Thickening / gelling agent

Abstract

The present invention provides a thickening / gelling agent which contains an organopolysiloxane X that is obtained by a method that comprises a step in which at least one addition compound selected from the group consisting of organic acid anhydrides and cyclic sulfonic acids is added to an organopolysiloxane X' represented by formula (I) and the resulting product is neutralized with a basic compound. If 10 parts by mass of this thickening / gelling agent is added to 100 parts by mass of decamethylcyclopentasiloxane, the transmittance as determined at the wavelength of 650 nm is 75% or more. The present invention also provides a composition for oily cosmetic preparations, the composition containing this thickening / gelling agent. A thickening / gelling agent according to the present invention is suitably used for the purpose of thickening / gelling a liquid organic compound such as a silicone oil, an organic compound with low polarity and a nonpolar organic compound in various fields such as fields of coating materials, inks, lubricating oils, agricultural products, aquatic products, cosmetic products, pharmaceutical products, fibers, resins, polymers, rubbers and metals.

Description

Thickener / gelling agent

[0001] The present invention relates to a thickening / gelling agent used to thicken and gel liquid organic compounds in various fields such as paints, inks, lubricants, agricultural products, marine products, cosmetics, pharmaceuticals, fibers, resins, polymers, rubber, and metals, and to an oil-based cosmetic composition containing the thickening / gelling agent.

[0002] Liquid organic compounds such as silicone oils, low-polarity organic compounds, and non-polar organic compounds are useful raw materials in a variety of fields, including paints, inks, lubricants, agricultural products, marine products, cosmetics, pharmaceuticals, fibers, resins, polymers, rubber, and metals. As gelling agents for these liquid organic compounds, gelling agents having an organopolysiloxane as the main skeleton have been investigated (see Patent Documents 1 and 2).

[0003] JP 2007-1996 A JP 2007-1868 A

[0004] However, the gelling agents of Patent Documents 1 and 2 have the drawback that they do not have a sufficient thickening effect, or even if they are effective in thickening or gelling, they reduce the transparency of the composition to which they are blended.

[0005] An object of the present invention is to provide a thickening / gelling agent that can thicken and / or gel a liquid organic compound without impairing transparency, and an oil-based cosmetic composition containing the thickening / gelling agent.

[0006] The present invention provides: [1] a compound represented by formula (I):

[0007]

[0008] (In the formula, R １ represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms; R ２ represents an unsubstituted or substituted divalent hydrocarbon group having 1 to 10 carbon atoms; R ３ Ha-CH ２ CH ２ -NH ２ group or —CH ２ CH ２ -NH-CH ２ CH ２ -NH ２ A is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms; ２CH ２ CH ２ -NH ２ group or —CH ２ CH ２ CH ２ -NH-CH ２ CH ２ -NH ２ group, x is 5 to 10,000, y is 0 to 100, and when y is 0, at least one of A is —CH ２ CH ２ CH ２ -NH ２ group or —CH ２ CH ２ CH ２ -NH-CH ２ CH ２ -NH ２ [1] a thickening / gelling agent comprising organopolysiloxane X obtained by a method including the steps of adding at least one addition compound selected from the group consisting of organic acid anhydrides and cyclic sulfonic acids to organopolysiloxane X' represented by formula (III):

[0009]

[0010] (In the formula, R ７ [3] The thickening / gelling agent according to [1] above, wherein X is an alkyl or alkenyl group having 4 to 18 carbon atoms; [4] The thickening / gelling agent according to any one of [1] to [3] above, wherein, in formula (I), x is 10 to 1000 and y / (x+y) is 0.001 to 0.2; [5] The thickening / gelling agent according to any one of [1] to [3] above, wherein an alkylene oxide compound is further used as the additional compound; [6] The thickening / gelling agent according to formula (IV), wherein organopolysiloxane X is bonded to a Si atom:

[0011]

[0012] (In the formula, R ８ and R ９are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms), and / or a group represented by formula (V):

[0013]

[0014] (In the formula, R ７ is an alkyl or alkenyl group having 4 to 18 carbon atoms, and M is an alkali metal atom), and the molar ratio of the group represented by formula (IV) to the group represented by formula (V) is 0 or more and 4 or less; [6] The thickening / gelling agent according to any one of [1] to [5] above, further comprising at least one hydrophilic substance selected from the group consisting of glycols having 1 to 8 carbon atoms, glycerin, polyglycerin having an average degree of polymerization of 2 to 20, and fatty acid esters thereof; [7] The thickening / gelling agent according to any one of [1] to [6] above, for thickening and gelling silicone oil, non-polar organic compounds, or low-polarity organic compounds; [8] The thickening / gelling agent according to [7] above, wherein the silicone oil is a hydrophobic silicone oil; [9] The thickening / gelling agent according to any one of [1] to [8] above, which has a viscosity of 100 mPa·s or more at 25°C when added in an amount of 10 parts by mass per 100 parts by mass of decamethylcyclopentasiloxane, and

[10] a composition for oil-based cosmetics containing the thickening / gelling agent according to any one of [1] to [9] above.

