JP2000086466A - Oil-in-alcohol type hair-setting agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an oil-in-alcohol type hair-setting agent composition having excellent set-retainability and good feeling and useful for hair cream, styling mixture, etc., by including an oil, a lower alcohol, a specific emulsifier, etc. SOLUTION: The objective agent contains (A) an oil, (B) a lower alcohol, (C) water, (D) an emulsifier comprising one or more kinds of polyether-modified silicones of formula I [A is methyl or the like; B is C3H6O(C2H4O)a(C3H6O)bR'; R' is H or the like; (a) and (b) are each 5-50; R is methyl or the like; (m) is 50-1,000; (n) is 0-40] and (E) one or more kinds of cationic resins produced by copolymerizing 50-90 wt.% of a polymerizable unsaturated monomer of formula II (R1 is H or the like; R2 is a 1-4C alkylene; R3 and R4 are each a 1-4C alkyl; X is O or the like) and 10-50 wt.% of a polymerizable unsaturated monomer of formula III (R5 is H or the like; R6 is a 12-24C alkyl), etc., and modifying the obtained copolymer with a cationizing agent of formula; YE (Y is bromine or the like; E is a 1-12C alkyl or the like).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oil-in-alcohol type hair setting composition, and more particularly to a hair setting agent which imparts excellent gloss to a hair, imparts a smooth feel, and has good holding power. And an oil-in-alcohol type hair setting composition capable of adhering and repairing split ends of hair.

[0002]

2. Description of the Related Art Hair setting agents which have been widely used in the past are obtained by dissolving a film-forming polymer compound in water, a lower alcohol or a mixed solvent thereof. The polymer compound blended here has the effect of fixing the hairs together and holding the set, but the ones that have been used conventionally have stickiness in the process of applying to the hair and drying it. It wasn't smooth. In order to solve such disadvantages, attempts have been made to improve the feel in use by adding oils and fats for cosmetics, surfactants, and the like to the polymer compound. However, a hair setting agent having both sufficiently satisfactory set holding power and use feeling has not yet been obtained.

[0003] In recent years, hair treatment agents containing an amphoteric polymer compound and a cationic polymer (JP-B 2-44446).
And Japanese Patent Publication No. 3-14805, and a hair treatment agent containing an amphoteric polymer compound and an anionic polymer (Japanese Patent Publication No. 3-21524). However, these treatment agents are not satisfactory in terms of non-stickiness and smoothness from application to drying, and also have a feeling of roughened finished hair, which is not satisfactory.

Further, for the purpose of coating the split ends of hair, a hair cosmetic using a combination of a polysiloxane-oxyalkylene copolymer and a silicone derivative has been developed, which has a good feel. And has been reported to be excellent in adhesion of split ends (Japanese Patent Laid-Open No. 6-1).
No. 57247). However, even this method was still incomplete in terms of set holding power and hair smoothness.

[0005] Therefore, the fixing force between the hairs is sufficient,
It is desired to develop a hair setting agent composition which has a resilient and non-sticky coating film, has excellent style holding power, and is non-sticky, smooth and easy to give in the process from application to drying. I was

On the other hand, the present inventors have developed an oil-in-alcohol emulsion composition in which an oil phase is uniformly and stably dispersed in an external phase mainly composed of lower alcohol by using a specific polyether-modified silicone as an emulsifier. (International Publication Number: WO97 / 0288)
8).

[0007]

Under such circumstances, the present inventors have conducted intensive studies and as a result, have found that a specific copolymer has been added to an oil-in-alcohol emulsion composition using the above-mentioned polyether-modified silicone as an emulsifier. It has been found that a hair setting agent composition having both excellent set holding power and good feel can be obtained by using this in combination, thereby completing the present invention.

That is, the present invention provides (a) an oil component, and (b)
(C) water, (d) one or more polyether-modified silicones represented by the following general formula (1) as an emulsifier, and (e) polymerization represented by the following general formula (2) 50 to 90% by weight of a polymerizable unsaturated monomer, 10 to 50% by weight of a polymerizable unsaturated monomer represented by the following general formula (3)
% By weight, and a copolymer obtained by copolymerizing 0 to 25% by weight of another polymerizable monomer copolymerizable with each of the above-mentioned polymerizable unsaturated monomers, to obtain a copolymer represented by the general formula YE [wherein , Y is a bromine atom,
A chlorine atom, an iodine atom or an alkyl sulfate residue (the alkyl group has 1 to 4 carbon atoms), and E is an alkyl group having 1 to 12 carbon atoms, a benzyl group or 1 to 3 carbon atoms. (The alkyl group has 1 to 4 carbon atoms). ] An oil-in-alcohol hair setting composition characterized by comprising one or more cationic resins modified with a cationizing agent represented by the formula:

[0009]

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[In the formula, A represents a methyl group, a phenyl group or B described below, and B represents a general formula: -C ₃ H ₆ O (C ₂ H
_{4 O) a (C 3 H} 6 O) bR '( where, R' is hydrogen atom, an acyl group, and a group selected from the group consisting of alkyl group having 1 to 4 carbon atoms, a is 5 to An integer of 50, b
Is an integer of 5 to 50. ), R is a methyl group or a phenyl group, m is an integer of 50 to 1000, and n is an integer of 0 to 40. However, at least one has a polyoxyalkylene group in the molecule. ]

[0011]

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(Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 4 carbon atoms, R ³ and R ⁴ are each an alkyl group having 1 to 4 carbon atoms,
X is an oxygen atom or an NH group. )

[0013]

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(In the formula, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is an alkyl group having 12 to 24 carbon atoms.)

