JP2978423B2 - Hair treatment composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hair treatment composition, and more particularly to a hair treatment composition containing an amino group-containing organopolysiloxane which does not generate an amine odor with time.

[0002]

Technical background of the invention and its problems Amino-modified silicone has an amino group in the molecule, so it has an affinity for proteins on the hair surface and chemically adsorbs to form a persistent film on the hair surface. I do. Therefore, a conditioning effect superior in water resistance and hair wash resistance can be imparted as compared with the conventional silicone oil. The result is better combing, faster drying, reduced static electricity generation during brushing, reduced hair dryer usage time for hair styling, and the stickiness, resin stickiness, and glossiness associated with hairspray sets. The effect is improved. However, the amino group-containing silicone has a problem in that it has an amine odor and is therefore difficult to use for hair treatment.

[0003]

An object of the present invention is to solve such disadvantages and to provide a hair treatment composition containing an amino group-containing organopolysiloxane which does not generate an amine odor with time.

[0004]

The present inventors have conducted intensive studies to achieve the above object, and as a result, focused on a polymerization catalyst for an amino group-containing organopolysiloxane, and obtained an amino group-containing organopolysiloxane polymerized with a quaternary phosphonium compound. Siloxane has been found to be capable of suppressing amine odor over time, and has completed the present invention. That is, the present invention is 100 parts by weight of a mixture of an organosiloxane containing no silane and amino group containing organosiloxane or amino group containing i) amino group, _{^{b) R 3 4 P + (OR}} 4) - ( provided that Wherein R ³ is a substituted or unsubstituted monovalent hydrocarbon group,
R ⁴ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) or a reaction product of the quaternary phosphonium compound and a siloxane compound ;
A general formula prepared by heating and reacting a mixture consisting of 0.001 to 1 part by weight in terms of the weight of the compound.

[0005]

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(Wherein, R ¹ is a monovalent organic group containing an amino group, and R ² is a monovalent hydrocarbon group having 1 to 8 carbon atoms not containing an amino group or an alkoxy group having 1 to 6 carbon atoms.) , M,
n is a number that satisfies 1.8 <m + n <2.1, where n / m ≧ 3, and an organopolysiloxane containing an average of at least one amino group in a molecule represented by the formula: A composition.

Hereinafter, the present invention will be described in detail. The starting material in the amino group-containing organopolysiloxane used in the present invention is an amino group-containing organosiloxane or a mixture of an amino group-containing silane and an amino group-free organosiloxane. Since all of these siloxanes are advantageous in operation, the degree of polymerization is preferably 100 or less, but they may be any of cyclic siloxane, branched siloxane, and linear siloxane. . The amino group-containing organosiloxane or silane is represented by the general formula (I)

[0008]

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An amino group-containing silane or amino group-containing siloxane having a siloxy unit represented by the following formula: Wherein Z is a hydrogen atom, a phenyl group or a formula

[0010]

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Wherein e is an integer of 1 to 10, R ⁵ is a divalent hydrocarbon group having 1 to ⁶ carbon atoms, and R ⁶ is a monovalent hydrocarbon group having 1 to 8 carbon atoms. And Y is a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, c is 0, 1 or 2, d
Is 0, 1, 2 or 3, provided that 0 ≦ c + d ≦ 3.
Examples of other siloxy units include those represented by the following formula (II). R ⁷ _k SiO _{(4-k) / 2} (II) Here, R ⁷ is a monovalent hydrocarbon group having 1 to 8 carbon atoms, and k is 0, 1, 2, or 3. Specific examples of such an amino group-containing silane include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, and 3-aminopropylmethyldimethoxysilane. Silane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, aminomethyltrimethoxysilane, aminoethyltrimethoxysilane, aminomethylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl- Examples of 3-aminopropylmethyldimethoxysilane and the like, and examples of the amino group-containing siloxane include those represented by the following formulas, and their molecular structures are cyclic, linear, or branched. You may. Particularly preferred is a siloxane obtained by hydrolyzing and polymerizing only an amino group-containing silane.

[0012]

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Examples of the organosiloxane containing no amino group include those composed of siloxy units represented by the above formula (II), and examples thereof include the following.

