JPH09183715A - Resin composition for dressing hair and spray for dressing hair - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hair-dressing resin composition exhibiting an excellent hair-dressing effect on the hair also under the environments of a high temperature and a high humidity without generating insolubles also at low temperatures on the treatment of a single liquidized petroleum gas on the formation of an aerosol, and capable of being easily removed on the washing of the hair, and to provide a hair-dressing spray using the same. SOLUTION: This resin composition for hair dressing is obtained by copolymerizing (a) 5-35wt.% of at least a kind of monomer selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid, (b) 5-20wt.% of at least a kind of monomer selected from among the 10-18C aliphatic alcohol esters of acrylic acid and/or methacrylic acid, (c) 5-20wt.% of at least a kind of monomer selected from among the 4-18C aliphatic alcohol esters of acrylic acid and/or methacrylic acid, (d) 40-85wt.% of a monomer consisting of N- tertiary butyl acrylamide, and (e) 0-25wt.% of one or more other vinylic monomers, and subsequently neutralizing the copolymer with a water-soluble organic basic substance.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD [0001] The present invention adheres to hair and exhibits an excellent hair styling effect even in an environment of high temperature and high humidity.
Moreover, the present invention relates to a hair styling resin composition that can be easily washed and removed, and a hair styling spray using the same. Further, the present invention provides
The present invention relates to a hairdressing resin composition having the above-mentioned performance and excellent solubility in liquefied petroleum gas (LPG), and a hairdressing spray using the same.

[0002]

2. Description of the Related Art Nonionic resins, anionic resins and amphoteric resins are conventionally known as hair styling resins. As the nonionic resin, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymer, polyvinyl methyl ether and the like are known. However, the polyvinylpyrrolidone-based film has a large change in physical properties before and after moisture absorption such that the film to be formed is hard before moisture absorption, but suddenly becomes soft when moisture is absorbed, and exhibits a flaking phenomenon during drying. Further, when wet, there is a disadvantage that curls and sets are lost in a short time. Further, a copolymer of vinylpyrrolidone and vinyl acetate does not eliminate the flaking, and the transparency of the film is poor, and the natural appearance of hair cannot be provided. Further, polyvinyl methyl ether is added only as a plasticizer role of polyvinyl pyrrolidone because of its remarkable adhesion.

On the other hand, the anionic resin includes vinyl ether / maleic anhydride half ester, vinyl acetate /
There are crotonic acid copolymers, (meth) acrylic acid / (meth) acrylic acid ester copolymers, etc., and those in which the resin film has water solubility by neutralizing the carboxyl group in the polymer are currently available. It has become the mainstream of hairdressing resins. However, many of the anionic resins generally have low solubility in liquefied petroleum gas, and in the formulation of liquefied petroleum gas alone during aerosolization, insoluble matter may be generated when left at a low temperature. Has a drawback that it may cause a poor injection state or clogging and impair the intended function. In addition, in particular, (meth) acrylic acid / (meth) acrylic acid ester copolymer is
Although it is excellent in retaining the set under high humidity, it has the drawback that it is difficult to wash off easily when washing hair, and it often remains white. In order to solve these problems, JP-A-3-20024 discloses a hairdressing resin composition obtained by copolymerizing an N-substituted acrylamide such as diacetone acrylamide having both hydrophilicity and lipophilicity. . However, when these are copolymerized to have sufficient liquefied petroleum gas (LPG) solubility, the glass transition point of the copolymer tends to be too low.

In the present specification, (meth) acrylic acid is a generic term for acrylic acid and methacrylic acid, and (meth) acrylic acid ester is a generic term for acrylic acid ester and methacrylic acid ester, and further (meth) Acrylamide is a general term for acrylamide and methacrylamide.

[0005]

The problem to be solved by the present invention is as follows.
In the formulation of liquefied petroleum gas alone at the time of aerosolization, insoluble matter does not occur even at low temperatures, it exhibits an excellent hair styling effect in the environment of high temperature and high humidity, and further, it is a hair styling resin that can be easily removed when washing hair. It is intended to provide a composition and a hair styling spray using the composition.