Next, the configuration of the present invention will be described. The oil-in-alcohol-type hair setting composition according to the present invention is an oil-lower alcohol-water system in which a lower alcohol is present in excess with respect to water, and comprises one or more polyether-modified silicones represented by the general formula (1) or An oil-in-alcohol type hair setting composition comprising a stable cationic oil-in-alcohol emulsion using two or more types and the above-mentioned specific cationic resin.

That is, the oil-in-alcohol type hair setting composition of the present invention is completely different from the conventional emulsification and does not use a hydrophilic nonionic surfactant, but rather uses a polyether-modified silicone which gels when contacted with water. It is a completely new oil-in-alcohol hair setting composition which emulsifies an oil in a high alcohol concentration as the sole emulsifier and further incorporates the cationic resin.

The (a) oil used in the present invention includes:
Liquid paraffin, squalane, lanolin derivatives, higher alcohols, various ester oils, avocado oil, palm oil, tallow, jojoba oil, silicone oil, high molecular silicone rubber,
Examples include various modified silicone rubbers such as amino-modified or ammonium-modified, terpene-based hydrocarbon oils, and the like.
The oil content is 0.5 to 70.0% by weight, especially 1.0 to
50.0% by weight is preferred. If the amount is less than 0.5% by weight, the effect of the present invention, particularly the smoothness, cannot be realized, and
If it exceeds 0.0% by weight, stickiness occurs.

The type of the lower alcohol (b) used in the present invention is not particularly limited, but is preferably methanol or ethanol, and particularly preferably ethanol from the viewpoint of safety. In addition, i-propanol, n-propanol, t-butanol, s-butanol, etc. are too hydrophobic and are difficult to emulsify. The amount of the lower alcohol is preferably at least 3 times (weight ratio) the amount of water in the composition. If the amount of the lower alcohol is less than three times, the entire system is gelled by the polyether-modified silicone,
This is because the viscosity increases and it becomes difficult to emulsify. Further, in view of the difficulty in emulsifying an oil-in-alcohol type at a high alcohol concentration in the prior art, the compounding amount of the lower alcohol is 30.0% by weight or more, more preferably 40.0% by weight or more in the composition. In particular, the importance of the present invention is understood.

The amount of the water (c) used in the present invention is 0.5 to 20.0% by weight, particularly 1.0 to 10.0% by weight.
Is preferred.

The polyether-modified silicone (d) used in the present invention is an organopolysiloxane having a polyoxyalkylene group represented by the general formula (1).

Specific examples of the acyl group of R ′ include formyl group, acetyl group, propionyl group, butyryl group, acryloyl group, benzoyl group, and toluoyl group. Specifically, a methyl group, an ethyl group, an i-propyl group, an n-propyl group,
A t-butyl group and an n-butyl group are exemplified.

In the polyoxyalkylene group,
When a or b is less than 5, the polyether-modified silicone does not show a sufficient surfactant effect, and when a or b exceeds 50, the obtained hair setting composition has a sticky feeling. Will have.

The content of the polyoxyalkylene group is not particularly limited.
It is desirable to have more than% by weight. This is because when the content of the polyoxyalkylene group is 20% by weight or less, the thickening effect of the polyether-modified silicone is significantly reduced.

M is an integer of 50 to 1000;
n is an integer of 0 to 40. This is because when m is less than 50, the emulsion stability is poor, and when m exceeds 1000 and n exceeds 40, the obtained hair setting composition has a sticky feeling. Because it becomes.

The molecular weight of the polyether-modified silicone used in the present invention is not particularly limited, and its viscosity at 25 ° C. is not particularly limited. However, a hair setting agent composition which forms a particularly stable emulsion and has a dry feeling. In order to obtain a product, the polyether-modified silicone used in the present invention has a viscosity in the range of 1,000 to 100,000 mPa · s when a 50% by weight solution of octamethyltetrasiloxane or isoparaffin is used. Preferably, it is The molecular weight is 20,000 or more, preferably 300, from the viewpoint of stability and usability.
The range of 00 to 80000 is preferred.

The amount of the polyether-modified silicone used in the present invention is not particularly limited, but is preferably at least 1.0% by weight, more preferably at least 3.0% by weight. Further, preferably 30.0% by weight or less,
It is more preferably at most 20.0% by weight. In the hair setting composition of the present invention, if the amount of the polyether-modified silicone is less than 1.0% by weight, stable emulsification is difficult, and if it exceeds 30.0% by weight, the hair setting composition This is because the object has a sticky feeling. Such a polyether-modified silicone is known as a gelling agent, and is described, for example, in JP-A-5-311076.