[0015] The thickening / gelling agent of the present invention has the excellent effect of being able to thicken and / or gel a liquid organic compound without impairing transparency.

[0016] The thickening / gelling agent of the present invention has the formula (I):

[0017]

[0018] (In the formula, R １ represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms; R ２ represents an unsubstituted or substituted divalent hydrocarbon group having 1 to 10 carbon atoms; R ３ Ha-CH ２ CH ２ -NH ２group or —CH ２ CH ２ -NH-CH ２ CH ２ -NH ２ A is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms; ２ CH ２ CH ２ -NH ２ group or —CH ２ CH ２ CH ２ -NH-CH ２ CH ２ -NH ２ group, x is 5 to 10,000, y is 0 to 100, and when y is 0, at least one of A is —CH ２ CH ２ CH ２ -NH ２ group or —CH ２ CH ２ CH ２ -NH-CH ２ CH ２ -NH ２ The present invention contains organopolysiloxane X obtained by a method including the steps of adding at least one addition compound selected from the group consisting of organic acid anhydrides and cyclic sulfonic acids to organopolysiloxane X' represented by the following formula (wherein X is a substituted or unsubstituted group), and neutralizing the result with a basic compound. In the present invention, the term "thickening / gelling agent" refers to an additive that increases the viscosity of a liquid or solidifies it to eliminate its fluidity. Furthermore, the term "thickening / gelling" refers to thickening or gelation.

[0019] In formula (I), R １ may be the same or different and are unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms. The hydrocarbon group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms. Examples of the hydrocarbon group include alkyl groups such as methyl, ethyl, and propyl groups, and aromatic hydrocarbon groups such as phenyl groups. Examples of the substituent that the hydrocarbon group may have include a hydroxyl group and a halogen atom. The hydrocarbon group is preferably an unsubstituted methyl group.

[0020] R ２is an unsubstituted or substituted divalent hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms. Examples of the hydrocarbon group include alkylene groups such as a methylene group, an ethylene group, and a propylene group, and aromatic hydrocarbon groups such as a phenylene group. Examples of the substituent that the hydrocarbon group may have include a hydroxyl group and a halogen atom. The hydrocarbon group is preferably an unsubstituted methylene group.

[0021] R ３ is -CH ２ CH ２ -NH ２ group or —CH ２ CH ２ -NH-CH ２ CH ２ -NH ２ It is the base.

[0022] A is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, -CH ２ CH ２ CH ２ -NH ２ group or —CH ２ CH ２ CH ２ -NH-CH ２ CH ２ -NH ２ For unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, R １ The hydrocarbon group is the same as the hydrocarbon group in the above.

[0023] x is 5 to 10,000, preferably 10 to 10,000, and more preferably 100 to 3,000.

[0024] y is 0 to 100, preferably 1 to 100, more preferably 3 to 80, and even more preferably 3 to 50.

[0025] When y is 0, at least one of A is —CH ２ CH ２ CH ２ -NH ２ group or —CH ２ CH ２ CH ２ -NH-CH ２ CH ２-NH ２ It is the base.

[0026] When x is 10 to 1000, y / (x+y) is preferably 0.001 to 0.2, more preferably 0.002 to 0.1, and even more preferably 0.003 to 0.08.

[0027] The viscosity (kinetic viscosity) of organopolysiloxane X' at 25°C is preferably 300 to 100,000 mm from the viewpoint of thickening and gelling ability. ２ / s, more preferably 500 to 50,000 mm ２ / s, more preferably 600 to 10,000 mm ２ The viscosity is measured using a capillary viscometer according to JIS Z8803.

[0028] From the viewpoint of solubility in liquid organic compounds, the weight-average molecular weight of organopolysiloxane X′ is preferably 1,000 to 1,000,000, and more preferably 2,000 to 500,000. The weight-average molecular weight is measured by gel permeation chromatography (GPC).

[0029] The addition compound added to organopolysiloxane X′ represented by formula (I) is at least one selected from the group consisting of organic acid anhydrides and cyclic sulfonic acids, and from the viewpoints of solubility in liquid organic compounds and gelling ability, organic acid anhydrides are preferred.

