ n ≤ 5. In particular, when synthesized by the reaction of a vinylsiloxy group and a hydrosilyl group, n is 0. Furthermore, m is an integer satisfying 0 ≤ m ≤ 100, preferably 1 ≤ m ≤ 30. m1, m2, and m3 are integers satisfying 0 ≤ m1 ≤ 2, 0 ≤ m2 ≤ 2, and 0 ≤ m3 ≤ 2.

[0137] In formula (1), a, b, c, d, e, and f are each integers satisfying 0≤a≤100, 1≤b≤10, 1≤c≤10, 0≤d≤10, e≥0, and f≥0.

[0138] a is an integer satisfying 0≤a≤100, preferably 1≤a≤80, and more preferably 5≤a≤60.

[0139] b is an integer satisfying 1≤b≤10, preferably 1≤b≤8, and more preferably 1≤b≤5.

[0140] c is an integer satisfying 1≤c≤10, preferably 1≤c≤8, and more preferably 1≤c≤5.

[0141] d is an integer satisfying 1≤d≤10, preferably 1≤d≤8, and more preferably 1≤d≤3.

[0142] e is an integer satisfying e ≥ 0. Preferably, 0 ≤ e ≤ 10, more preferably, 0 ≤ e ≤ 5.

[0143] f is an integer satisfying f ≥ 0. Preferably, 0 ≤ f ≤ 10, more preferably, 0 ≤ f ≤ 5.

[0144] The organopolysiloxane of the present invention is preferably represented by the following formula (1-1):

[0145] [Chemistry 21]

[0146]

[0147] (Where R 1 、R 2 、R 3 、R 4 , a, b, c, and d have the same meanings as above.)

[0148] express.

[0149] The organopolysiloxane of the present invention represented by formula (1) can be prepared by combining an organohydrogenpolysiloxane (H) having a hydrosilyl group as a reactive site with R in formula (1). 2 、R 3 The raw material of the compound having an alkenyl group (carbon-carbon unsaturated bond) at the terminal and optionally becoming R 1 、R 4 The compound is synthesized by hydrosilylation reaction of a compound having an alkenyl group at a terminal of the raw material.

[0150] Examples of the organohydrogenpolysiloxane (H) having a hydrosilyl group as a reactive site include: 2 、R 3 , and R 4 Replaced by a hydrogen atom, optionally R 1 A compound in which a portion of the atoms are replaced by hydrogen atoms.

[0151] The carboxyl group represented by the above formula (4), which is a feature of the present invention, can be 3 The raw material of the present invention is introduced by subjecting the compound represented by the following formula (ii) having an alkenyl group at the terminal to a hydrosilylation reaction with the organohydrogenpolysiloxane (H).

[0152] (ii)

[0153] CH2=CH-R 3'

[0154] R 3 ' is -CH2CH2R 3 'Become R 3 That is, R 3 ' has a carboxyl group, but preferably the R 3 'The carboxyl group is replaced by a protecting group such as trimethylsilyl, tert-butyl, or benzyl. 3 The carboxyl group in ' is preferably replaced by a protecting group, thereby preventing a side reaction of the carboxyl group and inhibiting the catalyst in the hydrosilylation reaction with the organohydrogenpolysiloxane (H).

[0155] The (poly)glyceryl group or polyoxyalkylene group represented by the above formula (2) or (3) can be replaced by 2 The compound represented by the following formula (iii) and having an alkenyl group at the terminal as a raw material is introduced by a hydrosilylation reaction with the organohydrogenpolysiloxane (H).

[0156] (iii)

[0157] CH2=CH-R 2'

[0158] R 2 ' is -CH2CH2R 2 'Become R 2 group.

[0159] R in the above formula (1) 1 A part of can be made into R 1 The raw material of the present invention is introduced by subjecting the compound represented by the following formula (iv) having an alkenyl group at the terminal to a hydrosilylation reaction with the organohydrogenpolysiloxane (H).

[0160] (iv)

[0161] CH2=CH-R 1'

[0162] R 1 ' is -CH2CH2R 1 'Become R 1 group.

[0163] The group represented by the above formula (5), (6), (7), or (8) can be obtained by making R 4 The raw material is introduced by subjecting any one of the compounds represented by the following formula (v) having an alkenyl group at the terminal to a hydrosilylation reaction with the organohydrogenpolysiloxane (H).

[0164] [Chemistry 25]

[0165] (v)

[0166] CH2=CH-C n H 2n -(SiR 1 2O) m -SiR 1 3

[0167] CH2=CH-C n H 2n -SiR 1 m1 -(OSiR 1 3) 3-m1

[0168] CH2=CH-C n H 2n -SiR 1 m1 -(OSiR 1 m2 (OSiR 1 3) 3-m2 ) 3-m1

[0169] CH2=CH-C n H 2n -SiR 1 m1 -(OSiR 1 m2 (OSiR 1 m3 (OSiR 1 3) 3-m3 ) 3-m2 ) 3-m1

[0170] The hydrosilylation reaction can be carried out by a known method. The composition of formula (1) can be adjusted according to the raw materials used and their blending amounts. For example, the organohydrogenpolysiloxane (H), the compounds represented by formulas (ii) and (iii), and optionally the compounds represented by formulas (iv) and (v) are added to a reactor at a target molar ratio, and a platinum catalyst is added to carry out the reaction.

[0171] The order of adding the compounds represented by formula (ii), (iii), (iv), and (v) is not particularly limited, and for example, they can be added in the order of formula (iv), (ii), (v), and (iii).

[0172] There is no particular limitation on the platinum catalyst, and examples thereof include PtCl4, H2PtCl6·6H2O, Pt-ether complexes, Pt-olefin complexes, PdCl2(PPh3)2, PdCl2(PhCN)2, RhCl2(PPh3)3 (in the above formula, Ph is a phenyl group), platinum chloride, chloroplatinic acid or a complex of chloroplatinate and a vinyl-containing siloxane, etc.

[0173] These catalysts may be used alone or as a mixture of two or more.

[0174] Among these, the Karstedt catalyst (a complex of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane and a sodium bicarbonate neutralized product of chloroplatinic acid) is particularly preferred.

[0175] The amount of the platinum catalyst is not particularly limited, as long as it is a catalytic amount. The catalytic amount refers to an amount sufficient to cause the hydrosilylation reaction to proceed. For example, the amount of the platinum catalyst, calculated as platinum metal atoms, relative to 100 parts by mass of the organohydrogenpolysiloxane (H) is preferably 0.02 parts by mass or less, more preferably 0.00001 to 0.02 parts by mass, even more preferably 0.0001 to 0.01 parts by mass, and particularly preferably 0.0003 to 0.005 parts by mass.

[0176] The reaction is not particularly limited, and can be performed at, for example, 50 to 90°C.

[0177] It is preferred to use a solvent during the reaction. The solvent is not particularly limited, and examples thereof include isopropyl alcohol, tetrahydrofuran, and toluene.

[0178] When a compound represented by formula (ii) is used in which a carboxyl group is replaced with a protecting group such as a trimethylsilyl group, deprotection is performed. Deprotection can be performed, for example, by heating in the presence of an alcohol.

[0179] [Cosmetics]

[0180] The cosmetic of the present invention contains (A) a carboxyl-modified organopolysiloxane represented by formula (1), (B) an oil agent, and (C) water.

[0181] Furthermore, the cosmetic material in the present invention is in the form of a composition.

[0182] <(A)Component>

[0183] The component (A) is a carboxyl-modified organopolysiloxane having a (poly)glyceryl group or a polyoxyalkylene group represented by formula (1), and one type thereof can be used alone or two or more types thereof can be used in combination.

[0184] The amount of component (A) blended is not particularly limited, but is preferably 0.1 to 30% by mass, more preferably 0.1 to 15% by mass, based on the entire cosmetic.

[0185] <(B) Ingredient>

[0186] Component (B) of the present invention is an oil. The oil (B) of the present invention may be liquid, solid, or semisolid. Examples thereof include hydrocarbon oils, higher fatty acids, higher alcohols, natural animal and plant oils and fats, semi-synthetic oils, ester oils, silicone oils, and fluorine-based oils. These oils may be used alone or in combination of two or more.

