JPS6157803B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Background of the Invention] The present invention relates to a resin composition having a zwitterion that exhibits an excellent hair styling effect and is particularly suitable for use as an aerosolized hair styling agent.

Conventionally, nonionic, anionic or cationic resin compositions have been used as hair styling resin compositions. Nonionic resins include polyvinyl methyl ether, polyvinyl pyrrolidone, etc.
Polyvinylpyrrolidone-based resins are easily affected by humidity conditions, and while the film before moisture absorption is hard and prone to flaking, it becomes extremely flexible and causes blocking when exposed to high temperatures and humidity, causing hair to stick to each other. There is a risk that loading and brushing will become impossible. Furthermore, in polyvinyl methyl ether systems, the influence of humidity is even more significant.

Examples of anionic resins include copolymer resins containing vinylcarboxylic acids such as acrylic acid and methacrylic acid as ionic groups, which are currently the mainstream resins for hair styling. This anionic resin is less affected by humidity and exhibits better performance than nonionic resins, but its anionic nature means that it has a weak affinity for hair, and on the other hand, the film must be hard to enhance the hair styling effect. It won't be, but
This may cause a flaking phenomenon. Furthermore, since it is anionic, the addition of cationic substances is restricted, and there is also concern about the solidification phenomenon caused by rinse agents during hair washing.

Cationic resins have a greater affinity for hair than the former two, but like nonionic resins, they are susceptible to humidity conditions. Furthermore, since it is cationic, there are concerns about toxicity and skin irritation, and the addition of anionic substances is restricted, and the solidification phenomenon caused by shampoo (anionic) during hair washing is also a problem.

The inventor of the present application has already disclosed in Japanese Patent Application Laid-Open No. 1983-1971 that an excellent hair styling (hair fixing) resin composition can be obtained by using a resin containing amphoteric ions.
As disclosed in Publication No. 9732, in this case as well, if a sodium salt or potassium salt of halogenated acetic acid is used when modifying a copolymer, a precipitate may be formed during the modification, and this precipitate may be For the sake of
The properties of the film are not necessarily good, and the hair styling aerosol container tends to corrode easily.

[] Summary of the Invention As a result of various studies to solve the above-mentioned problems, the present inventors have developed an excellent hair styling product ( The present invention was achieved by discovering that a resin composition (for hair fixation) can be obtained.

That is, the hair styling resin composition of the present invention comprises polymerizable vinyl monomers having the following general formula or
60% by weight, 30 to 70% by weight of a polymerizable vinyl monomer having the following general formula, and 0 to 50% by weight of another polymerizable vinyl monomer in a hydrophilic solvent,
The copolymer resin is modified with a sodium salt or potassium salt of halogenated acetic acid, the resulting precipitate is filtered, and if necessary, the copolymer resin is further treated with an ion exchange resin.

In these formulas, R ₁ , R ₅ and R ₆ are each a hydrogen atom or a methyl group, R ₂ is an alkylene group having 1 to 4 carbon atoms, and R ₂ and R ₄ are each 1
an alkyl group with ~18 carbon atoms, R ₇ is 1
A saturated or unsaturated alkyl or cycloalkyl group having up to 18 carbon atoms, and A represents an oxygen atom or an NH group.

According to the present invention, a resin composition having properties particularly suitable for use as an aerosolized hair styling agent is provided. That is, the present composition is soluble in water or a hydrophilic organic solvent, and solutions obtained using these solvents exhibit good solubility in common propellants. Furthermore, the resin in the present invention can be easily washed away with a hair detergent.

In addition to the above-mentioned general features, the hair styling resin composition according to the present invention has the following features.

(1) It has a strong affinity for hair, has excellent hair styling effects despite the flexibility of the film, and does not cause flaking.

(2) No blocking feeling even under high temperature and high humidity conditions.

(3) Despite the film's hygroscopic properties, it has excellent hair styling effects under high temperature and humidity conditions. In addition, this moisture-absorbing effect produces an antistatic effect on the hair, making it difficult for dirt and the like to adhere to it.

(4) No shock phenomenon occurs when any charged substance is added, and no solidification occurs even when anionic or cationic active agents are used during hair washing.

(5) Excellent compatibility with additives. In particular, it has excellent compatibility with anionic activators and cationic activators.

(6) Very low toxicity and skin irritation.

(7) It has a nice texture and feels very natural.

(8) Corrosion of the hair conditioner aerosol container does not occur.