[0006]

The hair styling resin composition according to the present invention comprises: a. 5 to 35% by weight of at least one monomer selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid b. 10 to 10 carbon atoms of acrylic acid and / or methacrylic acid
5-20% by weight of at least one monomer consisting of esters of 18 aliphatic alcohols c. Acrylic acid and / or methacrylic acid having 4 to 8 carbon atoms
5-20% by weight of at least one monomer consisting of an ester of an aliphatic alcohol of d. 40-85% by weight of monomer consisting of N-tert-butyl acrylamide e. It is obtained by copolymerizing a polymerizable monomer composed of 0 to 25% by weight of another vinyl monomer and neutralizing it with a water-soluble organic basic substance.

The monomer a is involved in the hydrophilicity of the resin and the hair washability, and the amount thereof is 5 to 35% by weight, preferably 10 to
30% by weight. When the amount used is less than 5% by weight,
The obtained film is poorly soluble in water and has poor hair washability. On the other hand, when it exceeds 35% by weight, the moisture absorption of the film increases and the adhesiveness becomes remarkable, and the solubility of the resin in liquefied petroleum gas is also poor. Becomes In particular, the amount used is 10
When the content is up to 30% by weight, the film does not feel sticky, can be easily washed off with water, and has good solubility of the resin in liquefied petroleum gas, and therefore, when the resin is formulated into a hair styling spray, precipitation or The separation does not occur, and the formulation can be suitably performed.

As the monomer a, an unsaturated carboxylic acid monomer selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid can be used alone or in combination.

The monomer b is involved in the lipophilicity and flexibility of the resin, and the amount used is 5-20% by weight, preferably 10-1.
5% by weight. When the amount used is less than 5% by weight, the resin has poor solubility in liquefied petroleum gas, and the flaking phenomenon tends to occur during drying. On the other hand, when it exceeds 20% by weight, the resulting film is very soft. , The tackiness increases, and the hair washability also deteriorates. In particular, when the amount used is 10 to 15% by weight, the resin has an appropriate solubility in liquefied petroleum gas, and the film gives a soft feeling without sticking.

Specific examples of the monomer b include decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, ( Meta)
Pentadecyl acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate,
A (meth) acrylic acid ester of an alcohol having a linear or branched chain or an alicyclic hydrocarbon group such as oleyl (meth) acrylate can be used alone or in combination.

The monomer c also contributes to the lipophilicity, softness and hair washability of the resin, and the amount used is 5 to 20% by weight, preferably 10 to 14% by weight. When the amount used is less than 5% by weight, the solubility of the resin in liquefied petroleum gas is poor, while when it exceeds 20% by weight, the washability of the resin becomes poor. In particular, when the amount used is 10 to 14% by weight, a resin having a suitable solubility in liquefied petroleum gas and having a good washability of the film can be obtained.

Specific examples of the monomer c include, for example, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and (meth ) N-hexyl acrylate, n-octyl (meth) acrylate and the like can be used alone or in combination.

Comparing the monomers b and c with each other, the contribution of the resin to the lipophilicity and the effect of impairing the hair washability are greater in the former than in the latter, but the solubility of the resin in liquefied petroleum gas is higher. The former contributes more to the latter than the latter. In order to further increase the solubility of the resin in liquefied petroleum gas, the total amount of the monomer b and the monomer c is preferably 20% by weight or more.

The monomer d contributes to the improvement of the resin setting force at high temperature and high humidity without impeding the solubility of the resin in liquefied petroleum gas, and also contributes to the hardness of the film. The amount used is 40 to 85% by weight, preferably 52 to 70% by weight. When the amount used is less than 40% by weight, there is no improvement in the setting force under high temperature and high humidity. On the other hand, when it exceeds 85% by weight, the film becomes hard and the texture is impaired, and a flaking phenomenon is exhibited. Like In particular, when the amount used is from 52 to 70% by weight, the solubility of the resin in liquefied petroleum gas does not decrease and the washability of the film can be further improved.