[0187] Examples of the hydrocarbon oil include linear or branched hydrocarbon oils, and may be volatile or non-volatile. Specific examples include olefin oligomers, isododecane (INCI: Isododecane), dodecane (INCI: Dodecane), isohexadecane (INCI: Isohexadecane), undecane (INCI: Undecane), squalane (INCI: Squalane), squalene (INCI: Squalene), mineral oil (INCI: Mineral Oil), liquid isoparaffin, polyisobutene (INCI: Hydrogenated Polyisobutene), and (C13-15) alkane (INCI: C13-15 Alkane).

[0188] Examples of higher fatty acids include oleic acid (INCI: Oleic Acid), linoleic acid (INCI: Linoleic Acid), linolenic acid (INCI: Linolenic Acid), arachidonic acid (INCI: Arachidonic Acid), eicosapentaenoic acid (EPA) (INCI: Eicosapentaenoic Acid), docosahexaenoic acid (DHA) (INCI: Docosahexaenoic Acid), isostearic acid (INCI: Isostearic Acid), and hydroxystearic acid (INCI: Hydroxystearic Acid).

[0189] Examples of higher alcohols include linear saturated alcohols having 6 or more carbon atoms, such as lauryl alcohol (INCI), hexyldecanol (INCI), oleyl alcohol (INCI), isostearyl alcohol (INCI), octyldodecanol (INCI), decyltetradecyl alcohol (INCI), myristyl alcohol (INCI), cetyl alcohol (INCI), stearyl alcohol (INCI), and behenyl alcohol (INCI), and batyl alcohol (INCI). Furthermore, examples include sterols such as cholesterol (INCI), sitosterol (INCI: Beta-Sitosterol), phytosterol (INCI), and lanosterol (INCI).

[0190] Examples of natural plant and animal oils and semi-synthetic oils include avocado oil (INCI: Persea Gratissima (Avocado) Oil), linseed oil (INCI: Linum Usitatissimum (Linseed) Seed Oil), almond oil (INCI: Prunus Amygdalus Dulcis (Sweet Almond) Oil), olive oil (INCI: Olea Europaea (Olive) Fruit Oil), torreya oil (INCI: Torreya California (California Nutmeg) Oil), citronella oil (INCI: Cymbopogon Nardus (Citronella) Oil), shark liver oil (INCI: Shark Liver Oil), cod liver oil (INCI: Cod Liver Oil), and cod liver oil (INCI: Fish Liver Oil). Oil), Apricot Kernel Oil (INCI: Kyounin Yu), Sesame Oil (INCI: Sesamum Indicum (Sesame) Seed Oil), Rice Germ Oil (INCI: Oryza Sativa (Rice) Germ Oil), Rice Bran Oil (INCI: Oryza Sativa (Rice) Bran Oil), Camellia Oil (INCI: Camellia Kissi Seed Oil), Safflower Oil (INCI: Carthamus Tinctorius (Safflower) Seed Oil), Turtle Oil (INCI: Turtle Oil), Camellia Seed Oil (INCI: Camellia Japonica Seed Oil), Evening Primrose Oil (INCI: Oenothera Biennis (Evening Primrose) Oil), Corn Germ Oil (INCI: Zea Mays (Corn) Germ Oil), rapeseed oil (INCI: RAPE SHUSHI YU), wheat germ oil (INCI: Triticum Vulgare (Wheat) Germ Oil), peach kernel oil (INCI: ), palm oil (INCI: ElaeisGuineensis (Palm) Oil), Palm Kernel Oil (INCI: Elaeis Guineensis (Palm) Kernel Oil), Castor Oil (INCI: Ricinus Communis (Castor) Seed Oil), Hardened Castor Oil (INCI), Sunflower Seed Oil (INCI: Helianthus Annuus (Sunflower) Seed Oil), Grape Seed Oil (INCI: Vitis Vinifera (Grape) Seed Oil), Jojoba Oil (INCI: Simmondsia Chinensis (Jojoba) Seed Oil), Macadamia Nut Oil (INCI: Macadamia Ternifolia Seed Oil), Mink Oil (INCI: Mink Oil), Meadowfoam Seed Oil (INCI: Limnanthes Alba (Meadowfoam) Seed Oil), Cottonseed Oil (INCI: Gossypium Herbaceum (Cotton) Seed Oil), coconut oil (INCI: Cocos Nucifera (Coconut) Oil), hydrogenated coconut oil (INCI: Hydrogenated Coconut Oil), egg yolk oil (INCI: Egg Oil), etc.

[0191] The ester oil is a liquid oil in a form in which a fatty acid having 1 to 20 carbon atoms and an alcohol having 1 to 20 carbon atoms are condensed, and examples thereof include monoesters, diesters, and triesters. Specific examples include diisobutyl adipate (INCI: Diisobutyl Adipate), dihexyldecyl adipate (INCI: Diheptylundecyl Adipate), isostearyl isostearate (INCI: Isostearyl Isostearate), monoisostearate n-alkyl glycol esters such as isostearyl isostearate (INCI: Isocetyl Isostearate), trimethylolpropane triisostearate (INCI: Trimethylolpropane Triisostearate), glycol diethylhexanoate (INCI: Glycol Diethylhexanoate), cetyl ethylhexanoate (INCI: Cetyl Ethylhexanoate), Triethylhexanoin (INCI: Triethylhexanoin), Trimethylolpropane Triethylhexanoate (INCI: Trimethylolpropane Triethylhexanoate), Pentaerythrityl Tetraethylhexanoate (INCI: Pentaerythrityl Tetraethylhexanoate), Cetyl Caprylate (INCI: CetylEthylhexanoate), Octyldodecyl Stearoyl Stearate (INCI: OctyldodecylStearoyl Stearate), etc. Octyldodecyl esters, Oleyl Oleate (INCI: Oleyl Oleate), Octyldodecyl Oleate (INCI: Octyldodecyl Oleate), Decyl Oleate (INCI: Decyl Oleate), Neopentyl Glycol Dicaprylate (INCI: Neopentyl Glycol Diethylhexanoate), Neopentyl Glycol Dicaprate (INCI: Neopentyl Glycol Dicaprate), Triethyl Citrate (INCI: Triethyl Citrate), Diethylhexyl Succinate (INCI: DiethylhexylSuccinate), Amyl Acetate (INCI: AmylAcetate), Ethyl Acetate (INCI: EtylAcetate), Butyl Acetate (INCI: ButylAceetate), Isocetyl Stearate (INCI: Isocetyl Stearate), Butyl Stearate (INCI: ButylStearate), Diisopropyl Sebacate (INCI: Diisopropyl Sebacate), Diethylhexyl Sebacate (INCI: Diethylhexyl Sebacate), Sebacate), Cetyl Lactate (INCI: Cetyl Lactate), Myristyl Lactate (INCI: Myristyl Lactate), Isononyl Isononanoate (INCI: Isononyl Isononanoate), Isotridecyl Isononanoate (INCI: Isotridecyl Isononanoate), Isopropyl Palmitate (INCI: Isopropyl Palmitate), Ethylhexyl Palmitate (INCI: Ethylhexyl Isoparaffin) Palmitate, hexyldecyl palmitate (INCI: IsocetylPalmitate, HexyldecylPalmitate), palmitic acid esters such as cholesteryl hydroxystearate (INCI: CholesterylHydroxystearate), isopropyl myristate (INCI: IsopropylMyristate), octyldodecyl myristate (INCI: OctyldodecylMyristate), myristyl myristate (INCI: Myristyl Myristate) and other myristyl myristates, Ethylhexyl Laurate (INCI: EthylhexylLaurate), Hexyl Laurate (INCI: HexylLaurate), Dioctyldodecyl Lauroyl Glutamate (INCI: Dioctyldodecyl Lauroyl Glutamate), Isopropyl Lauroyl Sarcosinate (INCI: Isopropyl Lauroyl Sarcosinate), Diisostearyl Malate (INCI: DiisostearylMalate), Glyceryl Acetate (INCI: Glyceryl Lau ...Acetate), glyceryl stearate (INCI: Glyceryl Stearate), and glyceryl tri(caprylic acid / capric acid) esters (INCI: Caprylic / Capric Triglyceride).