In the present invention, the blending ratio (weight ratio) of the polyether-modified silicone and the lower alcohol is: polyether-modified silicone: lower alcohol = 1: 30 to 5:
It is preferably 5. If the polyether-modified silicone is less than 1/30 of the lower alcohol, it will not function as an emulsifier, and if the lower alcohol is less than the same amount of the polyether-modified silicone, the thickening effect of the polyether-modified silicone will be remarkable and stable. Emulsification becomes difficult.

Next, the cationic resin of the component (e) will be described. The raw material copolymer for obtaining the cationic resin is 50 to 90% by weight, preferably 55 to 85% by weight, of the polymerizable unsaturated monomer represented by the general formula (2), 3) a polymerizable unsaturated monomer represented by 10 to 5
0% by weight, preferably 15 to 45% by weight, and 0 to 25% by weight of another polymerizable unsaturated monomer copolymerizable with each of the above polymerizable unsaturated monomers. It is.

Among the polymerizable unsaturated monomers represented by the above general formula (2), particularly preferred are those wherein R ¹ is a methyl group, R ² is an alkylene group having 2 to 3 carbon atoms, R ³ and R ^{3 Four}
Is a methyl group or an ethyl group, and X is an oxygen atom. Specific examples of the polymerizable unsaturated monomer (2) include, for example, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, And diethylaminopropyl (meth) acrylamide. In addition, "(meth) acrylate" described in this specification
Is a general term for acrylate and methacrylate,
“(Meth) acrylamide” is a general term for acrylamide and methacrylamide (others conform to this).

As described above, the amount of the polymerizable unsaturated monomer (2) used is 50 to 90% by weight, preferably 55 to 85% by weight, based on the total amount of the monomers to be copolymerized. . If the amount is too small, the cationic resin finally obtained becomes sparingly soluble in water, and the removability at the time of hair washing becomes poor, and the cationic resin slips on the hair due to a decrease in cationic performance. Properties, combability, and the effect of imparting a conditioning effect are reduced. Conversely, if the amount used is too large, the resulting cationic resin will have a sticky feeling, or will cause problems such as a reduction in the hair styling effect.

Among the polymerizable unsaturated monomers represented by the general formula (3), particularly preferred are monomers in which R ⁵ is a methyl group and R ⁶ is an alkyl group having 13 to 20 carbon atoms. It is. Specific examples of the polymerizable unsaturated monomer (2) include lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate,
Behenyl (meth) acrylate and the like.

As described above, the amount of the polymerizable unsaturated monomer (3) used is 10 to 50% by weight, preferably 15 to 45% by weight, based on the total amount of the monomers to be copolymerized. . If the amount is too small, the cationic resin finally obtained will be sticky or poor in flexibility. On the other hand, if the amount is too large, the resulting cationic resin becomes sparingly soluble in water, and the washing and removing properties during hair washing deteriorate, and the hair conditioning effect deteriorates.

The polymerizable unsaturated monomers for copolymerization include:
In addition to the polymerizable unsaturated monomers (2) and (3), other polymerizable unsaturated monomers, which are not essential components, can be used. By appropriately selecting the other polymerizable unsaturated monomer to be used, the feel and the like can be adjusted by imparting appropriate flexibility and hardness to the finally obtained cationic resin.

Specific examples of other polymerizable unsaturated monomers that can be used include, for example, methyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth)
(Meth) acryl alkyl esters such as acrylates; acrylonitrile, hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethylene glycol (meth) acrylate, polyethylene glycol ( Meth) acrylate, propylene glycol (meth) acrylate,
1,3-butylene glycol di (meth) acrylate,
(Meth) acrylic derivatives such as diacetone acrylamide; aromatic unsaturated monomers such as styrene, chlorostyrene and vinyltoluene; and vinyl unsaturated monomers such as N-vinylpyrrolidone and vinyl acetate. .

These other monomers are, as described above,
It is not an essential component and its amount is from 0 to 25% by weight based on the total amount of monomers to be copolymerized. If the amount of the other monomer used is too large, the amount of the polymerizable unsaturated monomer (2) or (3) used will be reduced, causing a problem.

The copolymerization of the above-mentioned polymerizable unsaturated monomers (2) and (3) and other polymerizable unsaturated monomers used as required can be performed by a bulk polymerization method, a solution polymerization method, a suspension polymerization method or a suspension polymerization method. It can be carried out by various radical polymerization methods such as a polymerization method and an emulsion polymerization method. A preferred polymerization method is a solution polymerization method,
The polymerizable unsaturated monomer is dissolved in an appropriate solvent, a polymerization initiator is added, and the mixture is heated and stirred under a nitrogen stream to perform polymerization.