[0030] Examples of organic acid anhydrides include succinic anhydride, maleic anhydride, phthalic anhydride, oxalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, adipic anhydride, cyclohexanecarboxylic anhydride, butanetetracarboxylic anhydride, phenylsuccinic anhydride, itaconic anhydride, allylsuccinic anhydride, (2,7-octadien-1-yl)succinic anhydride, 2,2-dimethylsuccinic anhydride, butylsuccinic anhydride, (2-methyl-2-propenyl)succinic anhydride, 2-buten-1-ylsuccinic anhydride, hexylsuccinic anhydride, hexenylsuccinic anhydride, octylsuccinic anhydride, octenylsuccinic anhydride, and nonenylsuccinic anhydride. Examples of the succinic anhydride include cyclic carboxylic acid anhydrides such as succinic anhydride, decyl succinic anhydride, decenyl succinic anhydride, dodecyl succinic anhydride, dodecenyl succinic anhydride, hexadecyl succinic anhydride, hexadecenyl succinic anhydride, octadecyl succinic anhydride, octadecenyl succinic anhydride, tetradecyl succinic anhydride, tetradecenyl succinic anhydride, pentadecenyl succinic anhydride, [3-(trimethoxysilyl)propyl] succinic anhydride, and [(3-triethoxysilyl)propyl] succinic anhydride; and linear carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, and benzoic anhydride. Of these, cyclic carboxylic acid anhydrides are preferred from the viewpoints of removability after the reaction and cost.

[0031] In the present invention, the organic acid anhydride is preferably a compound represented by the formula (III):

[0032]

[0033] (In the formula, R ７ is an alkyl or alkenyl group having 4 to 18, preferably 6 to 16, carbon atoms. ７ is preferably an alkenyl group. Suitable examples of the succinic anhydride derivative represented by formula (III) include octenylsuccinic anhydride, dodecenylsuccinic anhydride, and pentadecenylsuccinic anhydride.

[0034] Examples of cyclic sulfonic acids include 1,3-propane sultone, 3-hydroxy-1-propanesulfonic acid 1,3-sultone, 3-fluoro-3-hydroxy-1-propanesulfonic acid sultone, 1,4-butane sultone, 1,8-naphtha sultone, 2,4-butane sultone, γ-butane sultone, and δ-hexadecane sultone.

[0035] The amount of the addition compound selected from the group consisting of organic acid anhydrides and cyclic sulfonic acids used is preferably 0.1 to 3.0 moles, and more preferably 0.5 to 1.5 moles, per mole of terminal amino groups contained in organopolysiloxane X'. When multiple types of compounds are used as the addition compound, it is preferable that the total amount of these compounds be within the above range.

[0036] When the addition compound is added to the organopolysiloxane X', it is preferable to further use an alkylene oxide compound as the addition compound from the viewpoint of adjusting viscosity and improving solubility.

[0037] Examples of the alkylene oxide compound include glycidol, ethylene oxide, propylene oxide, butylene oxide, lauryl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and laureth glycidyl ether.

[0038] The amount of alkylene oxide compound used is preferably 0.01 to 1.5 moles, and more preferably 0.02 to 1.0 moles, per mole of terminal amino groups contained in organopolysiloxane X'.

[0039] The addition reaction can be carried out by mixing organopolysiloxane X' and the addition compound in a solvent and appropriately stirring the mixture.

[0040] The solvent is not particularly limited as long as it is inert to the addition reaction, and examples thereof include isopropyl alcohol, tetrahydrofuran, dimethylformamide, and dimethyl sulfoxide.

[0041] The amount of solvent used is not particularly limited, but from the viewpoint of facilitating the reaction and obtaining effects according to the amount used, it is preferably about 50 to 200 parts by mass per 100 parts by mass of the total of organopolysiloxane X' and the addition compound.

[0042] The atmosphere during the reaction is not particularly limited, and may be air, but is preferably an inert gas such as nitrogen gas from the viewpoint of preventing coloration and suppressing side reactions.

[0043] The reaction temperature is not particularly limited, but from the viewpoint of preventing coloration and suppressing side reactions, it is preferably 0 to 100° C., more preferably 10 to 80° C. The reaction time cannot be generalized because it varies depending on the reaction temperature, but is usually preferably about 1 to 10 hours.

[0044] For example, when a carboxylic acid anhydride is used as the addition compound, the progress and end point of the reaction can be confirmed by infrared absorption analysis, where the characteristic absorption of the carboxylic acid anhydride disappears and an organic-modified alkylpolysiloxane having a carboxy group at the end of the organic group bonded to the silicon atom is produced.