[0192] Examples of silicone oils include trisiloxane (INCI: Trisiloxane), volatile dimethicone (INCI: Dimethicone), low-viscosity dimethicone (INCI: Dimethicone), cyclotetrasiloxane (INCI: Cyclotetrasiloxane), cyclopentasiloxane (INCI: Cyclopentasiloxane), cyclohexasiloxane (INCI: Cyclohexasiloxane), methyl trimethicone (INCI: Methyl Trimethicone), caprylyl methicone (INCI: Caprylyl Methicone), and phenyl trimethicone (INCI: Phenyl Trimethicone). Trimethicone), Methylphenyl Polysiloxane (INCI: DiphenylDimethicone), Diphenylsiloxy Phenyl Trimethicone (INCI: DiphenylsiloxyPhenyl Trimethicone), Ethyl Methicone (INCI: EthylMethicone), Ethyl Trisiloxane (INCI: EthylTrisiloxane), Hydrogen Dimethicone (INCI: Hydrogen Low to high viscosity linear or branched dimethylpolysiloxanes such as dimethicone, aminodimethicone (INCI: Amodimethicone), aminopropyl dimethicone (INCI: AminopropylDimethicone), highly polymerized viscous dimethylpolysiloxane (INCI: Dimethicone), viscous aminodimethicone (INCI: Amodimethicone), viscous dimethylsiloxane-methylphenylsiloxane copolymers and other silicone rubbers, silicone adhesives or cyclic organopolysiloxane solutions of silicone rubbers, amino acid-modified silicones, fluorine-modified silicones, silicone resins, and silicone resin dissolves.

[0193] Examples of the fluorine-based oil include perfluoropolyethers such as polyperfluoromethylisopropyl ether (INCI: Polyperfluoromethylisopropyl Ether), and perfluorocarbons such as perfluorodecalin (INCI: Perfluorodecalin) and perfluorohexane (INCI: Perfluorohexane).

[0194] As the component (B), at least one selected from silicone oil, hydrocarbon oil, and fatty acid ester is preferred.

[0195] The amount of the component (B) to be added is not particularly limited, but is preferably 1 to 50% by mass, more preferably 1 to 25% by mass, based on the entire cosmetic.

[0196] <(C) Ingredient>

[0197] Component (C) of the present invention is water. Examples of water include purified water and fruit or plant distilled water generally used in cosmetics, as well as seawater (INCI: Sea Water), hot spring water (Onsen-Sui), and peat water (INCI: Peat Water), which are defined by their names.

[0198] The amount of (C) water to be added is not particularly limited, but is preferably 5 to 95% by mass, more preferably 40 to 80% by mass, based on the entire cosmetic.

[0199] <(D) Ingredient>

[0200] The cosmetic of the present invention may further contain one or two or more polyhydric alcohols as needed in addition to the above-mentioned components (A) to (C).

[0201] Examples of the polyol include ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, pentanediol, glycerol, diglycerol, triglycerol, and polyglycerol. Among them, 1,3-butylene glycol, propylene glycol, diglycerol, glycerol, and combinations thereof are preferred.

[0202] When the component (D) is added, the amount thereof is not particularly limited, but is preferably 1 to 50% by mass, more preferably 1 to 25% by mass, based on the entire cosmetic.

[0203] The cosmetic of the present invention may contain optional components described below within a range not impairing the effects of the present invention.

[0204] The form of the cosmetic of the present invention is not particularly limited, and examples thereof include liquid, cream, paste, solid, mousse, spray, gel, and emulsion forms. Furthermore, the application is also not particularly limited, and for example, the cosmetic can be used as a skin care cosmetic, a makeup cosmetic, a hair cosmetic, or a sunscreen cosmetic. Specific examples of the cosmetic include skin creams, hair lotions, cleansers, makeup bases, concealers, liquid foundations, cream foundations, solid foundations, blushers, eyeshadows, mascara, eyeliners, eyebrow pencils, lipsticks, and other makeup cosmetics blended with the above-mentioned cosmetic ingredients, as well as UV protection cosmetics such as sunscreen lotions and sunscreens.

[0205] The cosmetic composition of the present invention is not particularly limited in form and can be used in any of oil-based cosmetics, water-based cosmetics, oil-in-water emulsion cosmetics, and water-in-oil emulsion cosmetics. However, the oil-in-water emulsion cosmetic composition is preferred. By adopting an oil-in-water emulsion, the organopolysiloxane of component (A) stabilizes the emulsified surface, resulting in an emulsion composition with excellent long-term stability. This improves the long-lasting effect and feel of the cosmetic.

[0206] Optional ingredients

[0207] The cosmetic of the present invention may further contain other optional ingredients commonly used in the cosmetic field. Optional ingredients include, for example, ultraviolet absorbers, surfactants other than component (A), film-forming agents, antiperspirants, antibacterial agents, preservatives, fragrances, salts, antioxidants, moisturizers, pH adjusters, chelating agents, cooling agents, anti-inflammatory agents, skin-beautifying ingredients (whitening agents, cell activators, rough skin improvers, blood circulation promoters, skin astringents, anti-seborrheic agents, etc.), vitamins, amino acids, nucleic acids, hormones, inclusion compounds, powders, organic resins, thickeners, and the like. These optional ingredients may be used alone or in combination of two or more in appropriate amounts.

[0208] As the UV absorber, there is no particular limitation as long as it is a raw material that can be mixed in general cosmetics, and one type can be used alone or two or more types can be used in combination. Specifically, as the oil-soluble UV absorber, homosalate (indicative name (INCI: Homosalate)), octocrylene (indicative name (INCI: Octocrylene)), t-butyl methoxydibenzoylmethane (indicative name (INCI: Butyl Methoxydibenzoylmethane)), ethylhexyl salicylate (indicative name (INCI: Ethylhexyl Salicylate)), diethylamino hydroxybenzoyl hexyl benzoate (indicative name (INCI: Diethylamino Hydroxybenzoyl Hexyl Benzoate) Benzoate), Oxybenzone-6 (INCI: Benzophenone-6), Oxybenzone-9 (INCI: Benzophenone-9), Oxybenzone-1 (INCI: Benzophenone-1), Polysilicone-15 (INCI: Polysilicone-15), Ethylhexyl Dimethoxybenzylidene Dioxoimidazolidine Propionate, Oxybenzone-2 (INCI: Benzophenone-2), Terephthalylidene Dicamphor Sulfonic Acid, Ethylhexyl Triazone (INCI: Ethylhexyl Triazone Triazone), Isopentyl Methyl Bis(Trimethylsiloxy) Silyl Trimethoxycinnamate (INCI: Isopentyl Trimethoxycinnamate Trisiloxane), Drometrizole Trisiloxane (INCI: Drometrizole Trisiloxane), Ethylhexyl Dimethyl PABA (INCI: EthylhexylDimethylPABA), Isopropyl p-Methoxycinnamate (INCI: IsopropylMethoxycinnamate), Ethylhexyl Methoxycinnamate (INCI: EthylhexylMethoxycinnamate), Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (INCI: Bis-EthylhexyloxyphenolMethoxyphenyl Triazine), Oxybenzone-3 (INCI: Benzophenone-3), Oxybenzone-4 (INCI: Benzophenone-4), Oxybenzone-5 (INCI: Benzophenone-5), Phenylbenzimidazole Sulfonic Acid (INCI: PhenylbenzimidazoleSulfonic Acid), Methylene Bis-Benzotriazolyl Tetramethylbutylphenol (INCI: Methylene Bis-Benzotriazolyl Tetramethylbutylphenol), Glyceryl Ethylhexanoate Dimethoxycinnamate (INCI: Glyceryl Ethylhexanoate Dimethoxycinnamate), Glyceryl PABA (INCI: Glyceryl PABA), diisopropyl methyl cinnamate (INCI: DiisopropylMethylCinnamate), cinoxate (INCI: Cinoxate), ethylhexyl dimethoxybenzylidene dioxoimidazolidine propionate (INCI: Ethylhexyl Dimethoxybenzylidene Dioxoimidazolidine Propionate), etc. In addition, UVA absorbers (for example, diethylamino hydroxybenzoyl hexyl benzoate (INCI: Diethylamino Hydroxybenzoyl HexylBenzoate)) and UVB absorbers (for example, ethylhexyl methoxycinnamate (INCI: Ethylhexyl Methoxycinnamate)) can be used in combination, or they can be combined arbitrarily.

