JPH072964A - Cationic polysiloxane polymer - Google Patents

Abstract

PURPOSE:To obtain a cationic polysiloxane polymer useful for obtaining a cosmetic which can give excellent gloss and luster and smooth touch to the hair without making it sticky by using a copolymer comprising a specified polysiloxane-group-containing unsaturated monomer and a cationic unsaturated monomer. CONSTITUTION:The polymer comprises repeating units derived from a polysiloxane-group-containing unsaturated monomer of the formula [wherein R<1> is H, phenyl, 1-10C alkyl, (ether- or ester-terminated) polyoxyalkylene, polyalkylenepolyamine or a fatty acid group; R<2> is vinyl, vinyl(hydroxy)alkylene or (meth)acryloxyalkylene; R<3> is R<1> or R<2>; m is 0-500; and n is 1-50; provided that the polysiloxane moiety may be in the form of a random copolymer or a block copolymer] and repeating units derived from a cationic unsaturated monomer (e.g. dimethylaminoethyl methacrylate).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a cationic polysiloxane polymer useful as, for example, a hair cosmetic polymer.

[0002]

2. Description of the Related Art Conventionally, polysiloxane polymers have been used in various wide applications. Shampoo,
In water and / or ethanol-based hair cosmetics such as rinses, treatments, setting agents and permanent wave liquids, silicone compounds are used for the purpose of imparting gloss, luster and smoothness to the hair.

Further, a cationic polymer compound, an ester compound, a hydrocarbon compound and the like have been used together with these. In particular, silicone compounds and cationic polymer compounds have been widely used in recent years because of their excellent properties.

[0004]

However, in the case of silicone oil-based and ether-modified silicone, when added in a large amount to hair cosmetics or used by the consumer for a long time, the hair becomes sticky or the silicone becomes There is a problem of reverse transfer from hair to hands and clothes. In addition, since silicone compounds that do not have a hydrophilic group such as a polyether group are difficult to remove by ordinary hair washing, if the product containing this is used by a consumer for a long period of time, the hair becomes hydrophobic, and Problems such as permanents sometimes occurred.

Further, when a cationic polymer compound is blended, the hair is temporarily provided with gloss, luster and smoothness, and is easily removed by washing the hair. There is also a problem that the hair becomes sticky when it contains moisture.

The object of the present invention is to solve the above problems and provide a cationic polysiloxane polymer which has both the properties of a cationic compound and the properties of a silicone compound and which can be used in a wide variety of applications such as hair cosmetic polymers. To do.

[0007]

The present inventors have completed the present invention as a result of intensive studies in view of the above problems.

That is, the present invention is a cation characterized by comprising a copolymer of a polysiloxane group-containing unsaturated monomer represented by the following general formula (1) and a cationic unsaturated monomer unit. Polysiloxane polymer:

[Chemical 2] (In the formula, R ¹ is a hydrogen atom, a phenyl group, or a carbon atom number of 1 to 1.
An alkyl group of 0, a polyoxyalkylene group, an ether- or ester-substituted polyoxyalkylene group at the terminal, a polyalkylenepolyamine group, and a fatty acid group, and one or more groups selected from the group consisting of R ² 1 is selected from the group consisting of a vinyl group, a vinylalkylene group, a vinylhydroxyalkylene group, an acryloyloxyalkylene group and a methacryloyloxyalkylene group.
Or unsaturated radicals having two or more radical polymerizability, R ³ is a hydrogen atom, a phenyl group, or a carbon atom number of 1 to 1.
10 alkyl groups, polyoxyalkylene groups, ether-ester substituted polyoxyalkylene groups, polyalkylenepolyamine groups, fatty acid groups, vinyl groups, vinylalkylene groups, vinylhydroxyalkylene groups, acryloyloxyalkylene groups and methacryloyloxy It is an unsaturated group having one or more radically-polymerizable groups selected from the group consisting of alkylene groups, and m is a number from 0 to 500 and n is a number from 1 to 50. However, R ¹ , R ² , and R ³ may be the same or different, and the polysiloxane may have a polymerization type of random or block.

The cationic unsaturated monomer used in the present invention is not particularly limited and any desired one can be used depending on the intended use. Specific examples include acrylic acid or methacrylic acid [hereinafter referred to as (meth ) Acrylic acid]], which is a derivative of (meth) acryloyloxyhydroxypropyltrimethylammonium halide, (meth) acryloyloxyhydroxypropyltriethylammonium halide, etc., and a trialkylamine having 1 to 4 carbon atoms. Monomers derived from epihalohydrin quaternary compounds; (meth) acrylic acid such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide or (meth) acrylamide and alkyl groups Dialky having 1 to 4 carbon atoms Derived from the alkanolamine (meth) amine derivatives of acrylic acid or (meth)
Acrylamide amine derivative; (meth) acrylic acid amine derivative; (meth) acrylamide amine derivative; (meth) acrylic acid amine derivative and (meth)
Neutralized products of amine derivatives of acrylamide with acids such as hydrochloric acid and lactic acid; modified products with alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, ethyl bromide, methyl iodide, ethyl iodide; ethyl monochloroacetate, Examples include modified products of halogenated fatty acid esters such as methyl monochloropropionate; modified products of dialkyl sulfuric acid such as dimethyl sulfate and diethyl sulfate; amine derivatives of allyl compounds such as diallyldimethylammonium halide and diallyldiethylammonium halide.