[0045] The reaction product produced by the addition reaction is reacted with a basic compound to neutralize it.

[0046] Examples of basic compounds include compounds having an amino group such as methylaminopropanediol, triethanolamine, diethanolamine, monoethanolamine, aminopropanediol, triisopropanolamine, 2-amino-2-hydroxymethyl-1,3-propanediol, and dimethylaminomethylpropanol, and alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, and sodium isopropoxide. Of these, compounds having an amino group are preferred from the viewpoint of application comfort, and alkali metal alkoxides are preferred from the viewpoint of thickening. In the alkali metal alkoxide, sodium and potassium are preferred as the alkali metal, and the number of carbon atoms in the alkoxide is preferably 1 to 10, more preferably 1 to 8.

[0047] The amount of the basic compound used is preferably 0.5 to 1.5 moles, and more preferably 0.8 to 1.2 moles, per mole of the addition compound added to the terminal amino groups of organopolysiloxane X'. The addition compound referred to here is an addition compound selected from the group consisting of organic acid anhydrides and cyclic sulfonic acids.

[0048] The reaction temperature is not particularly limited, but from the viewpoint of preventing coloration and suppressing side reactions, it is preferably 0 to 100° C., more preferably 10 to 80° C. The reaction time cannot be generalized because it varies depending on the reaction temperature, but is usually preferably about 30 minutes to 10 hours.

[0049] The progress and end point of the reaction can be confirmed by measuring the acid value or the like.

[0050] After the reaction is complete, the resulting neutralized product (organopolysiloxane X) can be isolated by distilling off the low-boiling components or other procedures.

[0051] -CH ２ CH ２ CH ２ -NH-CH ２ CH ２ -NH ２ When succinic anhydride or succinic anhydride and glycidol are added to organopolysiloxane X' having a group, and the resulting mixture is neutralized with a basic compound having an amino group, -CH ２ CH ２ CH ２ -NH-CH ２ CH ２ -NH ２ Succinic anhydride or succinic anhydride and glycidol are added to the terminal amino group of the group, and the terminal carboxy group of the added succinic anhydride is neutralized to form, for example, a compound of the formula (II):

[0052]

[0053] (In the formula, R ４ , R ５ , and R ６is an unsubstituted or one or more hydroxyl group-containing linear or branched alkyl group having 1 to 4 carbon atoms, a and b are the average number of moles added, a is 0.4 to 1.5, preferably 0.5 to 1.4, and b is 0 to 2.0, preferably 0 to 0.5, and more preferably 0 to 0.3), thereby producing an organopolysiloxane X having a group represented by the formula:

[0054] The higher the proportion of a, the easier it is to gel, and the higher the proportion of b, the easier it is to thicken.

[0055] Also, -CH ２ CH ２ CH ２ -NH-CH ２ CH ２ -NH ２ When a succinic anhydride derivative represented by formula (III) or the succinic anhydride derivative and at least one glycidyl compound selected from the group consisting of glycidol, alkyl glycidyl ether, and alkenyl glycidyl ether is added to an organopolysiloxane X′ having a —CH group, and the resulting mixture is neutralized with an alkali metal alkoxide, a —CH ２ CH ２ CH ２ -NH-CH ２ CH ２ -NH ２ A succinic anhydride derivative or a glycidyl compound is added to the terminal amino group of the group, and the terminal carboxy group of the added succinic anhydride derivative is neutralized to form, for example, a compound represented by formula (IV):

[0056]

[0057] (In the formula, R 8 and R 9 are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms), and / or a group represented by formula (V):

[0058]

[0059] (wherein M is an alkali metal atom, R ７is the same as above), the molar ratio of the group represented by formula (IV) to the group represented by formula (V) is preferably 0 or more and 4 or less, and from the viewpoint of improving solubility in liquid organic compounds, it is more preferably 0.2 to 3, even more preferably 0.5 to 2.5, and even more preferably 0.5 to 1.

[0060] The organopolysiloxane X having a group represented by formula (IV) and / or a group represented by formula (V) may be a group represented by formula (VI):

[0061]

[0062] (wherein m+n is 0 to 100, m is 0 to 80, n is greater than 0 and less than 100, p and q are such that p+q is 5 to 10,000, m / n is 0 to 4, and R １ , R ７ ~R ９ , A and M are the same as above), and an organopolysiloxane represented by formula (VIa):

[0063]

[0064] Organopolysiloxanes represented by the formula: (wherein m, n, p, and q are the same as defined above) are more preferred.