[0209] Among them, preferred are ethylhexyl methoxycinnamate (INCI: EthylhexylMethoxycinnamate), diethylamino hydroxybenzoyl hexyl benzoate (INCI: Diethylamino Hydroxybenzoyl Hexyl Benzoate), octyl salicylate (INCI: EthylhexylSalicylate), polysilicone-15 (INCI: Polysilicone-15), t-butylmethoxydibenzoylmethane (INCI: ButylMethoxydibenzoylmethane), oxybenzone (INCI: Benzophenone-6), methylene bis-benzotriazolyl tetramethylbutylphenol (INCI: Methylene Bis-Benzotriazolyl Tetramethylbutylphenol) One or more oil-soluble UV absorbers selected from the group consisting of tetramethylbutylphenol, bis-ethylhexyloxyphenol methoxyphenyl triazine (INCI: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine), homosalate (INCI: Homosalate), and octocrylene (INCI: Octocrylene).

[0210] Surfactants other than component (A) include nonionic, anionic, cationic, and amphoteric surfactants, and are not particularly limited. Any surfactant used in conventional cosmetics can be used. Among these surfactants, preferred are partially cross-linked polyether-modified silicone, partially cross-linked polyglycerol-modified silicone, linear or branched polyoxyethylene-modified organopolysiloxane, linear or branched polyoxyethylene-polyoxypropylene-modified organopolysiloxane, linear or branched polyoxyethylene-alkyl co-modified organopolysiloxane, linear or branched polyoxyethylene-polyoxypropylene-alkyl co-modified organopolysiloxane, linear or branched polyglycerol-modified organopolysiloxane, and linear or branched polyglycerol-alkyl co-modified organopolysiloxane pyrrolidone-modified organopolysiloxane. Among these surfactants, the amount of hydrophilic polyoxyethylene, polyoxyethylene-polyoxypropylene, or polyglycerol residues in the molecule is preferably 10 to 70% by mass. In addition, when partially cross-linked polyether-modified silicone or partially cross-linked polyglycerol-modified silicone is used, in a composition comprising the cross-linked organopolysiloxane and an oily agent that is liquid at 25°C, the cross-linked organopolysiloxane preferably swells with respect to the liquid oily agent, wherein the liquid oily agent contains more than the weight of the cross-linked organopolysiloxane. As the liquid oily agent, liquid organosilicone, hydrocarbon oil, ester oil, natural animal and vegetable oil, semi-synthetic oil, or fluorine-based oil, which are optional components of the oily agent, can be used. For example, an oily agent having a kinematic viscosity of 0.65 to 100 mm at 25°C can be used. 2 / s low-viscosity silicone, liquid paraffin, hydrocarbon oils such as squalane, isododecane, and isohexadecane, glyceride oils such as triethylhexanoin, ester oils such as isotridecyl isononanoate, N-acyl glutamate, and lauroyl sarcosinate, and natural animal and plant oils such as macadamia nut oil. Specific examples include KSG-210, KSG-240, KSG-310, KSG-320, KSG-330, KSG-340, KSG-320Z, KSG-350Z, KSG-710, KSG-810, KSG-820, KSG-830, KSG-840, KSG-820Z, and KSG-850Z manufactured by Shin-Etsu Chemical Co., Ltd. Specific examples of surfactants that are not cross-linked organopolysiloxanes include KF-6011, KF-6013, KF-6043, KF-6017, KF-6028, KF-6038, KF-6048, KF-6100, KF-6104, KF-6105, and KF-6106 manufactured by Shin-Etsu Chemical Co., Ltd. In any case, the amount of surfactant blended is preferably 0.1 to 20% by mass of the overall cosmetic. A blend of 0.1% by mass or more can fully demonstrate the functions of dispersion and emulsification, while a blend of 20% by mass or less can avoid the cosmetic becoming sticky, and is therefore preferred. The HLB value of the surfactant is not limited, but is preferably 2 to 14.5 for the purpose of maintaining the water resistance of the cosmetic.

[0211] The film-forming agent is mainly added in order to further maintain the effect of the cosmetic material for a long time. Although not particularly limited, from the viewpoint of imparting water repellency, a silicone composition is preferred. Specifically, trimethylsiloxysilicate (indicative name (trimethylsiloxysilicate (INCI)), acrylic-silicone film-forming agent, silicone-modified norbornene, silicone-modified pullulan, etc. can be used. The film-forming agent can be dissolved in an oil agent that is liquid at room temperature in advance and then mixed into the cosmetic material. As the liquid oil agent, liquid silicone, hydrocarbon oil, ester oil, natural animal and plant oil, semi-synthetic oil, etc., and fluorine-based oil in the oil agent of the optional component can be used, for example, a kinematic viscosity of 0.65 to 100 mm at 25°C can be listed. 2 / s low-viscosity silicone, liquid paraffin, hydrocarbon oils such as squalane, isododecane, and isohexadecane, glyceride oils such as triethylhexanoin, ester oils such as isotridecyl isononanoate, N-acyl glutamate, and lauroyl sarcosinate, and natural animal and plant oils such as macadamia nut oil. Specific examples of these include KF-7312J, a silicone solution of trimethylsiloxysilicate, manufactured by Shin-Etsu Chemical Co., Ltd., silicone solutions of acrylic-silicone coating agents such as KP-545 and KP-549, silicone solutions of silicone-modified norbornene such as NBN-30-ID, silicone-modified pullulan such as TSPL-30-ID, and silicone solutions such as TSPL-30-D5.

[0212] When the cosmetic material of the present invention is a deodorant, an antiperspirant can be optionally blended. As long as the antiperspirant is an ingredient that suppresses the production of sweat by astringing the skin, there is no particular limitation, and a wide range of general-purpose ingredients can be used. For example, chlorohydroxyaluminum, aluminum chloride, chlorohydroxyaluminum allantoin, aluminum salt of allantoin, tannic acid, potassium aluminum sulfate, zinc oxide, zinc p-phenolsulfonate, burnt alum, tetrachlorohydroxyaluminum zirconium glycine hydrate, trichlorohydroxyaluminum zirconium glycine, etc. can be mentioned. In particular, as an ingredient that shows a high effect, an antiperspirant active ingredient selected from aluminum halides, hydroxyaluminum halides, and complexes or mixtures thereof with zirconyl oxyhalides and zirconyl oxyhalides is preferred. These antiperspirants can be dissolved in water and blended, or the powder can be directly blended into the preparation and used. Commercially available antiperspirants can also be used. The commercially available product used may be in the form of a mixed raw material with other ingredients. There is no particular limitation on the blending amount of the antiperspirant and it can be appropriately changed according to the blending amount of other ingredients. In order to obtain a deodorant with excellent antiperspirant effect and reduced skin irritation, the amount of the compounding agent is preferably 0.001 to 30% by mass, more preferably 0.01 to 20% by mass, based on the entire cosmetic.

[0213] Antimicrobial agents are not particularly limited as long as they are ingredients that achieve a deodorizing effect by inhibiting the proliferation of bacteria resident on the skin that cause body odor. For example, antimicrobial agents such as triclosan, benzalkonium chloride, benzethonium chloride, chlorhexidine hydrochloride, chlorhexidine gluconate, halogenated carbenes, and m-cresol are commonly used. In addition, substances having antimicrobial properties such as green tea dry distillation extract, and essential oils and extracts from herbal medicines may be incorporated. As antibacterial agents with a deodorizing effect such as essential oils and extracts derived from herbs, for example, green tea extract, lavender extract, scutellaria baicalensis extract, coptis chinensis extract, phellodendron amurense extract, artemisia capillaris extract, aloe vera extract, sophora flavescens root extract, kumquat leaf extract, garlic extract, witch hazel extract, black tea extract, sage extract, Zanthoxylum bungeanum extract, ginger root extract, calamus root extract, ivy extract, houttuynia cordata extract, peach fruit extract, peach leaf extract, peppermint leaf extract, ligusticum chuanxiong extract, eucalyptus leaf extract, peanut seed coat extract, litchi extract, and sanguisorba officinalis extract can be used.