The solvent used in this case is water; alcohols such as methanol, ethanol, isopropanol, ethylene glycol and butyl cellosolve; ketones such as acetone and methyl ethyl ketone; hydrocarbons such as hexane and toluene; ethyl acetate and butyl acetate. Acetates such as are preferred. These solvents can be used as a mixture of two or more kinds as appropriate.
Examples of the polymerization initiator include peroxides such as benzoyl peroxide and lauroyl peroxide, and azo compounds such as azobisisobutyronitrile.

At the time of polymerization, it is general that all kinds and amounts of the monomer and the polymerization initiator are present in the polymerization system from the beginning of the polymerization.
Alternatively, a divided addition method can be used for the amount.
The amount of solvent used is such that the polymer concentration of the resulting copolymer solution is 1
Preferably, the amount is from 0 to 65% by weight.

The molecular weight of the obtained copolymer is preferably in the range of 5,000 to 500,000 in terms of weight average molecular weight.
The molecular weight is controlled by controlling the polymerization conditions such as the polymerization temperature, the type and amount of the polymerization initiator, the amount of the chain transfer solvent such as ethanol and isopropanol, and the amount of the chain transfer agent such as butyl mercaptan and lauryl mercaptan. It can be performed by selection and adjustment.

When the copolymer obtained by the above-mentioned copolymerization is subjected to a modification reaction with a cationizing agent represented by the aforementioned general formula YE, the cationic resin used in the present invention is obtained. Specific examples of the cationizing agent include alkyl halides such as methyl chloride, butyl chloride and ethyl iodide; benzyl halides such as benzyl chloride and benzyl bromide; sulfates such as dimethyl sulfate and diethyl sulfate. Monohalogenated fatty acid esters such as ethyl monochloroacetate, propyl monobromide propionate, and butyl monochloroacetate;

Modification of the copolymer with a cationizing agent, that is, a cationization reaction, is carried out by adding a cationizing agent to a copolymer solution and stirring the mixture at 40 to 100 ° C. under an inert atmosphere, for example, under a nitrogen stream. Heating is carried out at a temperature for 4 to 30 hours.

As described above, the modification with a cationizing agent is generally carried out after copolymerization, and is preferable. However, as an alternative, at the monomer stage, that is, in the above-mentioned general formula (2), Before the polymerization, the polymerizable monomer represented is cationized by reacting with a cationizing agent in advance, and then copolymerized using the cationized polymerizable monomer to form a cationic resin. Can also. The present invention also includes embodiments according to this alternative method. The obtained cationic resin may be a solution of the produced cationic resin as it is, or may be a solid cation after once removing the solvent from the produced solution of the cationic resin solution by evaporating the solvent. A cationic resin may be used, or the solid cationic resin may be used by re-dissolving it in another solvent.

Examples of the cationic resin of the present invention include those disclosed in JP-A-5-310538.

The content of the cationic resin in the hair setting composition of the present invention is 0.1 to 5 as a dry solid component.
It is 0.0% by weight, preferably 1.0 to 30.0% by weight. If the amount of the cationic resin is less than 0.1% by weight, the effect as a setting agent cannot be obtained. If the amount exceeds 50.0% by weight,
This is undesirably applied to the hair in large amounts, causing problems in hair washing.

The oil-in-alcohol type hair setting composition of the present invention may further comprise, in addition to the above essential components, liquid paraffin and squalane, within a quantitative and qualitative range according to the purpose, without impairing the effects of the present invention. , Lanolin derivatives, higher alcohols, various ester oils, avocado oil, palm oil, tallow,
Oils such as jojoba oil, silicone oil, polyalkylene glycol polyether and its carboxylic acid oligoester compounds, terpene hydrocarbon oils, and water-soluble solutions such as ethylene glycol, propylene glycol, 1,3-butylene glycol, glycerin, sorbitol, and polyethylene glycol Moisturizers such as hydrophilic polyhydric alcohols, hyaluronic acid, chondroitin sulfate, and pyrrolidone carboxylate, ultraviolet absorbers, ultraviolet scattering agents, resins such as acrylic resins, silicone resins, polyvinylpyrrolidone, soy protein,
Proteins or proteolysates such as gelatin, collagen, silk fibroin and elastin, preservatives such as ethylparaben and butylparaben, activators such as various amino acids, biotin and pantothenic acid derivatives, γ-oryzanol, dextran sodium sulfate, vitamin E derivatives , Blood circulation promoters such as nicotinic acid derivatives, antiseborrheic agents such as sulfur and thianthol, diluents such as ethanol, isopropanol, tetrachlorodifluoroethane, thickeners such as carboxyvinyl polymer, drugs, flavors, coloring agents, etc. May be appropriately compounded depending on the conditions.

In a particularly preferred embodiment of the oil-in-alcohol hair setting composition of the present invention, since the external phase is alcohol, the composition is hardly foamed, and is aerosol hair spray, pump hair spray, hair mist, set lotion. Liquid or gel-like materials such as hair liquid, hair cream, and hair gel are preferred.