The monomer e is involved in the hardness of the film and the solubility of the resin in liquefied petroleum gas, and the amount used is 0 to 25% by weight, and is used as necessary. The amount used is
In order to obtain the desired effect sufficiently, it is desirable that the content is 1% by weight or more, but if it exceeds 25% by weight, the solubility of the resin in liquefied petroleum gas becomes poor.

Specific examples of the monomer e include, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, isopropyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, (meth) acrylamide, acrylonitrile, vinyl acetate, styrene, vinylpyrrolidone, diacetone acrylamide, N -Octyl acrylamide, N-tert-octyl acrylamide, 2-hydroxyethyl (meth) acrylate,
2-Hydroxypropyl (meth) acrylate, glyceryl (meth) acrylate and the like can be used alone or in combination.

Of the monomers e, methyl acrylate,
Ethyl acrylate, propyl acrylate, isopropyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, acrylonitrile, vinylpyrrolidone,
Acrylamide, N-octyl acrylamide, N-tert-octyl acrylamide, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid-2-
When hydroxypropyl or monoglyceryl (meth) acrylate is used, a relatively flexible film can be obtained. Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, ethoxyethyl methacrylate, methacrylamide, vinyl acetate When styrene is used, a film that is harder and less sticky than the former can be obtained.

The above-mentioned copolymerization of the monomers a to e is carried out by ordinary solution polymerization in a hydrophilic solvent, for example, by dissolving each monomer in the hydrophilic solvent, adding a polymerization initiator, and adding nitrogen under a stream of nitrogen. , The boiling point of the solvent or a temperature close to the boiling point of the solvent. The monomers are copolymerized by allowing all species and all amounts thereof to be present from the beginning of the polymerization, or by performing divided addition or continuous dropping with respect to the types and / or amounts of the monomers. The solvent is preferably used such that the solid content in the resin solution is 30 to 60% by weight.

Examples of hydrophilic solvents include water-soluble aliphatic alcohols such as methanol, ethanol, 2-propanol and butanol, hydrous alcohols such as 95% by volume ethanol, acetone, methyl cellosolve,
Ethyl cellosolve, dioxane, methyl acetate, ethyl acetate, dimethylformamide and the like can be used alone or in combination.

As the polymerization initiator, for example, peroxides such as benzoyl peroxide and lauroyl peroxide, 2,2 '
-Azobisisobutyronitrile, 2,2'-azobis-
2-methylbutyronitrile, 2,2'-azobis-2,
4-dimethylvaleronitrile, 1,1'-azobis-1
It is preferable to use azo compounds such as -cyclohexanecarbonitrile, 4,4'-azobis-4-cyanovaleric acid, and 2,2'-azobis- (2-amidinopropane) -dihydrochloride.

The copolymer is made water-soluble by adding a water-soluble organic basic substance to the resin-containing liquid obtained by the above copolymerization. In this case, it is preferable to neutralize the copolymer at a neutralization rate of 50 to 100 mol%.

As the water-soluble organic basic substance, for example, morpholine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 2-amino-2-methyl-1-propanol,
2-amino-2-methyl-1,3-propanediol,
2-Amino-2-ethyl-1,3-propanediol and the like can be used alone or in combination. Of these, when amine is used, a resin composition containing no water is obtained, which is suitable for producing a hair styling spray that repels water.

The resin composition obtained as described above is
The weight average molecular weight of the copolymer is 5,000 to 200,000.
It is preferably in the range of 0, and the hydrophilic solvent liquid obtained by the copolymerization can be used as it is, or can be used as a water-containing solvent system.

The resin composition according to the present invention has 1 to 4 carbon atoms.
Dissolved in a hydrophilic solvent such as aliphatic alcohol, hydrous alcohol such as 95% by volume ethanol, acetone, methyl cellosolve, ethyl cellosolve, dioxane, methyl acetate, ethyl acetate, etc. It can be a hairdressing spray.