[0214] Examples of preservatives include alkyl parahydroxybenzoates, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, and phenoxyethanol. Examples of antibacterial agents include benzoic acid, salicylic acid, carbolic acid, sorbic acid, alkyl parahydroxybenzoates, parachlorometacresol, hexachlorophene, triclocarbam, and photosensitizers.

[0215] Fragrances include natural and synthetic fragrances. Natural fragrances include plant-based fragrances isolated from flowers, leaves, wood, and fruit peels, as well as animal-based fragrances such as musk and civet. Synthetic fragrances include hydrocarbons such as monoterpenes, alcohols such as aliphatic and aromatic alcohols, aldehydes such as terpene aldehydes and aromatic aldehydes, ketones such as alicyclic ketones, esters such as terpene esters, lactones, phenols, oxides, nitrogen-containing compounds, and acetals.

[0216] Examples of salts include inorganic salts, organic acid salts, amine salts, and amino acid salts. Examples of inorganic salts include sodium, potassium, magnesium, calcium, aluminum, zirconium, and zinc salts of inorganic acids such as hydrochloric acid, sulfuric acid, carbonic acid, and nitric acid. Examples of organic acid salts include salts of organic acids such as acetic acid, dehydroacetic acid, citric acid, malic acid, succinic acid, ascorbic acid, and stearic acid. Examples of amine and amino acid salts include salts of amines such as triethanolamine and salts of amino acids such as glutamic acid. Furthermore, salts of hyaluronic acid, chondroitin sulfate, aluminum zirconium glycine complexes, and neutralized acid-base salts used in cosmetic formulations may also be used.

[0217] Examples of the antioxidant include carotenoids, ascorbic acid and its salts, ascorbyl stearate, tocopheryl acetate, tocopherol, p-tert-butylphenol, butylated hydroxyanisole, butylated hydroxytoluene, phytic acid, ferulic acid, thiotaurine, hypotaurine, sulfites, sorbic acid and its salts, chlorogenic acid, epicatechin, epigallocatechin, epigallocatechin gallate, apigenin, kaempferol, myricetin, and quercetin.

[0218] Examples of the moisturizing agent include glucose, xylitol, maltitol, polyethylene glycol, hyaluronic acid, chondroitin sulfate, pyrrolidone carboxylate, polyoxyethylene methyl glucoside, polyoxypropylene methyl glucoside, egg yolk lecithin, soybean lecithin, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, phosphatidylinositol, and sphingolipids.

[0219] Examples of the pH adjuster include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium bicarbonate, and ammonium bicarbonate.

[0220] Examples of the chelating agent include alanine, edetate sodium salt, sodium polyphosphate, sodium metaphosphate, phosphoric acid, aspartic acid diacetic acid, and ethylenediamine disuccinic acid.

[0221] Examples of the cooling agent include L-menthol and camphor.

[0222] Examples of the anti-inflammatory agent include allantoin, glycyrrhizic acid and its salts, glycyrrhetinic acid and stearyl glycyrrhetinic acid, tranexamic acid, and azulene.

[0223] Examples of skin-beautifying ingredients include whitening agents such as vitamin C derivatives, hydroquinone, tranexamic acid, arbutin, phenylethylresorcinol, kojic acid, and plant extracts; cell activators such as royal jelly, photosensitizers, cholesterol derivatives, and calf blood extracts; skin roughness improvers, blood circulation promoters such as valinamide nonanoate, benzyl nicotinate, β-butoxyethyl nicotinate, capsaicin, zingerone, chelidonium tincture, ichthyol, caffeine, tannic acid, α-camphenol, tocopheryl nicotinate, inositol hexanicotinate, cyclomandelate, cinnarizine, triazoline, acetylcholine, verapamil, cepharanthin, and γ-oryzanol; skin astringents such as zinc oxide and tannic acid; and anti-seborrheic agents such as sulfur and methylthiophenol.

[0224] Examples of vitamins include vitamin A oil, retinol, retinol acetate, retinol palmitate and other vitamins A, riboflavin, riboflavin butyrate, flavin adenine nucleotide and other vitamins B2, pyridoxine hydrochloride, pyridoxine dioctanoate, pyridoxine tripalmitate and other vitamins B6, vitamin B 12 and its derivatives, vitamin B 15and its derivatives, such as vitamin B; L-ascorbic acid, L-ascorbyl dipalmitate, sodium L-ascorbic acid-2-sulfate, dipotassium L-ascorbyl diester phosphate, such as vitamin C; calciferol, cholecalciferol, such as vitamin D; α-tocopherol, β-tocopherol, γ-tocopherol, dl-α-tocopheryl acetate, dl-α-tocopheryl nicotinate, dl-α-tocopheryl succinate, such as vitamin E; niacin, benzyl nicotinate, niacinamide, such as niacin, vitamin H, vitamin P, calcium pantothenate, D-panthenol, panthenyl ethyl ether, acetyl panthenyl ethyl ether, such as pantothenic acid; biotin, etc.

[0225] Examples of the amino acid include glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine, lysine, aspartic acid, glutamic acid, cystine, cysteine, methionine, and tryptophan.

[0226] Examples of nucleic acids include deoxyribonucleic acid and the like.

[0227] Examples of the hormone include estradiol and vinylestradiol.

[0228] Examples of inclusion compounds include cyclodextrin and the like.

[0229] Examples of the powder include fine-particle metal oxide powder, coloring pigments, inorganic powder, metal powder, organic powder, and inorganic / organic composite powder.

[0230] The fine-particle metal oxide powder is one or more selected from fine-particle titanium oxide (INCI: Titanium Dioxide), iron-containing titanium oxide, zinc oxide (INCI: Zinc Oxide), cerium oxide (INCI: Cerium Oxide), and composites thereof. These metal oxides may be composite powders with other powders.

[0231] Coloring pigments are generally not particularly limited as long as they are pigments used for the purpose of coloring cosmetics, and include red iron oxides (INCI: Iron Oxides), yellow iron oxides (INCI: Iron Oxides), white titanium oxide (INCI: Titanium Dioxide), black iron oxides (INCI: Iron Oxides), ultramarine (INCI: Ultramarines), cyan blue (INCI: Ferric Ferrocyanide, Ferric Ammonium Ferrocyanide), manganese violet (INCI: Manganese Violet), cobalt titanate (INCI: Cobalt Titanium Oxide), chromium hydroxide (INCI: Chromium Hydroxide Green), chromium oxide (INCI: Chromium Oxide Greens), aluminum / cobalt oxide (INCI: Cobalt Aluminum) Inorganic brown pigments such as titanium nitride (INCI: Titanium Nitride), ferrous hydroxide (INCI: Iron Hydroxide), and inorganic brown pigments such as γ-iron oxide, inorganic yellow pigments such as loess, and colored pigments such as products obtained by laking tar-based pigments and products obtained by laking natural pigments can be used.

[0232] From the perspective of hiding power, coloring pigments may have a particle size, i.e., a volume average particle size, ranging from 150 to 600 nm. The volume average particle size can be measured using a TEM or other method. If the particle size is less than 150 nm, the hiding power is low, which may reduce the coloring efficiency of the cosmetic. Furthermore, if the particle size is larger than 600 nm, the feel during use may be deteriorated. Furthermore, the pigments of the present invention may be partially or fully surface-treated with inorganic compounds such as aluminum oxide (INCI: Alumina), aluminum hydroxide (INCI: Aluminum Hydroxide), silicon dioxide (INCI: Silica), or hydrated silicon dioxide (INCI: Hydrated Silica).