[0065] The content of organopolysiloxane X in the thickening / gelling agent is preferably 90 to 100% by mass, more preferably 95 to 99.8% by mass, and even more preferably 97 to 99.5% by mass.

[0066] From the viewpoint of enhancing the thickening property, the thickening / gelling agent of the present invention preferably contains at least one hydrophilic substance selected from the group consisting of glycols having 1 to 8 carbon atoms, glycerin, polyglycerin having an average degree of polymerization of 2 or more and 20 or less, and fatty acid esters thereof.

[0067] Examples of glycols include 1,4-butylene glycol, 1,3-butylene glycol, pentylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, etc. The number of carbon atoms of the glycol is preferably 2 to 6.

[0068] The average degree of polymerization of polyglycerol is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. The average degree of polymerization of polyglycerol in this specification is the average degree of polymerization of polyglycerol calculated from the hydroxyl value by terminal group analysis, and is the average degree of polymerization calculated from (Equation 1) and (Equation 2). (Equation 1) Average degree of polymerization = (112.2 × 10 ３ −18 × hydroxyl value) / (74 × hydroxyl value − 56.1 × 10 ３ ) (Formula 2) Hydroxyl value = (a - b) x 28.05 / sample amount (g) a: Amount of 0.5N potassium hydroxide solution consumed in blank test (ml) b: Amount of 0.5N potassium hydroxide solution consumed in main test (ml) The hydroxyl value in the above (Formula 1) is calculated using (Formula 2) in accordance with "Japan Oil Chemists' Society Standards for Analysis of Fats, Oils and Related Materials (I) 1996 Edition," compiled by the Japan Oil Chemists' Society.

[0069] Examples of fatty acids constituting the fatty acid esters with glycol, glycerin, or polyglycerin include fatty acids having 6 to 18 carbon atoms, such as caproic acid, capric acid, caprylic acid, lauric acid, myristic acid, palmitic acid, and stearic acid.

[0070] The hydrophilic substance may be mixed with organopolysiloxane X and incorporated into the thickening / gelling agent, or may be added to the reaction system together with the basic compound in the neutralization step when organopolysiloxane X is prepared.

[0071] The content of the hydrophilic substance is preferably 0.05 to 0.5 mol, more preferably 0.1 to 0.4 mol, and even more preferably 0.15 to 0.30 mol per mol of the addition compound added to the terminal amino groups of organopolysiloxane X'. The addition compound referred to here is an addition compound selected from the group consisting of organic acid anhydrides and cyclic sulfonic acids.

[0072] The thickening / gelling agent of the present invention can be used to thicken and gel a liquid organic compound.

[0073] Examples of liquid organic compounds that can be used with the thickening / gelling agent of the present invention include silicone oils, non-polar organic compounds, and low-polarity organic compounds. Of these, silicone oils, non-polar organic compounds, and low-polarity organic compounds are preferred.

[0074] The silicone oil may have a cyclic, linear, or branched structure, but from the viewpoint of ease of gelation, hydrophobic silicone oils are preferred. The viscosity of the silicone oil at 25°C is preferably 0.65 to 100,000 mPa·s, more preferably 0.65 to 10,000 mPa·s. Specific examples of silicone oils include cyclic diorganopolysiloxanes such as cyclopentasiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane; linear diorganopolysiloxanes such as hexamethyldisiloxane, dimethylpolysiloxanes capped at both ends with trimethylsiloxy groups, methylphenylpolysiloxanes capped at both ends with trimethylsiloxy groups, and methylalkylpolysiloxanes capped at both ends with trimethylsiloxy groups; and branched organopolysiloxanes such as methyltristrimethylsiloxysilane, ethyltristrimethylsiloxysilane, propyltristrimethylsiloxysilane, and tetraquistrimethylsiloxysilane. Of these, volatile linear dimethylpolysiloxanes, branched methylpolysiloxanes, and cyclic dimethylpolysiloxanes are preferred, with decamethylcyclopentasiloxane being more preferred.