[0047]

The present invention will be described in more detail with reference to the following examples. The present invention is not limited by these. All amounts are by weight. Prior to the examples, production examples of the cationic resin used in the present example will be described.

Preparation Example 1 of a Cationic Resin A five-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a glass tube for nitrogen replacement, and a stirrer was charged with 55 parts of dimethylaminoethyl methacrylate, 15 parts of lauryl acrylate, and cetyl. 20 parts of methacrylate, 10 parts of behenyl methacrylate, and 100 parts of absolute ethanol
Azobisisobutyronitrile (hereinafter referred to as “AI
BN ". ) Add 0.3 part and add 80
The mixture was refluxed at C, and after 2 hours, 0.6 parts of AIBN was added and polymerization was carried out at the same temperature for 6 hours. Next, 53.9 parts of diethyl sulfate (equimolar amount to dimethylaminoethyl methacrylate) and 10 parts of anhydrous ethanol were added thereto.
0 parts were added, and denaturation reaction was further performed at 50 ° C. for 10 hours under a nitrogen stream. Then, the content of ethanol was adjusted to obtain a cationic resin solution having a polymer content of 30%.
The weight average molecular weight of this resin before modification was 120,000.

Preparation Example 2 of a Cationic Resin A flask similar to that of Preparation Example 1 was charged with 85 parts of dimethylaminoethyl methacrylate and 15 parts of stearyl methacrylate.
And 54 parts of anhydrous ethanol, 0.1 part of AIBN was added, and the mixture was refluxed and heated at 80 ° C. in a nitrogen stream. After 2 hours, 0.6 parts of AIBN was added and polymerization was carried out at the same temperature for 6 hours. I let you. Next, 72.8 parts of ethyl monochloroacetate (1.1 times the molar amount with respect to dimethylaminoethyl methacrylate) and 100 parts of absolute ethanol were added thereto, and the mixture was further denatured by heating under reflux at 80 ° C. for 12 hours under a nitrogen stream. I let it. Then, the content of ethanol was adjusted to obtain a cationic resin solution having a polymer content of 25%.
The weight average molecular weight of this resin before modification was 200,000.

Preparation Example 3 of Cationic Resin A flask similar to Preparation Example 1 was charged with 80 parts of dimethylaminoethyl methacrylate and 12 parts of tridecyl methacrylate.
Parts, 8 parts of stearyl acrylate and 400 parts of absolute ethanol, 2.0 parts of AIBN was added, and the mixture was refluxed and heated at 80 ° C. under a nitrogen stream. After 2 hours, 0.6 parts of AIBN was added and the mixture was heated at the same temperature for 6 hours. Polymerized. Then
32.9 parts of butyl chloride (0.7 mole times the amount of dimethylaminoethyl methacrylate) were added, and the mixture was heated under reflux at 80 ° C. under a nitrogen stream to carry out a denaturation reaction for 30 hours.
Then, the ethanol content was adjusted to adjust the polymer content to 30.
%, And passed through a column previously filled with activated carbon for deodorization. Furthermore, the processing solution is put in a flask,
Water was added while ethanol was distilled off to obtain a cationic resin aqueous solution having a polymer content of 35%. The weight average molecular weight of the cationic resin before modification was 6,000.

Preparation Example 4 of Cationic Resin In the same flask as in Preparation Example 1, 70 parts of diethylaminoethyl methacrylate, 5 parts of cetyl acrylate, 10 parts of stearyl methacrylate and 10 parts of N-vinylpyrrolidone
Parts, 5 parts of butyl methacrylate, and 10 parts of acetone
0 parts, and 0.3 parts of AIBN are added.
The mixture was heated under reflux at 0 ° C., and after another 2 hours, 0.1 part of AIBN was added, and a polymerization reaction was carried out at the same temperature for 15 hours under a nitrogen stream.
Then, 68.6 parts of diethyl sulfate (equimolar amount to diethylaminoethyl methacrylate) and 100 parts of absolute ethanol were added, and further added at 50 ° C. under a nitrogen stream at 1 ° C.
The mixture was heated at reflux for 0 hour to perform a denaturation reaction. Ethanol as a solvent was removed from the obtained viscous liquid at 70 ° C. under reduced pressure to obtain a solid. After pulverizing the solid, it was thoroughly washed with diethyl ether and dried again at 70 ° C. under reduced pressure to obtain a solid cationic resin. The weight average molecular weight of this resin before modification was 400,000.

Example 1 Hair Cream (Set Type) (1) Dimethylpolysiloxane (n = 3000) 2.0% by weight (2) Light liquid isoparaffin 30.0 (3) Polyether-modified silicone 20.0 (General In the formula (4), m = 400, n = 10, a = 24, b = 24, where a 50% solution of isoparaffin is used.) (4) Ethanol 37.4 (5) Cationicity obtained in Production Example 3 Resin aqueous solution 8.6 (actually 3.0) (6) Ion-exchanged water 2.0 (7) Suitable amount of fragrance (8) Suitable amount of paraben (9) Suitable amount of antioxidant (Production method) (1), (2), ( While stirring part of (3) and (4) and (6) at room temperature with a homomixer, add the remainder of (4) and the mixture of (5), (7), (8) and (9) and emulsify. To give a hair cream.