[0233] Examples of the inorganic powder include zirconium oxide (INCI: Zirconium Dioxide), zinc oxide (INCI: Zinc Oxide), cerium oxide (INCI: Cerium Oxide), magnesium oxide (INCI: Magnesium Oxide), barium sulfate (INCI: Barium Sulfate), calcium sulfate (INCI: Calcium Sulfate), magnesium sulfate (INCI: Magnesium Sulfate), calcium carbonate (INCI: Calcium Carbonate), magnesium carbonate (INCI: Magnesium Carbonate), talc (INCI: Talc), cleaved talc (INCI: Talc), mica (INCI: Mica), kaolin (INCI: Kaolin), sericite (INCI: Mica), synthetic fluorphlogopite (INCI: Synthetic Fluorphlogopite), Biotite (INCI: Biotite), Potassium Silicate (INCI: Potassium Silicate), Silica (INCI: Silica), Fumed Silica, Aluminum Silicate (INCI: Aluminum Silicate), Magnesium Silicate (INCI: Magnesium Silicate), Silicic Acid (Aluminum / Magnesium) (INCI: Magnesium Aluminum Silicate), Calcium Silicate (INCI: Calcium Silicate), Silicic Acid (Aluminum / Calcium / Sodium) (INCI: Aluminum Calcium Sodium Silicate), Silicic Acid (Lithium / Magnesium / Sodium) (INCI: Lithium Magnesium Sodium Silicate), Silicic Acid (Sodium / Magnesium) (INCI: Sodium Magnesium Silicate), Borosilicate (Calcium / Aluminum) (INCI: Calcium Aluminum Borosilicate)), borosilicate (calcium / sodium) (INCI: Calcium SodiumExamples of inorganic pearl pigments include fine particles composed of inorganic pigments such as borosilicate, hydroxyapatite (INCI: Hydroxyapatite), bentonite (INCI: Bentonite), montmorillonite (INCI: Montmorillonite), hectorite (INCI: Hectorite), zeolite (INCI: Zeolite), alumina (INCI: Alumina), aluminum hydroxide (INCI: Aluminum Hydroxide), boron nitride (INCI: Boron Nitride), and glass (INCI: Glass). Examples of inorganic pearl pigments include pearlescent agents such as titanium oxide-coated mica, bismuth oxychloride (INCI: Bismuth Oxychloride), and bismuth oxychloride coated with titanium oxide (INCI: Titanium Dioxide). Pearl pigments include talc (INCI: Talc) coated with titanium oxide (INCI: Titanium Dioxide), fish scale foil, and mica coated with titanium oxide (INCI: Titanium Dioxide).

[0234] Examples of the metal powder include metal fine particles made of aluminum (INCI: Aluminum Powder), copper (INCI: Copper Powder), and silver (INCI: Silver Powder).

[0235] Examples of organic powders include powders composed of silicone, polyamide, polyacrylic acid-acrylate, polyester, polyethylene, polypropylene, polystyrene, styrene-acrylic acid copolymer, divinylbenzene-styrene copolymer, polyurethane, vinyl resin, urea-formaldehyde resin, melamine resin, benzoguanamine, polymethylbenzoguanamine, tetrafluoroethylene, polymethyl methacrylate (e.g., polymethyl methacrylate), cellulose, silk, nylon, phenolic resin, epoxy resin, polycarbonate, and the like. In particular, examples of silicone include silicone resin particles (specifically, polymethylsilsesquioxane (INCI: Polymethylsilsesquioxane), silicone resin-coated silicone rubber powder (specifically, (vinyl dimethicone / methyl polysiloxane silsesquioxane) crosspolymer (INCI: Vinyl Dimethicone / Methicone Silsesquioxane Crosspolymer), (diphenyl dimethicone / vinyl diphenyl dimethicone / silsesquioxane) crosspolymer (INCI: Diphenyl Dimethicone / Vinyl Diphenyl Dimethicone / Silsesquioxane) crosspolymer). Crosspolymer), polysilicone-1 crosspolymer (INCI: Polysilicone-1 Crosspolymer), polysilicone-22 (INCI: Polysilicone-22), etc. In addition, metal soaps and the like can also be mentioned. Specific examples include zinc stearate (INCI: Zinc Stearate), aluminum stearate (INCI: Aluminum Stearate), calcium stearate (INCI: Calcium Stearate), magnesium stearate (INCI: Magnesium Stearate), zinc myristate (INCI: Zinc Myristate), magnesium myristate (INCI: Magnesium Myristate), cetyl phosphate (zinc / sodium) (INCI: Sodium Zinc Cetyl Phosphate), potassium cetyl phosphate (INCI: Potassium Cetyl Phosphate) and the like. Furthermore, organic pigments can also be mentioned, and specific examples include Red 3, Red 104 (1) (Indication name (INCI: Red 28, Red 28 Lake)), Red 106, Red 201 (Indication name (INCI: Red6)), Red 202 (Indicated Name (INCI: Red 7)), Red 204, Red 205, Red 220 (Indicated Name (INCI: Red 34)), Red 226 (Indicated Name (INCI: Red 30)), Red 227 (Indicated Name (INCI: Red 33, RED 33Lake)), Red 228 (Indicated Name (INCI: Red 36)), Red 230 (1) (Indicated Name (INCI: Red 22, Red 22Lake)), Red 230 (2), Red 401, Red 505, Yellow 4 (Indicated Name (INCI: Yellow 5)), Yellow 5 (Indicated Name (INCI: Yellow 6, Yellow 6Lake)), Yellow 202 (1) (Indicated Name (INCI: Yellow 8)), Yellow 203 (Indicated Name (INCI: Yellow 10, Yellow 10 Lake)), Yellow 204 (Indication Name (INCI: Yellow 11)), Yellow 401 (Indication Name (INCI:)), Blue 1 (Indication Name (INCI: Blue 1, Blue 1 Lake)), Blue 2, Blue 201, Blue 205 (Indication Name (INCI: Blue 4)), Blue 404, Green 3 (Indication Name (INCI: Green 3, Green 3 Lake)), Green 201 (Indication Name (INCI: Green 5)), Green 202 (Indication Name (INCI: Green 6)), Green 204 (Indication Name (INCI: Green 8)), Green 205, Orange 201 (Indication Name (INCI: Orange 5)), Orange 203 (Indication Name (INCI: Pigment Orange 5)), Orange 204, Orange 205 (Indication Name (INCI: Orange 4, Orange 4 Lake)), Orange 206 (Indication Name (INCI: Orange 10)), Orange 207 (INCI: Orange 11), cochineal (INCI: Cochineal), lacquer acid (INCI: Laccaic Acid), safflower (INCI: Carthamus Tinctorius (Safflower) Flower Extract), ginkgo root extract (INCI: Lithospermum Officinale Root Extract), gardenia yellow, gardenia blue (INCI: Hydrolyzed Gardenia Florida Extract), and other natural pigments.

[0236] Examples of the inorganic-organic composite powder include composite powders obtained by coating the surface of an inorganic powder with an organic powder by a known and commonly used method.

[0237] The powder may be subjected to a hydrophobizing treatment. The hydrophobizing agent used to treat the surface of the raw material powder is not particularly limited as long as it can impart hydrophobicity. Specific examples include silicone treatment agents, waxes, paraffins, organofluorine compounds such as perfluoroalkyl and phosphates, surfactants, amino acids such as N-acylglutamic acid, and metal soaps such as aluminum stearate (INCI: Aluminum Stearate) and magnesium myristate (INCI: Magnesium Myristate).

[0238] Among them, silicone treatment agents are preferably used, and examples thereof include silanes or silanizing agents such as triethoxycaprylylsilane (INCI: Triethoxycaprylylsilane) or trimethoxysilyldimethicone (INCI: TrimethoxysilylDimethicone), silicone oils such as dimethylpolysiloxane (INCI: Dimethicone), hydrogendimethicone (INCI: Hydrogen Dimethicone), and triethoxysilylethyl polydimethylsiloxyethylhexyldimethicone (INCI: Triethoxysilylethyl Polydimethylsiloxyethyl Hexyl Dimethicone), and (acrylates / tridecyl acrylate / triethoxysilylpropyl methacrylate / dimethicone methacrylate) copolymer (INCI: Acrylates / Tridecyl Acrylate / Triethoxysilylpropyl Methacrylate / Dimethicone Methacrylate). Copolymer) and (acrylate / dimethicone) copolymer (INCI: Acrylates / Dimethicone Copolymer). The surface hydrophobizing agent can be used alone or in combination of two or more.