[0075] Examples of non-polar organic compounds and low-polar organic compounds include hydrocarbons such as hexane, heptane, toluene, xylene, mesitylene, liquid paraffin, petrolatum, n-paraffin, isoparaffin, isododecane, hydrogenated polyisobutylene, ozokerite, ceresin, squalane, and pristane; avocado oil, almond oil, olive oil, sesame oil, camellia oil, safflower oil, soybean oil, camellia oil, corn oil, rapeseed oil, persic oil, castor oil, cottonseed oil, peanut oil, and cocoa. Vegetable fats and oils such as oat butter, palm oil, palm kernel oil, Japan wax, and coconut oil; animal fats and oils such as mink oil, egg yolk oil, beef tallow, lard, and hardened oil; waxes such as beeswax, carnauba wax, spermaceti, lanolin, liquid lanolin, reduced lanolin, hard lanolin, candelilla wax, jojoba oil, and microcrystalline wax; palmityl alcohol, stearyl alcohol, oleyl alcohol, lanolin alcohol, cholesterol, phytosterol, 2-hexyldecanol, isostearate higher alcohols such as methyl formate, ethyl formate, ethyl acetate, propyl acetate, butyl acetate, cetyl octanoate, isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, oleyl oleate, decyl oleate, octyldodecyl myristate, hexyldecyl dimethyloctanoate, isononyl isononanoate, cetyl lactate, myristyl lactate, diethyl phthalate, dibutyl phthalate, lanolin acetate, ethylene glycol monostearate, propylene glycol monostearate, propylene glycol dioleate, glyceryl monostearate, glyceryl monooleate, glyceryl tri-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, and the like; liquid fatty acid triglyceride, artificial sebum (a mixture of squalane, liquid fatty acid triglyceride, and oleic acid).

[0076] When 10 parts by mass of the thickening / gelling agent of the present invention is added to 100 parts by mass of decamethylcyclopentasiloxane, the viscosity at 25°C is preferably 100 mPa s or more, more preferably 150 mPa s or more, and even more preferably 200 mPa s or more.

[0077] The thickening / gelling agent of the present invention can thicken and gel without impairing the transparency of the compound to which it is added. When 10 parts by mass of the thickening / gelling agent of the present invention is added to 100 parts by mass of decamethylcyclopentasiloxane, the transmittance measured at a wavelength of 650 nm is 75% or more, preferably 80% or more, and more preferably 85% or more. When an acid anhydride without a hydrocarbon group, such as succinic anhydride or maleic anhydride, is used as an adduct to organopolysiloxane X' represented by formula (I) and neutralized with an alkali metal alkoxide, the hydrophilicity becomes too high, and the resulting compound either does not dissolve in silicone oil or, even if it does, has a cloudy appearance, making it difficult to meet the transmittance requirement. Therefore, when an acid anhydride without a hydrocarbon group is used as an adduct, it is preferable to neutralize it with a basic compound such as a compound having an amino group. On the other hand, when an acid anhydride with a hydrocarbon group is used, either an alkali metal alkoxide or a compound having an amino group may be used for neutralization, but from the viewpoint of thickening, an alkali metal alkoxide is preferred.

[0078] The present invention further provides a composition for oily cosmetics containing an oil and the thickening / gelling agent of the present invention. The thickening / gelling agent is blended in an amount suitable for thickening and gelling the oil depending on the intended use, and the content of the thickening / gelling agent is preferably about 3 to 25 parts by mass, more preferably 5 to 20 parts by mass, per 100 parts by mass of the oil.

[0079] The oil agent is preferably at least one selected from the group consisting of the silicone oil, non-polar organic compounds, and low-polarity organic compounds.

[0080] The viscosity of the oil is preferably 50 mPa·s or less, more preferably 40 mPa·s or less, and even more preferably 30 mPa·s or less. Here, the viscosity of the oil is measured using a rotational viscometer. The viscosity of the silicone oil is also measured using the same method.

[0081] The content of the oil agent in the oil-based cosmetic composition is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and even more preferably 20 to 70% by mass.

[0082] Examples of additives contained in oil-based cosmetic compositions include surfactants, ultraviolet absorbers, powders, antioxidants, preservatives, fragrances, colorants, chelating agents, cooling agents, thickeners, plant extracts, vitamins, neutralizing agents, moisturizing agents, anti-inflammatory agents, pH adjusters, and amino acids.

[0083] The oil-based cosmetic composition can be prepared by heating and mixing the oil agent, thickening / gelling agent, and additives to be added as needed in any order, and then stirring and cooling to room temperature.

[0084] Examples of uses of the oil-based cosmetic composition include, in the case of a high-viscosity composition, sunscreen cream, foundation, cleansing agent, nail oil, body oil, cosmetic oil, hair care products, etc., and in the case of a gel composition, lip gloss, mascara, eyeliner, stick cosmetics, etc. Furthermore, the oil-based cosmetic composition of the present invention can also be used to prepare non-oily cosmetics such as emulsion cosmetics. Examples of such cosmetics include emulsion-type cleansing cosmetics, milky lotions, creams, beauty serums, O / W-type sunscreen cosmetics, hair conditioners, hair masks, hair styling products, etc.