As the propellant, liquefied petroleum gas (LPG) containing propane, butane and isobutane as main components, trichloromonofluoromethane (CFC 11), dichlorodifluoromethane (CFC 12) and dichlorotetrafluoroethane (CFC 114). , Halogenated hydrocarbons containing methylene chloride, etc., and dimethyl ether,
Carbon dioxide or the like alone or a mixture thereof can be used. For example, the resin composition has a solid content of 0.5
Dissolve in a hydrophilic organic solvent so as to be ˜15% by weight, and 20-20% by weight of the resulting solution and 80-20% by weight of the propellant are pressure-sealed in a pressure resistant container to obtain a hair styling spray. can do.

The resin composition according to the present invention is dissolved in water and a hydrophilic organic solvent, and various additives for a hair styling agent are added thereto to prepare a hair cream, a hair lotion, a non-gas aerosol (hair mist), a hair foam (hair armose).
It can also be used as a component of hair styling products such as. Further, the resin composition can be mixed with a hair coloring agent as a coloring fixing agent for hair and used for color spray, color foam, mascara and the like. In addition to the above applications, the resin composition can also be suitably used as a coating agent for the skin wound surface such as a film forming component of a facial pack and a barrier forming component of a hand cream.

[0027]

EXAMPLES The present invention will be described below based on examples.
In addition, "%" and "part" described below are based on weight.

Table 1 shows the monomer composition, neutralization ratio and average molecular weight of the resins in Examples 1 to 7 and Comparative Examples 1 to 5 corresponding thereto, and Table 2 shows the resin composition of each resin composition shown in Table 1. Performance evaluations such as aerosol stability, curl retention, flaking, smoothness, film properties and feel will be described. Production of resin composition in each Example and Comparative Example,
The preparation and performance evaluation of the hairdressing spray are carried out by the following methods.

[Production of Resin Composition] A 1-liter four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen displacement tube, and a stirrer was charged with 200 parts of the polymerizable monomers a to e, 100 parts of ethanol, and initiation of polymerization. 0.5 to 4 parts of the agent is added, and polymerization is carried out for 5 hours under reflux (about 80 ° C.) under a nitrogen stream. After polymerization, the mixture is cooled, an ethanol solution of a water-soluble organic basic substance is added at 50 ° C., and diluted with ethanol so that the solid content is 50%.

[Preparation of hair styling spray] Using the resin compositions (solid content: 50%) of the examples and comparative examples, three types of formulations A to C having the following compositions (unit:%) were prepared. A hairdressing spray was prepared by enclosing in a pressure resistant glass bottle for aerosol.

[0031]

Liquefied petroleum gas here is propane 25%
And butane 75%, about 3.0 Kg / at 20 ° C
cm ² was used.

[Performance Evaluation] (1) Aerosol Stability (Compatibility of Resin with Propellant) Hair styling sprays A to C obtained by the preparation of the hair styling spray were left in a freezer at -10 ° C for 24 hours. The state of the solution was evaluated as follows. ○: transparent, △: slightly cloudy, ×: separated

(2) Setting power (curl retention) Hair having a length of 22 cm and a weight of about 2 g is washed with a commercial shampoo, treated with a commercial rinse, air-dried, and 1 is applied to the lower end of the hair.
A 0 g clip was attached and attached to a motor rotating at 30 rpm. Next, while rotating the hair, about 15c
Spray a hairdressing spray evenly from a distance of m for 10 seconds, immediately spread the adhered droplets with a finger, wind it on a rod of about 1.2 cm in diameter, and fix it with a clip. For 30 minutes, cool it well in a desiccator, untwist it in a spiral and attach it to a vertically graduated glass plate at 30 ° C, 95%
R. H. The hair was allowed to stand in a thermo-hygrostat regulated to 10 and the tip position of the hair after 10 hours was recorded, and the curl retention was measured based on the following formula.