[0014]

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The component (a) in the present invention is an aminosiloxane containing an amino group or a mixture of an amino group-containing silane and an amino group-free organosiloxane as described above. The ratio may be determined arbitrarily according to the amount of amino groups to be contained in the target organopolysiloxane, but is preferably based on 100 parts by weight of the amino group-containing organosiloxane or the amino group-containing silane. The aminosiloxane-free organosiloxane is used in an amount of from 100 to 10,000 parts by weight, particularly preferably from 500 to 5,000 parts by weight. Furthermore, in the obtained siloxane, the amino group content is
It is preferable to mix them so as to be 0.01 to 20% by weight, particularly 0.05 to 5% by weight.

Next, the b) quaternary phosphonium compound used in the present invention has a general formula R ³ ₄ P ⁺ (OR ⁴ ) ^- (wherein R ³ is a substituted or unsubstituted monovalent hydrocarbon group,
R ⁴ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), and R ³ is an alkyl group, an aryl group, a cycloalkyl group, an alkenyl group, or a group in which these groups are substituted with a halogen atom or the like. Although what was done is illustrated,
Among them, an alkyl group having 1 to 8 carbon atoms, a phenyl group and a cyclohexyl group are preferable, and an n-butyl group is particularly preferable.
R ⁴ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom.
Such quaternary phosphonium compounds include, for example, tetramethylphosphonium hydroxide, tetra-n-
Examples thereof include butylphosphonium hydroxide, phenyltrimethylphosphonium hydroxide, tetramethylphosphonium methoxide, tetrabutylphosphonium butoxide, butyltricyclohexylphosphonium hydroxide and the like. Particularly, a compound which has been reacted with a siloxane compound and once silanolated is desirable. Examples of the siloxane compound include those similar to the aforementioned organosiloxane containing no amino group. If the basic equilibration catalyst (quaternary phosphonium compound) is added in an amount of less than 0.001 part by weight per 100 parts by weight of the organosiloxane mixture as the component (a), the equilibration reaction of the organosiloxane is slowed down and 1 part by weight. If the amount is more than 0.1 parts by weight, no further effect can be obtained, so the amount may be in the range of 0.001 to 1 part by weight, but the preferable range is 0.01 to 0.05 parts by weight.

The preparation of the organopolysiloxane according to the present invention comprises the above-mentioned (a) a mixture of an organosiloxane containing an amino group or a silane containing an amino group and an organosiloxane containing no amino group,
B) A predetermined amount of a quaternary phosphonium compound or a reaction product of the quaternary phosphonium compound and a siloxane compound is mixed and uniformly mixed, and then heated to carry out an alkali equilibrium reaction. The temperature is preferably 240 ° C. or lower, preferably 80 ° C. to 130 ° C., according to which the equilibration of the amino group-containing organosiloxane proceeds smoothly, and the amino group-containing organopolysiloxane can be easily obtained. However, since the viscosity of the organopolysiloxane can be freely controlled, an industrial usefulness that an amino group-containing organopolysiloxane can be advantageously obtained is provided.