[0085] The present invention will be specifically explained below with reference to examples, but the present invention is not limited to these examples in any way.

[0086] Example 1 Formula (Ia):

[0087]

[0088] 11.2 g of dimethylsiloxane-methyl(3-(2-aminoethyl)aminopropyl)siloxane copolymer (KF-867S (manufactured by Shin-Etsu Chemical Co., Ltd.), viscosity (25 ° C): 1300 mm ２To a mixture of 20 g of glycidol (1.32 mmol) and 20 g of isopropyl alcohol (1.32 mmol), 0.53 g of succinic anhydride (5.27 mmol) was added, and the mixture was stirred for 5 hours at 30-40°C under a nitrogen stream. Infrared absorption (IR) analysis revealed that the characteristic absorption of carboxylic acid anhydride had disappeared, and an organically modified methylpolysiloxane having a carboxy group at the end of the organic group bonded to the silicon atom had been produced. Note that x and y in formula (Ia) were calculated from the weight average molecular weight (20,000) and functional group equivalent (1700 g / mol) measured by GPC using "KF-867S." After the reaction product was cooled to room temperature (25° C.), 0.55 g (5.27 mmol) of methylaminopropanediol and 0.12 g (1.32 mmol) of glycerin were added, and the reaction product and methylaminopropanediol were reacted at room temperature for 30 minutes. Subsequently, low-boiling components were distilled off under reduced pressure with heating, yielding 11.2 g of a transparent solid composition.

[0089] Examples 2 to 5 Transparent solid compositions were obtained in the same manner as in Example 1, except that the compounds shown in Table 1 were used as the hydrophilic substance.

[0090] Examples 6 to 11 Transparent solid compositions were obtained in the same manner as in Example 1, except that glycidol was not used and the addition compounds, basic compounds and hydrophilic substances shown in Table 1 were used instead.

[0091] Examples 12 to 19 Transparent solid compositions were obtained in the same manner as in Example 1, except that glycerin was not used and the addition compounds and basic compounds shown in Tables 1 and 2 were used.

[0092] Comparative Examples 1 to 4 Transparent solid compositions were obtained in the same manner as in Example 1, except that glycidol was not used and the addition compounds and basic compounds shown in Table 1 were used instead.

[0093] [Thickener Test] Using the compositions obtained in Examples 1 to 19 and Comparative Examples 1 to 4, 100 parts by weight of decamethylcyclopentasiloxane and 10 parts by weight of the composition were stirred at 90°C and cooled to room temperature. As a result, the compositions of Examples 1 to 19 and Comparative Example 4 acted as thickening / gelling agents, and thickened / gelled compositions were obtained. However, the dissolution time tended to be shorter for compositions containing an alkylene oxide compound. For example, in Examples 12 and 14, it took one day for the composition to dissolve, whereas in Examples 15 to 19, the composition dissolved within 30 minutes to several hours. The dissolution time for the compositions of Examples 12, 14 to 19, and Comparative Example 4 is shown in Table 2 as an index of solubility. On the other hand, in Comparative Examples 1 to 3, the composition did not dissolve in the oil (decamethylcyclopentasiloxane) and separated, resulting in no thickened / gelled composition being obtained.

[0094] The viscosity at 25°C and transmittance at 650 nm of the thickened / gelling compositions containing the compositions of Examples 1 to 19 and Comparative Example 4 were measured by the following method immediately after preparation (the point at which it was confirmed that all of the thickening / gelling agent had dissolved in the oil). Furthermore, the thickened / gelling compositions containing the compositions obtained in Examples 12, 14 to 19, and Comparative Example 4 were stored at high temperature (50°C) for one month, and the viscosity at 25°C and transmittance at 650 nm of the compositions after storage were measured again. The results are shown in Tables 1 and 2. Note that the viscosity of decamethylcyclopentasiloxane at 25°C is 4 mPa s, and the transmittance at 650 nm is 100%.

[0095] [Viscosity] The viscosity of the thickened / gelled composition was measured for dynamic viscoelasticity by frequency dispersion under the following conditions. －１ The complex viscosity obtained in the above is taken as the viscosity. Apparatus: Rotational rheometer ARES-G2 dynamic viscoelasticity measuring apparatus (manufactured by TA instruments) Jig: 50 mm 0.02 rad cone plate, stainless steel Temperature: 25°C

[0096] [Transmittance] 2.5 mL of the thickened / gelling composition was placed in a quartz cell with an optical path length of 1.0 cm, and the transmittance at a wavelength of 650 nm was measured using a spectrophotometer manufactured by Hitachi High-Tech Science Corp. Here, the transmittance of ion-exchanged water was taken as 100%.