[0053]

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Example 2 Styling Mist (1) Dimethylpolysiloxane (6 mPa · s) 4.0% by weight (2) Dimethylpolysiloxane (n = 1000) 4.0 (3) Deionized water 1.0 (4) Ethanol 69.2 (5) Perfume Appropriate amount (6) 2-Hydroxy-4-methoxybenzophenone 0.1 (7) Polyether-modified silicone 5.0 (In the above general formula (4), m = 500, n = 20, a = 40, b = 40, provided that a 50% solution of decamethylcyclopentasiloxane is used. (8) The aqueous cationic resin solution obtained in Production Example 1 16.7 (actually 5.0) (production method) ), Part of (2), (3) and (4), while stirring (7) at room temperature with a homomixer, remove the mixture of (4) and the mixture of (5), (6) and (8). It was added to obtain a styling mist.

Example 3 Aerosol spray (1) Dimethylpolysiloxane (6 mPa · s) 6.0% by weight (2) Dimethylpolysiloxane (100 mPa · s) 1.5 (3) Amino-modified silicone 0.6 (4) Isoparaffin 4.8 (5) Polyether-modified silicone 2.1 (In the general formula (4), m = 300, n = 30, a = 30, b = 30, but a 50% solution of isoparaffin) (6) ) Ethanol 12.0 (7) Perfume suitable amount (8) Cationic resin aqueous solution obtained in Production Example 2 1.2 (actual 0.3) (9) Deionized water 2.8 (10) Liquefied petroleum gas 69 0.0 (Preparation method) (1), (2), (3), (4) and (5) are added to the mixture of (6) and (7), and the mixture is emulsified by stirring with a homomixer. Then (8),
(9) is added to obtain a stock solution for spraying. This undiluted solution is packed in a can, and the valve is opened and (10) is filled.

Example 4 Styling lotion (1) Dimethylpolysiloxane (6 mPa · s) 3.0% by weight (2) Dimethylpolysiloxane (n = 1000) 3.0 (3) Deionized water 1.0 (4) Ethanol 86.9 (5) Perfume Appropriate amount (6) 2-Hydroxy-4-methoxybenzophenone 0.1 (7) Polyether-modified silicone 3.0 (In the above general formula (4), m = 400, n = 10, a = 19, b = 19, but 50% solution of octamethylcyclotetrasiloxane) (8) Solid cationic resin obtained in Production Example 4 3.0 (Production method) (1), (2), While stirring a part of (3) and (4) and (7) at room temperature with a homomixer, add the remainder of (4) and the mixture of (5), (6) and (8) to form a styling lotion. Obtained.

Example 5 Styling Gel (1) Dimethylpolysiloxane (6 mPa · s) 8.0% by weight (2) Dimethylpolysiloxane (n = 2000) 8.0 (3) Ion-exchanged water 3.0 (4) Ethanol 52.6 (5) Perfume appropriate amount (6) Octyl methoxycinnamate 0.1 (7) Polyether-modified silicone 15.0 (In the above general formula (4), m = 300, n = 30, a = 30, b = 30, where 50% solution of decamethylcyclopentasiloxane) (8) Cationic resin solution obtained in Production Example 1 13.3 (actually 4.0) (Production method) (1), (2) ), A portion of (3), (4), and (7) are stirred at room temperature with a homomixer, and the remaining (4) and the mixture of (5), (6), (8) are added for styling. Got a gel.

Example 6 Styling lotion (1) Dimethyl polysiloxane (20 mPa · s) 15.0% by weight (2) Dimethyl polysiloxane (5000 mPa · s) 15.0 (3) Ion exchange water 1.0 (4) Ethanol 33.9 (5) Perfume appropriate amount (6) Octyl methoxycinnamate 0.1 (7) Polyether-modified silicone 15.0 (In the above general formula (4), m = 500, n = 20, a = 40, b = 40, however, 50% solution of isoparaffin) (8) Cationic resin solution obtained in Production Example 2 20.0 (actually 5.0) (Production method) (1), (2), (3) ), A part of (4) and (7) were stirred at room temperature with a homomixer, and the remainder of (4) and a mixture of (5), (6) and (8) were added to obtain a styling lotion. .

Comparative Example 1 Hair Cream (Set Type) (1) Carrageenan 1.0% by weight (2) Polyoxyethylene hydrogenated castor oil (60EO) 1.0 (3) Carboxyvinyl polymer 0.6 (4) Dimethylpoly Siloxane (n = 1000) 5.0 (5) Triethanolamine appropriate amount (pH = 7.5) (6) Glycerin 2.0 (7) Flavor appropriate amount (8) Octyl methoxycinnamate 0.1 (9) Ethanol 18.0 (10) Ion-exchanged water 62.3 (11) Cationic resin solution obtained in Production Example 10.0 (actually 3.0) (Production method) Add (2) and (4) to (6) Emulsify (emulsified parts). After adding (1) and (3) to (10) and dissolving uniformly, (5),
The mixture obtained by adding (7), (8), (9) and (11) was mixed with emulsified parts to obtain a hair cream (set type).