These cationic unsaturated monomers may be subjected to copolymerization in the form of the above-mentioned monomers, but as an alternative method, they may be subjected to copolymerization in the form of their precursors and then so-called modified. It is also possible to cationize with an agent.

Specifically, for example, it is subjected to copolymerization in the form of dimethylaminoethyl (meth) acrylate as a precursor, and then a denaturing agent (hydrochloric acid, ethyl monochloroacetate, dimethylsulfate, etc.) is added to form a cation. It is also possible to convert.

The amount of the cationic unsaturated monomer used is preferably 5 to 99.9% by weight based on all the monomers. If it is less than 5% by weight, the resulting copolymer tends to be poorly soluble in water and / or ethanol-based solvent, and it may be difficult to wash and remove the hair during washing.

The preferred upper limit can be arbitrarily selected according to the application. That is, when the cationic polysiloxane polymer of the present invention is used as the set polymer, it is generally 5 to 6
0% by weight, and when added for the purpose of exerting a conditioning function, generally 15 to 99.5% by weight is preferable.

The polysiloxane group-containing unsaturated monomer used in the present invention is a monomer having at least one radical-polymerizable unsaturated group and a polysiloxane group in the molecule. It is a compound represented by the following general formula (1):

[Chemical 3] (In the formula, R ¹ , R ² , R ³ , m, and n have the same meanings as described above.)

In the above general formula (1), the sum of m and n is preferably 1 to 501, more preferably m ≠ 0, and most preferably m ≠ 0 and m.
+ N = 4 to 400 is preferable. If the sum of m and n is less than the above, it may be difficult for the polymer obtained by copolymerization to exhibit the advantages of the silicone compound. On the other hand, if it exceeds the above range, the copolymerizability with the cationic unsaturated monomer tends to decrease, which is not preferable.

The amount of copolymerization of the polysiloxane group-containing unsaturated monomer is preferably 0.1 to 95% by weight, more preferably 0.5 to 95% by weight, based on the total monomers. If the amount is less than the above amount, it tends to be difficult for the resulting copolymer to impart excellent gloss and luster to hair, and a smooth feel, and if the amount exceeds the above amount, it is incorporated into a cosmetic composition. In some cases, repeated use over a long period of time tends to cause hydrophobicization of hair.

Specific examples of the polysiloxane group-containing unsaturated monomer include, for example, unsaturated monomers represented by the following general formulas (2) and (3):

[Chemical 4]

[Chemical 5] In the formula, R ^{4 to} R ⁶ and p, q, and r each independently have the following meaning between formulas: R ⁴ = hydrogen atom or methyl group R ⁵ = alkylene group having 1 to 4 carbon atoms R ⁶ = alkylene group having 1 to 10 carbon atoms or phenyl group p = integer of 1 or more q = integer of 1 or more r = integer of 1 or more (however, the sum of p + q + r is 4 to 400)

In the present invention, when the polysiloxane group-containing unsaturated monomer represented by the general formula (1) and the cationic unsaturated monomer are copolymerized, the copolymerization method is a known polymerization method, that is, Known polymerization initiators such as azo-based and / or peroxide-based polymerization initiators in solution polymerization in water or in an organic solvent capable of dissolving both monomers, or bulk polymerization, suspension polymerization, emulsion polymerization, etc. In the presence of a polymerization regulator, if necessary, it is copolymerized by using heat, light or the like.

The cationic polysiloxane polymer of the present invention thus obtained can be widely used in applications requiring both the properties of a cationic compound and the properties of a silicone compound. For example, a polymer for hair cosmetics. Known shampoo, conditioner, treatment,
In a composition such as a set agent, a permanent wave liquid,
It can be added and used in a ratio of 0.1 to 10% by weight.

The hair cosmetics used additionally may be in any form such as liquid, cream, emulsion and gel. Further, it may be used in combination with a conventionally used known natural polymer, natural modified polymer, or synthetic polymer.