[0097]

[0098]

[0099] From the above results, it can be seen that using the compositions of Examples 1 to 19 as thickening / gelling agents makes it possible to thicken silicone oils without impairing transparency. In particular, a comparison of Examples 15 and 17 reveals that the use of a succinic anhydride derivative as an additive compound maintains viscosity without reducing viscosity even after extended periods at high temperatures. Furthermore, a comparison of Examples 14 with Examples 16 and 19 reveals that the use of an alkylene oxide compound significantly improves solubility, and a comparison of Examples 16 to 18 reveals that increasing the amount of alkylene oxide compound used further improves solubility. In contrast, the compositions of Comparative Examples 1 to 3 do not function as thickening / gelling agents, and the composition of Comparative Example 4, while having a thickening / gelling effect, exhibits a significant decrease in transparency.

[0100] Formulation examples of the oily cosmetic composition of the present invention (sunscreen cream, hair oil, lip gloss, liquid foundation, oil mousse) are shown in Tables 3 to 8. These formulations were excellent not only in thickening ability but also in water resistance and sebum resistance.

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107] The thickening / gelling agent of the present invention is suitable for use in various fields such as paints, inks, lubricating oils, agricultural products, marine products, cosmetics, pharmaceuticals, fibers, resins, polymers, rubber, and metals to thicken and gel liquid organic compounds such as silicone oils, low-polarity organic compounds, and non-polar organic compounds.

Claims

1. Formula (I): 【Chemical 1】 (In the formula, R １ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ２ is an unsubstituted or substituted divalent hydrocarbon group having 1 to 10 carbon atoms, R ３ is -CH ２ CH ２ -NH ２ group or -CH ２ CH ２ -NH-CH ２ CH ２ -NH ２ group, A is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, -CH ２ CH ２ CH ２ -NH ２ group or -CH ２ CH ２ CH ２ -NH-CH ２ CH ２ -NH ２ group, x is 5 to 10,000, y is 0 to 100, and when y is 0, at least one of A is -CH ２ CH ２ CH ２ -NH ２ group or -CH ２ CH ２ CH ２ -NH-CH ２ CH ２ -NH ２ group) An organopolysiloxane X obtained by a method including a step of adding at least one addition compound selected from the group consisting of an organic anhydrous acid and a cyclic sulfonic acid to an organopolysiloxane X' represented by the formula, and neutralizing with a basic compound, and containing the organopolysiloxane X, a thickening / gelling agent, when 10 parts by mass is added to 100 parts by mass of decamethylcyclopentasiloxane, the transmittance measured at a wavelength of 650 nm is 75% or more, a thickening / gelling agent.

2. The addition compound is represented by formula (III): 【Chemical 2】 (In the formula, R ７ is an alkyl group or an alkenyl group having 4 to 18 carbon atoms) The thickening / gelling agent according to claim 1, which is a succinic anhydride derivative represented by

3. In formula (I), x is 10 to 1000, and y / (x + y) is 0.001 to 0.

2. The thickening / gelling agent according to claim 1.

4. The thickening / gelling agent according to claim 1, further using an alkylene oxide compound as an addition compound.

5. The organopolysiloxane X is a group represented by formula (IV) bonded to an Si atom: [Chemical Formula 3] (In the formula, R ８ and R ９ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms) and / or a group represented by formula (V): [Chemical Formula 4] (In the formula, R ７ is an alkyl group or an alkenyl group having 4 to 18 carbon atoms, and M is an alkali metal atom) The thickening / gelling agent according to claim 1, having a group represented by formula (IV) and a molar ratio of the group represented by formula (IV) to the group represented by formula (V) of 0 or more and 4 or less.

6. The thickening / gelling agent according to claim 1, further containing at least one hydrophilic substance selected from the group consisting of glycols having 1 to 8 carbon atoms, glycerin, polyglycerin having an average degree of polymerization of 2 or more and 20 or less, and fatty acid esters thereof.

7. The thickening / gelling agent according to claim 1 for thickening / gelling a silicone oil, a nonpolar organic compound, or a low-polarity organic compound.

8. The thickening / gelling agent according to claim 7, wherein the silicone oil is a hydrophobic silicone oil.

9. The thickening / gelling agent according to claim 1, wherein when 10 parts by mass is added to 100 parts by mass of decamethylcyclopentasiloxane, the viscosity at 25°C is 100 mPa·s or more.

10. An oily cosmetic composition comprising the thickening / gelling agent according to any one of claims 1 to 9.

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