Comparative Example 2 Styling Mist (1) Decamethylcyclopentasiloxane 6.0% by weight (2) Octamethylcyclotetrasiloxane 4.0 (3) Dimethylpolysiloxane (n = 1000) 3.0 (4) 1 3,3-butylene glycol 3.0 (5) Polyoxyethylene hydrogenated castor oil (60EO) 2.0 (6) Ethanol 5.0 (7) Deionized water 67.0 (8) Betained dialkylaminoalkyl acrylate copolymer Combination 10.0 (actually 3.0) (trade name: Yuka Former AM75-SM (manufactured by Mitsubishi Chemical Corporation)) (9) Appropriate amount of fragrance (production method) Dissolve (3) in (1), (2), and ( The mixture was emulsified with the mixture of (4) and (5), and (6), (7), (8) and (9) were mixed to obtain a styling mist.

Comparative Example 3 Set lotion (1) Polyvinylpyrrolidone / vinyl acetate copolymer 5.0% by weight (2) Cetyl-2-ethylhexanoate 1.0 (3) Stearyltrimethylammonium chloride 0.3 (4 ) Ethanol 70.0 (5) Deionized water 23.7 (6) Appropriate amount of perfume (Preparation method) (4), (5) are stirred and mixed, and (1) to (3) and (6) are further dissolved. To get a set lotion.

Comparative Example 4 Hair Cream (Set Type) (1) Dimethylpolysiloxane (n = 3000) 2.0% by weight (2) Light liquid isoparaffin 30.0 (3) Polyether-modified silicone 20.0 (General In the formula (4), m = 400, n = 10, a = 24, b = 24, but a 50% solution of isoparaffin) (4) Ethanol 43.0 (5) Acrylic resin alkanolamine solution (50%) 0 (6) Ion-exchanged water 2.0 (7) Suitable amount of perfume (8) Suitable amount of paraben (9) Suitable amount of antioxidant (Production method) (1), (2), part of (3), (4), and While stirring (6) at room temperature with a homomixer, the remainder of (4), (5), (7), (8), (9)
Was added and emulsified to obtain a hair cream.

Comparative Example 5 Aerosol spray (1) Dimethylpolysiloxane (n = 3000) 0.8% by weight (2) Light liquid isoparaffin 2.0 (3) Polyether-modified silicone 8.0 (the above general formula (4) Where m = 400, n = 10, a = 24, b = 24, but a 50% solution of isoparaffin) (4) Ethanol 17.2 (5) Hydroxypropyl acrylate / butylaminoethyl methacrylate / octyl acrylate Amide copolymer 1.2 (trade name: AMPHOMER LV-71, manufactured by Nippon NSC Ltd.) (6) Ion-exchanged water 0.8 (7) Perfume proper amount (8) Paraben proper amount (9) Antioxidant (10) Liquefied petroleum gas 70.0 (Production method) Add (1), (2), (3), (6) to the mixture of (4) and (7), stir with a homomixer, and emulsify. I do. Then (8), (9)
To obtain a stock solution for spraying. This undiluted solution is packed in a can, and the valve is opened and (10) is filled.

As described above, the one obtained in Examples 1 to 6 and the one obtained in Comparative Examples 1 to 5 were (1) less sticky to dry after coating, and (2) dried after coating. (3) set holding power, and (4) less stiffness of the finished hair. Table 1 shows the results. The evaluation method is as follows.

[Evaluation method] (1) Low stickiness until drying after application A sample of 3 g was applied to a hair strand (4 g) by 20 subjects, the shape was adjusted with a comb, and the stickiness until drying was measured. Sensory evaluation was performed. The evaluation criteria are as follows. ：: very good (the number of subjects who answered good is 18 or more) ○: good (the number of subjects who answered good is 8 or more and less than 18) △: somewhat poor (the number of subjects who answered good) More than 5 and 8
×: poor (less than 5 subjects answered good)

(2) Smoothness after application After drying, 20 test subjects applied a 3 g sample to a hair strand (4 g), adjusted the shape with a comb, and evaluated the smoothness until drying. The evaluation criteria are the same as in the above (1).

(3) Set Retention Force A 0.5 g sample was evenly applied to a hair bundle having a length of 15 cm and a weight of 1 g, wound around a rod having a diameter of 2 cm, and allowed to stand in a high-temperature room at 45 ° C. for 6 hours. And dried. After drying, the rod was removed, and the apparent length (L ₁ ) of the hair bundle was measured.
Next, the hair bundle is hung in a thermostatic chamber at a temperature of 25 ° C. and a humidity of 90%, taken out after 30 minutes, and again taken as the apparent length (L) of the hair bundle.
₂ ) was measured, and the set retention effect was determined by the following equation.