The amino group-containing organopolysiloxane thus obtained does not emit an amine odor over time, and does not emit an amine odor when used as hair cosmetics. There is no. When the composition of the present invention is formulated as a hair conditioner such as a hair rinse, a hair treatment, a hair conditioner, a hair cream, a shampoo, and a hair liquid, the increase in the amine odor with time is small, and the physiological discomfort is small. Has utility. Incidentally, the hair treatment agent of the present invention, if necessary,
As long as the effects of the present invention are not impaired, surfactants, polymer compounds, and other additives generally used in hair cosmetics can be added. Specifically, examples of the anionic activator include linear / branched alkylbenzene sulfonates,
EO / PO addition type alkyl / alkenyl ether sulfate, alkyl / alkenyl sulfate, olefin sulfonate,
Alkanesulfonates, saturated / unsaturated fatty acid salts, EO / PO
Addition type alkyl / alkenyl ether carboxylate, α
-Sulfo fatty acid salts / esters, sulfosuccinic acid type activators, phosphate ester type activators, amino acid type activators, etc.
Nonionic activators include EO / PO / BO-added nonionic activators, higher fatty acid alkanolamides / alkylene oxide adducts thereof, and sugar-based nonionic activators. Cationic activators include dilong chain alkyl quaternary ammonium. Salt, mono long chain alkyl quaternary ammonium salt, di long chain alkyl polyoxyethylene quaternary ammonium salt, mono long chain alkyl polyoxyethylene quaternary ammonium salt, bis (hydroxyalkyl) quaternary ammonium salt, amide / Quaternary ammonium salts having an ester bond and the like, as amphoteric activators, alkylamino oxide, betaine type (for example, carbobetaine, amidobetaine, sulfobetaine, hydroxysulfobetaine, amidosulfobetaine), imidazoline type, amidoamine type And the like. Examples of the polymer compound include a polyvinylpyrrolidone polymer compound, an acidic vinyl ether polymer compound, an acidic acrylic polymer compound, an alkaline acrylic polymer compound, a cationic cellulose derivative, a cationic starch, and diallyl quaternary ammonium. / Acrylamide copolymer, quaternized polyvinylpyrrolidone, polyglycolpolyamine condensate, cationized guar gum, alginic acid derivative, carrageenan, gum arabic, tragacanth gum, cellulose derivative, polyvinyl alcohol derivative, polyvinyl alkyl ether derivative,
Examples include polyethylene oxide derivatives and carboxybetaine-type derivatives. Additives generally used in hair cosmetics include polyhydric alcohols, fats and oils, hydrocarbon oils, alcohols, silicone oils, waxes, wax esters, plant extracts, antioxidants, preservatives,
Examples include vitamins, sequestering agents, pH adjusters, oxidizing agents, reducing agents, dyes, fragrances, and ultraviolet absorbers. In the hair treatment composition of the present invention, the amount of the amino group-containing organopolysiloxane is not particularly limited,
Generally, it is preferably 0.01 to 20% by weight, particularly preferably 0.1 to 10% by weight. Further, in the hair treatment composition of the present invention, the amino group-containing organopolysiloxane has a viscosity
Those having 200 to 20,000 cP, particularly 500 to 5,000 cP are preferred, and those having an amino group content of particularly 0.1 to 2% by weight are preferably used.

[0019]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Synthesis Example 1 N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane 1800 was placed in a 2-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet.
g, and the mixture was heated to 35 ° C. and stirred. Ion exchange water 1
56 g were added dropwise over 30 minutes. After dropping, the temperature was raised to 80 ° C,
The pressure was gradually reduced, and the stirring was continued for 3 hours after the degree of reduced pressure reached 20 mmHg or less, cooled to normal temperature to break the reduced pressure, colorless and transparent, viscosity was 300 cP, and the amino group content was 17.2% by weight.
The amino group-containing organopolysiloxane (synthesis 1) was obtained.

Synthesis Example 2 [(CH) was added to a reactor equipped with a stirrer, a decompression device, a heater, a solvent inlet, a cooler, a receiver, and an inlet for introducing nitrogen through a dehydration tube and a decarbonation tube. ₃ ) ₂ SiO] ₃ 4.8% by weight, [(CH ₃ ) ₂ SiO] ₄ 77.4% by weight, [(CH ₃ ) ₂ SiO] ₅ 17.4% by weight and [(CH ₃ ) ₂ SiO] ₆ 0.4% by weight 136 parts by weight of a cyclic polydimethylsiloxane mixture,
10 parts by weight of an aqueous solution containing 40% by weight of n-butylphosphonium was charged, and stirring was performed while maintaining the temperature at 30 ° C. while feeding a small amount of nitrogen from which water and carbon dioxide had been removed. Under these conditions, the pressure was gradually reduced. After the degree of reduced pressure reached 50 mmHg or less, stirring was continued for 8 hours. After confirming that water did not evaporate from the reactor at all, the mixture was cooled at room temperature to break the reduced pressure to obtain a viscous and transparent liquid phosphonium group-containing polysiloxane (synthetic compound 2). The phosphonium group content of the obtained phosphonium group-containing polysiloxane is 2.2.
% By weight.