Hair cosmetics in which the cationic polysiloxane polymer of the present invention is used include aerosol hair sprays, pump hair sprays, foam hairs for the purpose of maintaining (setting) the hair shape. Spray, hair mist, set lotion, hair styling gel, hair liquid, hair cream, hair oil, etc.
Shampoo, conditioner, treatment liquid, permanent liquid, which is added for the purpose of repairing hair loss and providing conditioning functions such as easiness of cohesion,
Permanent wave liquid etc. can be mentioned.

[0022]

The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples. Example 1 A five-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen introducing tube, and a stirrer was used as a compound represented by the general formula (2) as a polysiloxane group-containing unsaturated monomer (R ⁴ =
Methyl group, R ⁵ = propylene group, R ⁶ = methyl group, p + r
= 90, q = 1) 30 parts by weight, 70 parts by weight of dimethylaminoethyl methacrylate as a cationic unsaturated monomer, and 200 parts by weight of absolute ethanol are added, 1 part of azobisisobutyronitrile is added, and a nitrogen stream is added. The mixture was heated under reflux at 80 ° C. for 6 hours for polymerization. Next, a 50% anhydrous ethanol solution of dimethylsulfuric acid in an equimolar amount to the added dimethylaminoethyl methacrylate was dropped into a five-necked flask with a dropping funnel, and further heated under reflux at 80 ° C under a nitrogen stream for 6 hours to perform a cationization reaction. And a cationic polysiloxane polymer having the following structural formula (hair cosmetic polymer)
Got (1):

[0023]

[Chemical 6] In the formula, Me is a methyl group, p + r = 90,
j: k = 1: 104. The repeating units represented by j and k are random. X is 1 or 0
And y is also 1 or 0, but x ≠ y.

Example 2 Reaction was carried out in the same manner as in Example 1 except that the polysiloxane group-containing unsaturated monomer was 50 parts by weight and the cationic unsaturated monomer was 50 parts by weight. A polysiloxane polymer (hair cosmetic polymer) (2) was obtained.

Example 3 Reaction was carried out in the same manner as in Example 1 except that the polysiloxane group-containing unsaturated monomer was changed to 5 parts by weight and the cationic unsaturated monomer was changed to 95 parts by weight. A polysiloxane polymer (hair cosmetic polymer) (3) was obtained.

Example 4 Reaction was carried out in the same manner as in Example 1 except that the polysiloxane group-containing unsaturated monomer was changed to 70 parts by weight and the cationic unsaturated monomer was changed to 30 parts by weight. A polysiloxane polymer (hair cosmetic polymer) (4) was obtained.

Example 5 Reaction was carried out in the same manner as in Example 1 except that the polysiloxane group-containing unsaturated monomer was changed to 95 parts by weight and the cationic unsaturated monomer was changed to 5 parts by weight. A polysiloxane polymer (hair cosmetic polymer) (5) was obtained.

Example 6 The polysiloxane group-containing unsaturated monomer in Example 1 was a compound represented by the general formula (3) (R ⁶ = methyl group, p + r = 9).
A reaction was performed in the same manner as in Example 1 except that 0 and q = 1) to obtain a cationic polysiloxane polymer (hair cosmetic polymer) (6).

Example 7 A cationic polysiloxane polymer (hair cosmetic polymer) (7) was prepared in the same manner as in Example 1 except that dimethylaminoethyl acrylate was used as the cationic unsaturated monomer. Got

Example 8 Reaction was carried out in the same manner as in Example 1 except that methyldiallylamine was used as the cationic unsaturated monomer.
A cationic polysiloxane polymer (hair cosmetic polymer) (8) was obtained.

Example 9 In a five-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen introducing tube and a stirrer, a compound represented by the general formula (2) as a polysiloxane group-containing unsaturated monomer ( R ⁴ =
Methyl group, R ⁵ = propylene group, R ⁶ = methyl group, p + r
= 90, q = 1) 30 parts by weight, 70 parts by weight of dimethyldiallylammonium chloride as a cationic unsaturated monomer, and 200 parts by weight of absolute ethanol are added, and 1 part by weight of azobisisobutyronitrile is added, The mixture was heated under reflux at 80 ° C. under a nitrogen stream for 6 hours for polymerization to obtain a cationic polysiloxane polymer (hair cosmetic polymer) (9).

Example 10 The reaction was performed in the same manner as in Example 9 except that the polysiloxane group-containing unsaturated monomer was changed to 50 parts by weight and the cationic unsaturated monomer was changed to 50 parts by weight. To obtain a polysiloxane polymer (hair cosmetic polymer) (10).

Example 11 The reaction was carried out in the same manner as in Example 9 except that the polysiloxane group-containing unsaturated monomer was changed to 70 parts by weight and the cationic unsaturated monomer was changed to 30 parts by weight. To obtain a polysiloxane polymer (hair cosmetic polymer) (11).