Curl retention (%) = {(L-Lt
) / (L−L0)} × 100

L: Length when the test hair is extended Lt: Tip position of the test hair after leaving for 10 hours in a thermo-hygrostat L0: Tip position of the test hair before being put in the thermo-hygrostat

(3) Flaking The amount of resin dropped off when combing the hair prepared in the same manner as in the evaluation of the set strength was evaluated as follows. ○: No dropout, △: Some dropout, ×: Many dropouts

(4) Smoothness The degree of difficulty in combing when evaluating flaking was evaluated as follows. ○: Easy combing, △: Somewhat difficult combing, ×: Comb does not pass

(5) Film property A predetermined amount of the solution before being aerosolized is taken on a glass plate and spread with a glass rod or the like so that the diameter becomes about 2 cm. The glass plate was placed at 20 ° C. and 60% R. H. It is left to stand in the atmosphere for 24 hours and dried at 60 ° C. for 1 hour. Regarding the detergency, the glass plate was immersed in an aqueous solution of 0.5% commercial shampoo at 40 ° C., and the dissolved state of the film was evaluated as follows. ◯: Melted within 1 minute, dissolved within 1 minute or more and 5 minutes or partially left, x: Remained after 5 minutes or more
H. The sample was left to stand for a whole day and night in a thermo-hygrostat regulated at 1, and then evaluated with the touch of a finger as follows. ○: No stickiness, △: slightly sticky, ×: much sticky

(6) Feeling As in the case of the evaluation of the set force, the sensory evaluation when the prepared hair was touched with the hand was evaluated as follows. ◯: Natural touch with dry touch, Δ: Roughness or stickiness, X: Roughness or stickiness

[0041]

[Table 1]

The weight average molecular weight in Table 1 was obtained by preparing a tetrahydrofuran solution such that the solid content of each resin composition was 10 mg / ml, and using a GPC measuring device "SHODEX SYSTEM 11" manufactured by Showa Denko KK Then, the measurement was performed under the following conditions. The conditions are as follows: sample solution: 100 μl, elution solvent: tetrahydrofuran, flow rate: 1.0 ml / min, column: HSG-60S,
40S, 20S, 15S (manufactured by Shimadzu Corporation) in series,
Detector refractive index: (1/64) 256 mV, measurement temperature: 4
5 ° C.

[0043]

[Table 2]

[0044]

As described above, the hairdressing resin composition according to the present invention can be easily aerosolized, and in particular, because of its excellent solubility in liquefied petroleum gas, it is insoluble at low temperature even in the case of liquefied petroleum gas alone. Does not produce a thing. In addition, the resin composition or a film formed by a hairdressing spray using the resin composition has no problems of adhesion and flaking, is excellent in smoothness, and exhibits excellent setting force even under high temperature and high humidity, Moreover, it has an excellent hair styling effect such as not impairing the feel, and can be easily washed and removed.

Claims (4)

[Claims] 1. A copolymerization of the following polymerizable monomers a to e,
A hairdressing resin composition neutralized with a water-soluble organic basic substance. a. 5 to 35% by weight of at least one monomer selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid b. 10 to 10 carbon atoms of acrylic acid and / or methacrylic acid
5-20% by weight of at least one monomer consisting of esters of 18 aliphatic alcohols c. Acrylic acid and / or methacrylic acid having 4 to 8 carbon atoms
5-20% by weight of at least one monomer consisting of an ester of an aliphatic alcohol of d. 40-85% by weight of monomer consisting of N-tert-butyl acrylamide e. Other vinyl monomers 0-25% by weight 2. The hairdressing resin composition according to claim 1, wherein the amount of the monomer c is 10 to 14% by weight. 3. The hairdressing resin composition according to claim 1, wherein the amount of the monomer d is 52 to 70% by weight. 4. A hair styling spray comprising the hair styling resin composition according to claim 1.