Synthesis Example 3 1650 g of octamethylcyclotetrasiloxane was placed in a 2 liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet.
93.5 g, 31.9 g of dimethylpolysiloxane having an average degree of polymerization of 10 whose molecular chain end is blocked with a trimethylsilyl group was charged, heated at 150 ° C. for 30 minutes, refluxed, and dehydrated. Add 23g and with stirring
The equilibration reaction was performed at 110 ° C. for 2 hours. Next, the temperature was gradually raised to 150 ° C. over 1 hour, and then the mixture was heated at 140 to 150 ° C. for 2 hours under a reduced pressure of 10 mmHg to strip off unreacted products. This is a pale yellow transparent liquid, volatile matter (105 ° C x 3 hours) 2.3% by weight, viscosity
720cP, a refractive index of 1.4078, and an amino group content of 0.930% by weight.

Synthesis Example 4 1650 g of octamethylcyclotetrasiloxane was placed in a 2 liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet.
93.5 g, 31.9 g of dimethylpolysiloxane having an average degree of polymerization of 10 in which the molecular chain ends are blocked with trimethylsilyl groups were charged, heated at 110 ° C. for 30 minutes, refluxed, and dehydrated.
1.11 g of (nC ₄ H ₉ ) ₄ POH 40% aqueous solution was added dropwise, and an equilibration reaction was performed at 110 ° C. for 2 hours while stirring. After the reaction,
After the temperature was slowly raised to 150 ° C. over 1 hour, the mixture was heated at 140 to 150 ° C. under a reduced pressure of 10 mmHg for 2 hours to strip unreacted products. As a result, a synthesized product 4 was obtained. This is a pale yellow transparent liquid, 2.5% by weight of volatiles (105 ° C x 3 hours), viscosity 798cP, refractive index 1.4079, amino group content
0.930% by weight.

Synthesis Example 5 1650 g of octamethylcyclotetrasiloxane was placed in a 2 liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet.
93.5 g, 31.9 g of dimethylpolysiloxane having an average degree of polymerization of 10 in which the molecular chain ends are blocked with trimethylsilyl groups were charged, heated at 110 ° C. for 30 minutes, refluxed, and dehydrated.
1.11 g of (CH ₃ ) ₄ NOH 20% aqueous solution was added dropwise, and 9
The equilibration reaction was performed at 0 ° C. for 5 hours. After the reaction is over, 150
After the temperature was slowly raised to 1 ° C. over 1 hour, the mixture was heated at 140 to 150 ° C. for 2 hours under reduced pressure of 10 mmHg to strip unreacted products. As a result, a synthesized product 5 (comparative product) was obtained. This is a pale yellow transparent liquid, volatile matter (105 ℃ x 3 hours)
The content was 2.3% by weight, the viscosity was 720 cP, the refractive index was 1.4078, and the amino group content was 0.930% by weight.

Synthesis Example 6 1650 g of octamethylcyclotetrasiloxane and N-β (aminoethyl) -γ were placed in a 2-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet.
-Aminopropyldimethoxysilane (120 g), 31.9 g of dimethylpolysiloxane having an average degree of polymerization of 10 whose molecular chain end is blocked with a trimethylsilyl group were charged, heated at 110 ° C. for 30 minutes, refluxed, and dehydrated. (C ₄ H ₉ 1.81 g of a ₄ % aqueous solution of ₄ POH was added dropwise, and an equilibration reaction was carried out at 110 ° C. for 2 hours while stirring. After completion of the reaction, the temperature was slowly raised to 150 ° C. over 1 hour, and then 140 to 150 ° C. under a reduced pressure of 10 mmHg for 2 hours.
The unreacted material was stripped by heating at ° C., whereby a synthetic product 6 was obtained. This is a pale yellow transparent liquid, volatile matter (105 ° C x 3 hours) 3.2% by weight, viscosity 580cP, refractive index 1.
At 4075, the amino group content was 0.890% by weight.

Synthesis Example 7 1650 g of octamethylcyclotetrasiloxane was placed in a 2 liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet.
93.5 g, 31.9 g of dimethylpolysiloxane having an average degree of polymerization of 10 and having a molecular chain terminal blocked with a trimethylsilyl group were charged, heated at 140 ° C. for 30 minutes, refluxed, dehydrated, and dried.
Add 0.01 g of OH and 10 g of DMF, and add 140 g
Allowed to react for hours. After the completion of the reaction, 0.03 g of phosphoric acid was added,
Stir for 1 hour, neutralize, then gradually increase the degree of vacuum to 10 mmHg
The mixture was heated at 140 to 150 ° C. for 2 hours under the following reduced pressure, and the unreacted material was stripped.
was gotten. It is a translucent yellow liquid, with volatiles (1
(05 ° C x 3 hours) 2.4% by weight, viscosity 700cP, refractive index 1.4073
And the amino group content was 0.900% by weight.

