JPH02115110A - Material for cosmetic - Google Patents

Abstract

PURPOSE:To obtain a material for cosmetics containing a specific organopolysiloxane.polyoxyalkylene copolymer as a main material without essentially emitting rancid and irritant smell even in contact with water. CONSTITUTION:A material for cosmetics containing an organopolysiloxane.polyoxyalkylene copolymer expressed by the formula (R<1> is H, 1-18C monofunctional hydrocarbon, etc.; R<2> is 1-30C monofunctional hydrocarbon; l is 2-4; n is 3-100; m is 2 or 3; a and b are 0.01<a<=1; 1<b<=2.5) as a main material. The copolymer expressed by the formula is readily obtained by subjecting a carboxyl group-containing organopolysiloxane and a hydroxyl group-containing polyoxyalkylene compound to esterifying reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to cosmetic materials, particularly organopolysiloxane polyoxyal which are odorless and hypoallergenic.

[Prior art] Organopolysiloxane/polyoxyalkylene copolymers containing polyoxyalkylene groups such as polyoxyethylene groups and polyoxypropylene groups in their molecular chains have smoothness, spreadability, and gloss. Because of its excellent surfactant performance, represented by its compatibility and emulsifying properties,
Cosmetics field, such as shampoo, conditioner, hand cream.

It is widely used as an ingredient in makeup materials.

[Problems to be solved] However, this organopolysiloxane/polyoxyalkylene copolymer inherently has a rancid odor because the polyoxyalkylene structure contained therein is susceptible to oxidation. Therefore, various attempts have been made to make it odorless and hypoallergenic, such as adsorption treatment with activated carbon or activated clay, and deodorization with steam treatment. , a method of replacing with nitrogen gas, a method of adding tocopherol, which is well known as vitamin E (Japanese Patent Publication No. 55-41210
(see Japanese Patent Publication No. 63), method of adding phytic acid (see Japanese Patent Publication No. 63
-9531) and the like are known.

However, when treated with these methods, organopolysiloxane polyoxyalkylene copolymers can certainly reduce their odor, and if these methods are used alone or in combination, they can be treated immediately after production or when treated with nitrogen gas. Although an almost odorless product can be obtained under sealed storage, organopolysiloxane/polyoxyalkylene copolymers that have been reduced in odor by this method do not come into contact with sweat or moisture, or are exposed to When used as an active agent in an aqueous dispersion system, it has the disadvantage of producing a markedly rancid or irritating odor; therefore, when used as a cosmetic material, it is required to be odorless and hypoallergenic. In particular, the recent trend of favoring lightly scented cosmetics has the serious drawback of not being able to use them.
This solution is strongly needed.

[Means for Solving the Problems] The present invention relates to a cosmetic material that solves the above problems and does not generate rancid or irritating odors due to the wood structure even when it comes into contact with moisture. is the general formula % formula % (1) (where R+ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, R2 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 30 carbon atoms) , L is 2 to 4, n is 3 to
100, m is 2 or 3, a, b are 0.01<a≦1.
Organopolysiloxane represented by 1<b≦2.5)
It is characterized by being mainly made of polyoxyalkylene copolymer.

That is, the present inventors have investigated the rancid odor that occurs when the above-mentioned organopolysiloxane polyoxyalkylene copolymer comes into contact with human sweat or moisture, or when it is used as a surfactant in an aqueous dispersion system. As a result of various studies on the types of substances that cause pungent odors and the formation mechanism, we found that the substance that gives off this rancid odor and pungent odor is a specific aldehyde, and that its production is caused by organohydrodiene polysiloxane and allyl group-containing polyoxy This is due to the by-product of addition isomers when hydrosilylating an alkylene compound in the presence of a platinum catalyst. It was discovered that siloxane/polyoxyalkylene copolymers generate rancid and pungent odors when mixed with water and acid oil, and in order to prevent this, this organopolysiloxane/polyoxyalkylene copolymer If it has the structure shown by the general formula (1) above, even if it comes into contact with sweat or moisture, and even if it is used as a surfactant in an aqueous dispersion system, it will not become rancid or irritate. It was confirmed that no odor was generated, and the present invention was completed by conducting research on the production of various cosmetic materials to which this organopolysiloxane/polyoxyalkylene copolymer was added.

This will be explained in detail below.

The organopolysiloxane/polyoxyalkylene copolymer which is the main material of the cosmetic material of the present invention is represented by the general formula % (where R1 is a hydrogen atom, a methyl group, an ethyl group,
Monovalent carbons having 1 to 18 carbon atoms such as propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, oleyl group, linole group, etc. hydrogen group,
R2 is a methyl group.

Ethyl group, propyl group, butyl group, pentyl group.

Hexyl group, octyl group, nonyl group, 6-decyl group.

Dodecyl group, tetradecyl group, hexadecyl group.