[0239] Specific examples of the hydrophobic powder are shown below, but the present invention is not limited thereto.

[0240] As the fine-particle metal oxide powder that has been hydrophobized, commercially available products can also be used. For example, in fine-particle titanium oxide, with STR-100C-LP, STR-100A-LP, STR-100W, STR-100W-LP, STR-100W-OTS, STR-100C-LF, STR-40-LP (Sakai Chemical Industry Co., Ltd. system), MT-01, MT-05, MT-100Z, MT-100TV, MT-100AQ, MT-150EX, MT-500B, MT-505SAS, MT-700B, MT-014Z, SMT-500SAS (TAYCA Corporation system), ST-455, ST-455WS, ST-457ECS, ST-495M (Japan Titanium Industry Co., Ltd. system) and other trade names are commercially available. Among the fine zinc oxide, FINEX-50S-LP2, FINEX-30S-LP2, FINEX-50W, FINEX-30W, FINEX-50W-LP2, FINEX-52W-LP2, FINEX-30W-LP2, FINEX-33W-LP2, FINEX-50-LPT, FINEX-25-LPT, FINEX-50S-LPT, FINEX-30S-LPT, FINEX-30-OTS (Sakai Chemical Industry Co., Ltd.), MZ-150, MZ-200, MZ-300, MZ-306X, MZ-500HP, MZ-505T, MZ-506X, MZY-203S, MZY-210M3S, TMZ-HA1, and MZX-5080TS (produced by TAYCA Corporation).

[0241] Specific examples of the coloring pigment subjected to a hydrophobic treatment include the KTP-09 series, particularly KTP-09W, KTP-09R, KTP-09Y, and KTP-09B (produced by Shin-Etsu Chemical Co., Ltd.).

[0242] Example

[0243] The present invention will be described in detail below with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples.

[0244] Synthesis example

[0245] The components shown in Table 1 below were blended at the molar ratio shown in Table 1 below, and an organopolysiloxane was obtained by the method shown below.

[0246] [Table 1]

[0247]

[0248] The numerical values ​​in the table represent molar ratios.

[0249] The components shown in Table 1 above are as follows.

[0250] [Chemistry 26]

[0251]

[0252] [Chemistry 27]

[0253]

[0254] [Chemistry 28]

[0255]

[0256] [Chemistry 29]

[0257] (iv-1)

[0258] CH2=CH-C 10 H 21

[0259] (iv-2)

[0260] CH2=CH-C 14 H 21

[0261] [Chemistry 30]

[0262]

[0263] In the following Synthesis Examples 1 to 5, a reactor was charged with the components listed in Table 1, including (H) methylhydrogenpolysiloxane, (ii) trimethylsilyl undecenoate, (iv) olefin, and (v) organopolysiloxane, and a platinum catalyst was added to allow the reaction to proceed. Subsequently, (iii) (poly)glycerol monoallyl ether / polyoxyalkylene monoallyl ether was added to the reactor, and a platinum catalyst was further added to allow the reaction to proceed. Deprotection of the undecenoic acid was then performed.

[0264] [Synthesis example 1]

[0265] A reactor was charged with (H) methylhydrogenpolysiloxane, (ii) trimethylsilyl undecenoate, and (iv) an olefin. Furthermore, 3 ppm of a platinum catalyst (a silicone oil solution of a Karstedt catalyst [3% by mass in terms of platinum metal]) was added relative to the (H) methylhydrogenpolysiloxane, and the reaction was carried out at 80° C. Subsequently, (iii) (poly)glycerol monoallyl ether / polyoxyalkylene monoallyl ether was added to the reactor, and 40% by mass of the total isopropyl alcohol and 3 ppm of a platinum catalyst (a silicone oil solution of a Karstedt catalyst [3% by mass in terms of platinum metal]) relative to the (H) methylhydrogenpolysiloxane were added. After the reaction was carried out at 80° C., methanol was added so as to provide 30% by mass of the total, and the mixture was heated at 60° C. to deprotect the undecenoic acid. Furthermore, methanol and isopropanol were removed under reduced pressure and heating to obtain a=9, b=4, c=1, d=0, e=0, f=0 in formula (1), i=3, j1=9 in formula (3), L=9 in formula (4). 1 -C 10 H 20 -Carboxyl modified organopolysiloxane (A-1) having a polyglyceryl group or a polyoxyalkylene group of Synthesis Example 1. R in (A-1) 2 The content of R 3 The content of is 5% by mass.

[0266] Carry out (A-1) 1 H-NMR measurement confirmed that the compound (A-1) had a structure represented by the following structural formula: 1 The content of is 18% by mass. 1 H-NMR: 0.00ppm (75H), 0.49ppm (18H), 0.88ppm (12H), 1.22ppm (96H), 1.63ppm (2H), 2.34ppm (2H), 3.85ppm (152H).

[0267] [Chemistry 31]

[0268]

[0269] [Synthesis example 2]

[0270] The same steps as in Synthesis Example 1 were used, and the components were charged in the molar ratios listed in Table 1 and reacted to obtain a compound wherein a=5, b=1, c=2, d=0, e=0, f=0 in formula (1), i=3, j1=4 in formula (3), and L=1 in formula (4). 1 -C 10 H 20 -organopolysiloxane (A-2). R in (A-2) 2The content of R 3 The content of is 24% by mass.

[0271] [Chemistry 32]

[0272]

[0273] [Synthesis example 3]

[0274] The same steps as in Synthesis Example 1 were used, and the components were charged in the molar ratios listed in Table 1 and reacted to obtain a compound wherein a=36, b=2, c=2, d=2, e=0, f=0 in formula (1), i=3, j1=9 in formula (3), and L=1 in formula (4). 1 -C 10 H 20 -, an organopolysiloxane (A-3) wherein m=8 and n=0 in formula (5). R in (A-3) has 6 or more carbon atoms. 1 The content of R 2 The content of R 3 The content of is 5% by mass.

[0275] [Chemistry 33]

[0276]

[0277] [Synthesis Example 4]

[0278] The same steps as in Synthesis Example 1 were used, and the components were charged in the molar ratios listed in Table 1 and reacted to obtain a compound wherein a=15, b=1, c=1, d=0, e=0, f=0 in formula (1), g=3, h=3 in formula (2), and L=3 in formula (4). 1 -C 10 H 20 -organopolysiloxane (A-4). R in (A-4) 2 The content of R is 15% by mass 3 The content of is 10% by mass.

[0279] [Chemistry 34]

[0280]

[0281] [Synthesis example 5]

[0282] The same steps as in Synthesis Example 1 were used, and the components were charged in the molar ratios listed in Table 1 and reacted to obtain a compound wherein a=60, b=3, c=1, d=0, e=0, f=0 in formula (1), i=3, j1=9 in formula (3), and L=1 in formula (4). 1 -C 10 H 20-organopolysiloxane (A-5). R in (A-5) 2 The content of R 3 The content of is 3% by mass.

[0283] [Chemistry 35]

[0284]

[0285] [Examples 1 to 7, Comparative Examples 1 to 3]

[0286] The respective components in the amounts shown in Table 2 were mixed by the following production method to obtain an oil-in-water emulsion composition.

[0287] [Table 2]

[0288]

[0289] Table 2 Ingredients

[0290] (※1) Ammonium acryloyldimethyltaurate / VP copolymer; Aristoflex AVC (manufactured by Clariant)

[0291] (Manufacturing Method)

[0292] Step 1: Components (1) and (2) are mixed, and components (3) to (5) are added thereto to make them uniform.

[0293] Step 2: Mix component (6) and a portion of component (8).

[0294] Step 3: The mixture obtained in step 2 is added to the mixture obtained in step 1 under stirring and mixed.

[0295] Step 4: The remaining portion of component (7) and component (8) is further added to the mixture obtained in step 3 under stirring and mixed to obtain an oil-in-water emulsion composition.

[0296] [Examples 8 to 10, Comparative Examples 4 and 5]

[0297] The respective components in the amounts shown in Table 3 were mixed by the following production method to obtain an oil-in-water emulsion composition.