Examples 1 to 3 and Comparative Examples 1 to 2 Using the above-mentioned compounds 3 to 7 and blending them in the composition shown in Table 1, 40 to 50
C. to prepare an oil rinse.

[0027]

[Table 1]

Next, Examples 1 to 3 obtained as described above,
Each of the oil rinses of Comparative Examples 1 and 2 was placed in a 100 cc glass bottle, sealed, and cured in an oven at 50 ° C. for 2 weeks.
The change in amine odor after that is shown in Table 2.

[0029]

[Table 2]

Examples 4 to 6 and Comparative Examples 3 to 4 Using the above-mentioned Synthetic products 3 to 7 and blending them in the composition shown in Table 3, 40 to 50
The mixture was uniformly dissolved at a temperature of ° C to prepare a hair conditioner.

[0031]

[Table 3]

Next, Examples 4 to 6 obtained as described above,
100cc each of the hair conditioners of Comparative Examples 3 and 4
And sealed in a glass bottle, and cured in an oven at 50 ° C. for 2 weeks. The change in amine odor after that is shown in Table 4.

[0033]

[Table 4]

Examples 7 to 9 and Comparative Examples 5 to 6 Using the above-mentioned Compounds 3 to 7, the compositions shown in Table 5 were blended.
The mixture was uniformly dissolved at a temperature of ° C to prepare a foam treatment (mousse type).

[0035]

[Table 5]

Next, Examples 7 to 9 obtained as described above,
Each of the foamed treatments of Comparative Examples 5 and 6 was 1
It was sealed in a 00 cc glass bottle and cured in an oven at 50 ° C. for 2 weeks. The change in amine odor after that is shown in Table 6.

[0037]

[Table 6]

Examples 10 to 12 and Comparative Examples 7 to 8 Using the above-mentioned synthetic products 3 to 7, the compositions shown in Table 7 were blended to prepare hair rinses. As a preparation method, first, in each composition, was heated and uniformly dissolved at about 50 ° C., and then was added, mixed and made uniform.

[0039]

[Table 7]

Next, Examples 10 to 12 obtained as described above,
Each of the hair rinses of Comparative Examples 7 and 8 was placed in a 100 cc glass bottle, sealed, and cured in an oven at 50 ° C. for 2 weeks. The change in amine odor after that is shown in Table 8.

[0041]

[Table 8]

Examples 13 to 15 and Comparative Examples 9 to 10 The above-mentioned Syntheses 3 to 7 were blended according to the composition shown in Table 9 and uniformly mixed to prepare an oil shampoo.

[0043]

[Table 9]

Next, Examples 13 to 1 obtained as described above were used.
5, 100cc each of the oil shampoos of Comparative Examples 9-10
And sealed in a glass bottle, and cured in an oven at 50 ° C. for 2 weeks. Table 10 shows the change in the amine odor after that.

[0045]

[Table 10]

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) A61K 7/06 A61K 7/11

Claims (1)

(57) [Claims] 1. A a) 100 parts by weight of a mixture of an organosiloxane containing no silane and amino group containing organosiloxane or an amino group containing an amino group, _{^{b) R 3 4 P + (OR}} 4) - ( provided that Wherein R ³ is a substituted or unsubstituted monovalent hydrocarbon group,
R ⁴ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) or a reaction product of the quaternary phosphonium compound and a siloxane compound ;
A mixture of 0.001 to 1 part by weight, calculated as the weight of the compound, is reacted by heating. (Where R ¹ is a monovalent organic group containing an amino group, R ²
Is a monovalent hydrocarbon group having 1 to 8 carbon atoms containing no amino group or an alkoxy group having 1 to 6 carbon atoms, and m and n are n / m
A hair treatment composition comprising an organopolysiloxane containing an average of at least one amino group in a molecule represented by ≧ 3 and a number satisfying 1.8 <m + n <2.1).