Example 12 In Example 9, the polysiloxane group-containing unsaturated monomer was a compound represented by the general formula (3) (R ⁶ = methyl group, p + r = 9).
The reaction was performed in the same manner as in Example 9 except that 0 and q = 1) to obtain a cationic polysiloxane polymer (hair cosmetic polymer) (12).

Example 13 In Example 9, a polysiloxane group-containing unsaturated monomer was prepared by the following formula.

[Chemical 7] The reaction was performed in the same manner as in Example 9 except that the compound shown in 1 was used to obtain a cationic polysiloxane polymer (hair cosmetic polymer) (13).

Example 14 In Example 9, the polysiloxane group-containing unsaturated monomer was a compound represented by the general formula (3) (wherein R ⁶ = methyl group, p
The reaction was performed in the same manner as in Example 9 except that + r = 300 and q = 1) to obtain a cationic polysiloxane polymer (hair cosmetic polymer) (14).

Reference Example Using the hair cosmetic polymers obtained in Examples 1 to 14, a cosmetic composition having the following composition was prepared and their foaming property, conditioning property, and stickiness were evaluated according to the following criteria. ,evaluated. The results are shown in Table 1: Superior to general-purpose products: ○ Equivalent to general-purpose products: △ Inferior to general-purpose products: ×

Shampoo Composition A Sodium polyoxyethylene lauryl ether sulfate 15% by weight Coconut oil fatty acid diethanolamide 3% by weight Hair cosmetic polymer 1.5% by weight Fragrance 0.2% by weight Purified water balance Total 100% by weight

Shampoo Composition B Sodium lauryl sulfate 15% by weight Coconut oil fatty acid diethanolamide 3% by weight Hair cosmetic polymer 1.5% by weight Fragrance 0.2% by weight Purified water balance Total 100% by weight

Shampoo composition C C _14- Sodium olefin sulfonate 15% by weight Coconut oil fatty acid diethanolamide 3% by weight Hair cosmetic polymer 1.5% by weight Fragrance 0.2% by weight Purified water balance Total 100% by weight

Shampoo composition D Lauroyl sarcosine ethanolamine salt 15% by weight Coconut oil fatty acid diethanolamide 3% by weight Hair cosmetic polymer 1.5% by weight Fragrance 0.2% by weight Purified water balance Total 100% by weight

Rinse composition Stearyl trimethyl ammonium chloride 1.5 wt% Cetanol 2 wt% Hair cosmetic polymer 0.2 wt% Perfume 0.2 wt% Purified water balance Total 100 wt%

Hair oil composition Octamethylcyclotetrasiloxane 40% by weight Hair cosmetic polymer 8% by weight Absolute ethanol balance Total 100% by weight

[0044]

[Table 1] Comparative Example 1: Dimethylpolysiloxane Comparative Example 2: Polymethacryloyloxyhydroxypropyltrimethylammonium chloride

[0045]

The effect of the present invention is to provide a cationic polysiloxane polymer having both the properties of a cationic compound and the properties of a silicone compound, which can be used in a wide variety of applications. In particular, when the cationic polysiloxane polymer of the present invention is blended into cosmetics as a hair cosmetic polymer, it imparts excellent gloss and luster to the hair without stickiness and a smooth feel, and accumulates even after repeated use for a long period of time. There is no problem, and there is no problem in blending with cosmetics.

Claims (1)

[Claims] 1. A cationic polysiloxane polymer comprising a copolymer of a polysiloxane group-containing unsaturated monomer represented by the following general formula (1) and a cationic unsaturated monomer unit. : [Chemical 1] (In the formula, R ¹ is a hydrogen atom, a phenyl group, or a carbon atom number of 1 to 1.
An alkyl group of 0, a polyoxyalkylene group, an ether- or ester-substituted polyoxyalkylene group at the terminal, a polyalkylenepolyamine group, and a fatty acid group, and one or more groups selected from the group consisting of R ² 1 is selected from the group consisting of a vinyl group, a vinylalkylene group, a vinylhydroxyalkylene group, an acryloyloxyalkylene group and a methacryloyloxyalkylene group.
Or unsaturated radicals having two or more radical polymerizability, R ³ is a hydrogen atom, a phenyl group, or a carbon atom number of 1 to 1.
10 alkyl groups, polyoxyalkylene groups, ether-ester substituted polyoxyalkylene groups, polyalkylenepolyamine groups, fatty acid groups, vinyl groups, vinylalkylene groups, vinylhydroxyalkylene groups, acryloyloxyalkylene groups and methacryloyloxy It is an unsaturated group having one or more radically-polymerizable groups selected from the group consisting of alkylene groups, and m is a number from 0 to 500 and n is a number from 1 to 50. However, R ¹ , R ² and R ³ may be the same or different, and the polymerization type of polysiloxane may be random or block.)