[0298] [Table 3]

[0299]

[0300] Table 3 Ingredients

[0301] (※1) Ammonium acryloyldimethyltaurate / VP copolymer; Aristoflex AVC (manufactured by Clariant)

[0302] (※2) Hydrophobized titanium oxide; STR-100W-OTS (manufactured by Sakai Chemical Industry Co., Ltd., treated with triethoxyoctylsilane)

[0303] (※3) Hydrophobized zinc oxide; FINEX-30-OTS (manufactured by Sakai Chemical Industry Co., Ltd., treated with triethoxyoctylsilane)

[0304] (Manufacturing Method)

[0305] Step 1: A portion of component (2) and components (9) to (11) are mixed and dispersed in a portion of component (14).

[0306] Step 2: Component (7) is mixed with a portion of component (14) different from the portion used in step 1.

[0307] Step 3: Component (1) and the remaining portion of component (2) are mixed under stirring, components (3) to (6) are added thereto, and further component (8) and the remaining portion of component (14) are added to obtain a mixture.

[0308] Step 4: The mixture obtained in step 2 and the dispersion obtained in step 1 are added to the mixture obtained in step 3 under stirring, and then component (12) and component (13) are added and mixed to obtain an oil-in-water emulsion composition.

[0309] [Examples 11-12]

[0310] The respective components in the amounts shown in Table 4 were mixed by the following production method to obtain an oil-in-water emulsion composition.

[0311] [Table 4]

[0312]

[0313] (Manufacturing Method)

[0314] Step 1: Components (1) to (4) are uniformly mixed.

[0315] Step 2: Components (5) to (8) are uniformly mixed.

[0316] Step 3: The mixture obtained in step 2 was added to the mixture obtained in step 1 under stirring and emulsified to obtain a water-in-oil emulsion composition.

[0317] [Emulsion stability]

[0318] The resulting emulsion composition was stored in a 50 mL glass bottle at 50°C for three months. The viscosity of the emulsion composition immediately after preparation and one month after preparation was measured at 25°C using a B-type viscometer (TVB-10, manufactured by Toki Sangyo) using the method described in JIS K7117-1:1999. A change in viscosity of 0% or more but less than 25% compared to the immediately after preparation was designated as "◎," a change of 25% or more but less than 40% was designated as "○," and a change of 40% or more but less than 50% was designated as "△." Separation of the aqueous and oil phases or a change in viscosity of 50% or more was designated as "×." The results are shown in Tables 2 to 4.

[0319] As shown in the results of Tables 2 to 4, the emulsion compositions of Examples 1 to 12, which contain carboxyl-modified organopolysiloxanes having (poly)glyceryl or polyoxyalkylene groups, exhibit excellent emulsion stability. On the other hand, the emulsion compositions of Comparative Examples 1 to 5, which contain polyglyceryl-modified or polyether-modified organopolysiloxanes and carboxyl-modified silicones, exhibit poor storage stability.

[0320] [Example 13]

[0321] The respective components in the amounts shown in Table 5 were mixed by the following production method to obtain an oil-in-water liquid foundation.

[0322] [Table 5]

[0323]

[0324] Table 5 Ingredients

[0325] (※1) Ammonium acryloyldimethyltaurate / VP copolymer; Aristoflex AVC (manufactured by Clariant)

[0326] (※2) KF-9901 treated titanium dioxide manufactured by Shin-Etsu Chemical Co., Ltd.

[0327] (※3) Shin-Etsu Chemical Co., Ltd. KF-9901 treated iron oxide (red)

[0328] (※4) Shin-Etsu Chemical Co., Ltd. KF-9901 treated iron oxide (yellow)

[0329] (※5) Shin-Etsu Chemical Co., Ltd. KF-9901 treated iron oxide (black)

[0330] (Manufacturing Method)

[0331] Step 1: Mix component 13 with a portion of component 2, then add components 9 to 12.

[0332] Mix evenly.

[0333] Step 2: Mix ingredients 4 and 5 evenly.

[0334] Step 3: Mix the remaining portion of ingredient 1 and ingredient 2 evenly.

[0335] Step 4: Component 3, component 6, and the mixture obtained in step 2 are uniformly mixed.

[0336] Step 5: Component 7 and a portion of component 14 are uniformly mixed.

[0337] Step 6: The mixture obtained in step 4 was added to the mixture obtained in step 3, emulsified, and the mixture obtained in step 5 was further added.

[0338] Step 7: To the mixture obtained in step 6, the remaining portion of component 8 and component 14 and the mixture obtained in step 1 were added to obtain an oil-in-water (O / W) liquid foundation.

[0339] The oil-in-water liquid foundation obtained in Example 13 exhibited excellent long-term stability, spread well on the skin, and provided a smooth feel. Furthermore, the resulting makeup film was uniform, had good water resistance, and exhibited excellent long-lasting makeup.

Claims

1. A carboxyl-modified organopolysiloxane represented by the following formula (1): [Chemistry 1] (R 1 2SiO 2 / 2 ) a (R 1 R 2 SiO 2 / 2 ) p (R 1 R 3 SiO 2 / 2 ) e (R 1 R 4 SiO 2 / 2 ) d (R 1 SiO 3 / 2 ) e (SiO 4 / 2 ) f (R 1 3SiO 1 / 2 ) 2+e+2f (1) Where R 1 are independently monovalent hydrocarbon groups selected from alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 15 carbon atoms, and aralkyl groups having 7 to 15 carbon atoms, R 2 are independently a group represented by the following formula (2) or (3), [Chemistry 2] -C g H 2g -O-R 5 (2) Where R 5 In the following formula (2-1) [Chemistry 3] A group in which a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms is independently bonded to the oxygen atom terminal of a group represented by formula (2-1) or a group formed by connecting a plurality of groups represented by formula (2-1), wherein g in formula (2) is an integer satisfying 0≤g≤20, and R 5 The number h of the groups represented by formula (2-1) is an integer satisfying 1≤h≤10, [Chemistry 4] Where R 6 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, i is an integer satisfying 0≤i≤20, j1 and j2 are each integers satisfying 2≤j1≤100 and 0≤j2≤100, and the order of arrangement of the units enclosed by j1 and the units enclosed by j2 is arbitrary, R 3 are independently a group represented by the following formula (4), [Chemistry 5] -L 1 -((OR 7 ) k -L 2 ) z -COOH (4) Where, L 1 and L 2 Each is a divalent linking group having 2 to 20 carbon atoms, R 7 is a divalent alkylene group having 2 to 4 carbon atoms, k is an integer satisfying 0≤k≤100, z is 0 or 1, R 4 are independently a group represented by the following formula (5), (6), (7), or (8), [Chemistry 6] -(CH2)2-C n H 2n -(SiR 1 2O) m -SiR 1 3 (5) -(CH2)2-C n H 2n -SiR 1 m1 -(OSiR 1 3) 3-m1 (6) -(CH2)2-C n H 2n -SiR 1 m1 -(OSiR 1 m2 (OSiR 1 3) 3-m2 ) 3-m1 (7) -(CH2)2-C n H 2n -SiR 1 m1 -(OSiR 1 m2 (OSiR 1 m3 (OSiR 1 3) 3-m3 ) 3-m2 ) 3-m1 (8) Where R 1 As defined above, n and m are each an integer satisfying 0≤n≤5, 0≤m≤100, and m1, m2, and m3 are integers satisfying 0≤m1≤2, 0≤m2≤2, and 0≤m3≤2. a, b, c, d, e, and f each satisfy 0≤a≤100、 1≤b≤10、 1≤c≤10、 0≤d≤10、 Integers e≥0, f≥0, The arrangement order of the structural units enclosed by a to f is arbitrary.

2. The carboxyl-modified organopolysiloxane according to claim 1, wherein The organopolysiloxane is represented by the following formula (1-1): [Chemistry 7] Where R 1 、R 2 、R 3 、R 4 , a, b, c and d are synonymous with the above.

3. A cosmetic comprising: (A) the carboxyl-modified organopolysiloxane represented by formula (1) according to claim 1, (B) an oily agent, and (C) water.

4. The cosmetic according to claim 3, wherein The oil (B) is at least one selected from silicone oil, hydrocarbon oil and fatty acid ester. The cosmetic according to claim 3 , which is an oil-in-water emulsified cosmetic.

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