Monovalent hydrocarbon groups having 1 to 30 carbon atoms such as octadecyl group, triacontyl group and phenyl group, λ is 2 to 4 and C
uI2. If the oxyalkylene group represented by O is ethylene oxide, propylene oxide, butylene oxide, or a mixture thereof, and n is smaller than 3, the slipperiness, compatibility, and interfacial properties peculiar to polyoxyalkylene groups will not appear, and 1oO If it is larger, the fluidity will decrease, so it needs to be in the range of 3 to 100, m
Since is 2 or 3, (CH2) is assumed to be an ethylene group or a propylene group. Also, this a value is 0
．． If it is smaller than O, the slipperiness, compatibility, and interfacial properties characteristic of polyoxyalkylene groups will not appear, and if it is larger than 1, it will not be possible to produce it by a synthesis method within normal economic limits, so this is 0.01<a. It is necessary to keep the b value in the range of ≦1, and if the b value is less than 1, the siloxane structure will have more branches and the lubricity will decrease, and if it is larger than 2.5, the synthesis will be difficult, so the b value should be 1. <b≦2.5.

The structure of the organopolysiloxane moiety in this organopolysiloxane/polyoxyalkylene copolymer may be linear, monomolecular, or cyclic.
The structure of this polyoxyalkylene moiety may be such that it is bonded to either one end, nine both ends, a side chain, or both ends and side chain of the organopolysiloxane chain.

This organopolysiloxane/polyoxyalkylene copolymer is composed of a carboxyl group-containing organopolysiloxane represented by the general formula (where R2, m, a, and b are the same as above) and the general formula % formula % (3) (where R2, m, a, and b are the same as above). can be easily synthesized by carrying out an esterification reaction with a hydroxyl group-containing polyoxyalkylene compound represented by R' and f2.n are the same as above. This reaction is usually carried out at 50-150°C in the presence of a solvent and a catalyst.
Preferably, the temperature range is 80 to 130°C, and the solvent may be a mixture of the above-mentioned formulas (2) and (3), and any solvent that is inert to both and the catalyst. Although there are no particular restrictions, it is preferable to use benzene or toluene, which forms an azeotrope with water, rather than a dehydration reaction. In addition, as this catalyst, acids, alkalis, metal salts, ion exchange resins, etc. used in ordinary ester reactions may be used, but p-toluenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid and An example is sulfuric acid. This reaction is preferably carried out under the conditions of refluxing in a nitrogen gas stream within the above-mentioned temperature range and successively removing water produced in the ester adapter from the system.

The carboxyl group-containing organopolysiloxane represented by the formula (2) used here is a known one, but this one is obtained by distilling and purifying a hydrosilylated product of an organohydrodiene silane and an unsaturated group-containing nitrile compound. Afterwards, it is preferable to perform a hydrolysis reaction to obtain a carboxyl group-containing oligosiloxane, which is then polymerized with a cyclic siloxane. According to this method, an organohydrodiene silane and an unsaturated group-containing oligosiloxane Addition isomers as off-flavor components generated in the presence of water in the organopolysiloxane/polyoxyalkylene copolymer produced as a by-product during the hydrosilylation reaction during distillation purification of hydrosilylated products with nitrile compounds can be almost completely removed. Therefore, it is advantageous that the target organopolysiloxane/polyoxyalkylene can be made to have no fermentation odor or irritating odor even in the presence of water.

The organopolysiloxane/polyoxyalkylene copolymer obtained by this method is itself odorless and hypoallergenic, and even when it comes into contact with human sweat and moisture, it does not react at the interface. Even when used as an activator in an aqueous dispersion system, it does not produce rancid or irritating odors, making it a stable form suitable for use as a cosmetic material, but it also prevents oxidative deterioration due to heat etc. For this purpose, known methods such as adsorption treatment, treatment with tocophenol, phytic acid, etc., addition of various antioxidants, steam distillation, etc. may be applied.

[Example] Next, examples of the present invention will be given.

Example 1 Bis obtained by hydrolysis of rectified 2-cyanoethyldimethylchlorosilane in the presence of a potassium hydroxide catalyst was placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube. 7.5 g of (2-carboxyethyl)tetramethyldisiloxane and 17.9 g of 2-carboxyethyl methylsiloxane oligomer obtained by hydrolysis of rectified 2-cyanethylmethyldichlorosilane in the presence of a potassium hydroxide catalyst. and 170.3 g of octamethylcyclotetrasiloxane, and 0.3 g of trifluoromethanesulfonic acid was added while stirring at 60°C in a nitrogen gas stream.
When polymerized for 5 hours in the temperature range of 0.degree. C., a polysiloxane substituted with carboxyethyl groups was obtained.

Next, polyethylene glycol 1 having a molecular weight of about 550 and having one molecular chain end blocked with a methoxy group was added to the reaction mixture.
04.3 g of toluene and 300 g of toluene were added, and dehydration reaction was carried out using an ester adapter under toluene reflux. After completing the generation of water in about 4 hours, it was cooled to room temperature, and 0.2 g of sodium hydrogen carbonate was added. Stirring was carried out for a period of time, and a pressure of 200 mmHH was further applied for 7 hours in a nitrogen gas stream.
Toluene was stripped at a temperature range of 0 to 80°C and overloaded with 3 g of activated carbon to obtain 284 g of a pale yellow transparent liquid.