[0068]

[Formula 1] Set holding force = ｛(15−L ₂ ) / (15−
L ₁ )｝ × 100 (%)

Therefore, the closer this value is to 100, the higher the set holding effect. ◎: very good (set holding power 80% or more) ○: good (set holding power 50% or more, less than 80%) △: slightly bad (set holding power 30% or more, less than 50%) ×: bad (set holding power) Less than 30% force)

(4) Low Roughness of Finished Hair The dryness of the hair strands dried in (1) was sensory evaluated by 20 subjects. Evaluation criteria are
Same as (1) above.

[0071]

[Table 1] ────────────────────────────── (1) (2) (3) (4) ──── ────────────────────────── Example 1 ◎ ◎ ◎ ◎ Example 2 ◎ ◎ ◎ ◎ Example 3 ◎ ◎ ◎ ◎ ◎ Example 4 ◎ ◎ ◎ ◎ Example 5 ◎ ◎ ◎ ◎ ────────────────────────────── Comparative Example 1 ○ ◎ △ ◎ Comparative Example 2 ○ ◎ ◎ △ Comparative Example 3 ○ ◎ ○ ○ Comparative Example 4 △ × △ × Comparative Example 5 × △ × △ ──────────────────────── ──────

As is evident from the results in Table 1, the oil-in-alcohol type hair setting composition of the present invention was excellent in set holding power, non-sticky, and had a smooth and good feel.

[0073]

As described above, the oil-in-alcohol type hair setting composition of the present invention is non-greasy and easy to give in the process from application to dry finish, and the finished hair is smooth and non-sticky. It has a good feel and excellent set holding power.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C083 AB051 AC012 AC022 AC101 AC102 AC122 AC212 AC342 AC432 AC482 AC522 AC542 AC692 AD091 AD092 AD132 AD152 AD161 AD162 AD172 AD352 BB11 BB34 CC32 CC33 DD08 DD31 DD41 EE28 EE29

Claims (5)

[Claims] 1. An oil component, (b) a lower alcohol, (c) water, and (d) an emulsifier represented by the following general formula (1):
And (e) 50 to 90% by weight of a polymerizable unsaturated monomer represented by the following general formula (2), represented by the following general formula (3). 10 to 50% by weight of the polymerizable unsaturated monomer obtained, and 0 to 25% by weight of another polymerizable monomer copolymerizable with each of the above polymerizable unsaturated monomers. The copolymer is represented by a general formula YE, wherein Y is a bromine atom, chlorine atom, iodine atom or an alkyl sulfate residue (the alkyl group has 1 to 4 carbon atoms), and E is the number of carbon atoms. 1 to 12 alkyl groups, benzyl groups or alkyl ester residues of fatty acids having 1 to 3 carbon atoms (the alkyl group has 1 to 4 carbon atoms). ] An oil-in-alcohol hair setting composition comprising at least one cationic resin modified with a cationizing agent represented by the formula Embedded image [In the formula, A represents a methyl group, a phenyl group or a later-described B, B has the general _{formula: -C 3 H 6 O (C} 2 H 4 O) a (C 3 H 6
O) bR ′ (wherein, R ′ is a group selected from the group consisting of a hydrogen atom, an acyl group, and an alkyl group having 1 to 4 carbon atoms, a is an integer of 5 to 50, and b is 5 Is an integer of from 50 to 50), R is a methyl group or a phenyl group, and m is from 50 to 50.
It is an integer of 1000, and n is an integer of 0 to 40. However, at least one has a polyoxyalkylene group in the molecule. ] (Wherein, R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 4 carbon atoms, R ³ and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, and X is oxygen. An atom or an NH group.) (In the formula, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is an alkyl group having 12 to 24 carbon atoms.) (2) 0.5 to 70.0% by weight of an oil component
And (b) 30.0% by weight or more of lower alcohol,
(C) 0.5 to 20.0% by weight of water and (d) 1.0 to 30.0% by weight of the polyether-modified silicone,
(E) 0.1 to 5 cationic resin as a dry solid component
The oil-in-alcohol-type hair setting composition according to claim 1, which contains 0.0% by weight. 3. The blending amount of the lower alcohol (b) is as follows:
3. The alcohol-in-alcohol type hair setting composition according to claim 1 or 2, wherein the amount is at least 3 times (weight ratio) the amount of water (c). 4. The weight average molecular weight of the cationic resin is 5,000 in terms of the molecular weight of the copolymer before being modified with the cationizing agent.
The oil-in-alcohol type hair setting composition according to any one of claims 1 to 3, wherein the composition is from 500,000 to 500,000. 5. The compounding ratio (weight ratio) of (d) polyether-modified silicone and (b) lower alcohol is as follows:
The alcohol-in-alcohol hair setting composition according to any one of claims 1 to 4, wherein (b) = 1: 30 to 5: 5.