This material has a viscosity of 702 cS at 25°C and a specific gravity of 1
．． 051 showed physical properties of a refractive index of 1.4340, but as a result of chemical analysis, it was determined that it was a methylpolysiloxane polyoxyethylene copolymer represented by the following formula % (representing 2). confirmed.

The methylpolysiloxane/polyoxyethylene copolymer thus obtained is odorless and hypoallergenic, and 50g of this and 50g of water were placed in a sealed tube and heated at 60°C while shaking.
When the product was aged for 48 hours and smelled, it had no rancid or pungent odor and was suitable for use in cosmetics.

Comparative Example 1 In a glass reactor equipped with a stirring device, a reflux condenser with an ester adapter, and a thermometer, both ends were blocked with dimethylhydrodienesilyl groups, and an average of 5 methylhydrodienesiloxane units and an average of 85 methylhydrodienesiloxane units were placed. 672g of methylhydrodiene polysiloxane having dimethylsiloxane units of Add 373 g of allyl ether, 400 g of toluene, 1.5 g of a 50% aqueous solution of phytic acid, 0.8 g of potassium acetate, and 0.4 g of a 2% isopropanol solution of chloroplatinic acid, and heat under toluene reflux conditions to dehydrate. While 4
The reaction mixture was allowed to react for a period of time, and then toluene and other volatile components were stripped from the reaction mixture at 100°C and 50 mmHg under nitrogen gas aeration, followed by pressure filtration using diatomaceous earth as a filtering agent. A methylpolysiloxane/polyoxyethylene copolymer represented by the following formula % was obtained. 50 g of this copolymer and 50 g of water were put into a sealed tube and aged at 60°C for 48 hours with shaking. When I smelled it, it had a very rancid and pungent odor.

Examples 2 to 6 In addition to changing the bis(2-carboxyethyl)tetramethyldisiloxane in Example 1 to bis(2-carboxyethyl)tetramethyldisiloxane or hexamethyldisiloxane in the amount shown in Table 1, - The amounts of carboxyethylmethyldichlorosilane and octamethylcyclotetrasiloxane were set as shown in Table 1, and the polyoxyalkylene glycol shown in Table 1, such as polyethylene glycol, was treated in the same manner as in Example 1. Various methylpolysiloxane/polyoxyalkylene copolymers shown in Table 1 were obtained, and the physical properties of these were investigated, as well as the odor after aging at 60°C in the presence of water for 48 hours. As a result, none of these exhibited any rancid odor or irritating odor, and the results shown in Table 1 were obtained.

Example 7 Polyethylene glycol (molecule ff 120.000)
, absolute ethanol, and purified water in the proportions (parts by weight) shown in Table 2 to prepare a fragrance-free hair setting agent base. When 2 parts by weight of polysiloxane/polyoxyalkylene copolymer was added and the odor after aging at 60°C for 72 hours was examined, the results shown in Table 2 were obtained.

Example 8 A shampoo was made using lauryl sulfate triethanolamine salt and lauric acid ethanolamide as the main ingredients, and the formulations (parts by weight) shown in Table 3 were used. 72 parts by weight of organosiloxane/polyoxyalkylene copolymer was added at 60°C.
When the odor after time aging was examined, the results shown in Table 3 were obtained.

Example 9 A fragrance-free hair rinse composition was prepared with the formulation (parts by weight) shown in Table 4, and the organosiloxane/polyoxyalkylene copolymer obtained in Example 2.3.5 and Comparative Example 1 was added to this composition. 2 parts by weight and 40 parts by weight of these compositions.
When the stability after 240 hours at 60°C, the combability, and the odor after aging at 60°C for 72 hours were examined, the results shown in Table 4 were obtained.

Example 10 A fragrance-free cream was prepared with the formulation (parts by weight) shown in Table 5, and organopolysiloxane-polyoxyalkylene copolymer 2 obtained in Examples 1, 4.5 and Comparative Example was added to the cream. The texture of these particles, the smoothness when spread on the skin, and the odor after aging at 60°C for 72 hours were obtained, and the results shown in Table 5 were obtained. .

Example 11 A fragrance-free emulsion was prepared with the formulation (parts by weight) shown in Table 6, and the organopolysiloxane/polyoxyalkylene copolymer obtained in Examples 2, 3.5 and Comparative Example 1 was added to it. 2.0 parts by weight was added, and the stability after 240 hours at 40°C, smoothness when spread on the skin, and 6
When we examined the odor after aging at 0℃ for 72 hours,
The results shown in Table 6 were obtained.

Claims (1)

[Claims] 1. General formula▲ Numerical formula, chemical formula, table, etc.▼ (Here, R^1 is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, and R^2 is a Carbon number 1-30
unsubstituted or substituted monovalent hydrocarbon group, l is 2 to 4, n is 3 to 100, m is 2 or 3, a, b are 0.01<a≦
1. A cosmetic material characterized by being mainly composed of an organopolysiloxane/polyoxyalkylene copolymer represented by 1<b≦2.5).