[] Detailed description of the invention 1 Polymerizable vinyl monomer Examples of monomers having the general formula include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, N,N-dimethylethylmethacrylamide, etc. Examples of monomers having the general formula include 4-vinyl-pyridine, which is used in an amount of 20 to 60% by weight based on the total monomers. The usage of these monomers is 20
If the amount is less than % by weight, the resulting copolymer film will be poorly soluble in water, making it difficult to wash the hair. on the other hand
When the amount exceeds 60% by weight, the hygroscopicity increases, and the resulting copolymer film exhibits a blocking feeling, has poor hair styling ability, and has reduced solubility in propellants.

Examples of monomers having the general formula include stearyl (meth)acrylate, lauryl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, allyl methacrylate, ethyl (meth)acrylate, 2-ethylhexyl acrylate, etc. are used in a proportion of 30 to 70% by weight based on the total monomers. If the amount of this monomer used is less than 30% by weight, the resulting copolymer will have insufficient solubility in propellants. In addition, the copolymer's hygroscopicity increases, causing the film to have a blocking feel and resulting in poor hair styling ability. On the other hand, if it exceeds 70% by weight, the solubility of the copolymer film in water decreases, and there is a risk that the film will not easily separate from the hair during hair washing.

If desired, other polymerizable vinyl monomers can be added to the copolymer composition in order to impart appropriate flexibility and appropriate hardness to the resulting film.

Examples of other polymerizable vinyl monomers include acrylonitrile, diacetone acrylamide, acrylamide, styrene, chlorostyrene, vinyltoluene, vinyl acetate, hydroxyalkyl (meth)acrylate, polyethylene glycol or polypropylene glycol, and (meth)acrylic Examples include esters with acids, N-vinylpyrrolidone, etc., and are used in a proportion of 0 to 50% by weight. Further, by adding chlorstyrene or the like, solubility in propellants can be improved. That is, these monomers are used as necessary to maintain the overall balance of the copolymer.

Two or more of the above monomers can also be used in combination.

2. Polymerization Each of the above monomers is copolymerized in a hydrophilic solvent.
Aliphatic alcohols having 50 carbon atoms or mixtures thereof, hydrous alcohols such as 95% ethyl alcohol are used.

Polymerization is carried out using a conventional solution polymerization method, for example, by dissolving each monomer in the above-mentioned solvent, adding a polymerization initiator, and heating and stirring under a nitrogen stream. Preferred examples of the polymerization initiator include peroxides such as benzoyl peroxide and lauroyl peroxide, and azo compounds such as azobisisobutyronitrile.

3. Modification A halogenated acetate salt is added to the copolymer solution obtained above, and modification, that is, an amphoteric reaction is carried out under stirring in a conventional manner. As the halogenated acetate as an amphoteric agent, sodium salt or potassium salt of halogenated acetic acid is used. It can be obtained by neutralizing it inside. Further, other commonly used amphoteric agents may be used in combination.

It is also possible to modify the monomer having the general formula or before polymerizing it.

In any case, the amount of the amphoteric agent used is 70 to 130%, preferably 80 to 120% of the theoretically required amount, that is, equimolar to the monomer having the general formula or
Used within the range of

4. The denaturation produces salts and a precipitate in the solution. This precipitate can be removed by filtration. It is also possible to remove it by other commonly used methods such as centrifugation.

5 Ion exchange resin treatment The solution after the above treatment usually contains 0.1 to 1% by weight.
Contains some salt. If necessary, the ash content can be reduced to 0.1% by weight or less by further treating it with an ion exchange resin using a batch method or a flow tube method.

6 Usage form The resin composition of the present invention can be used as it is for hair styling, but in particular, it can be used in water-soluble solvents such as aliphatic alcohols having 1 to 4 carbon atoms, dioxane, methyl ethyl ketone, acetone, methyl cellosolve, and ethyl cellosolve. It is preferable to dissolve it in a liquid and pressurize it into a container together with a propellant to use it as an aerosolized hair styling agent. Usable propellants include common propellants, such as freon, butane gas, halogenated hydrocarbons, and petroleum-based liquefied gas. As other additives, since the resin is amphoteric, any charged substance may be added, such as higher alcohol esters of higher fatty acids, plasticizers such as glycerin and polyethylene glycol, appropriate fragrances, and polishes. Addition of additives, colorants, hair nutrients, etc., does not cause deterioration of the additives or the resin itself. An example of a common hair spray composition is as follows.

Weight% Propellant (Freon) Approximately 60 Resin 2-10 Ethanol 37-34 Polishing agent (PEG compound) Approximately 1 Fragrance, etc. Some amount In addition, the zwitterionic resin in the present invention can be used in setting lotions, hair lotions, hair liquids, It can also be used in shampoos, conditioners, hair creams, etc.

Example 1 90 parts of dimethylaminoethyl methacrylate, 70 parts of butyl methacrylate, and lauryl methacrylate were placed in a 5-necked flask equipped with an electric current cooler, dropping funnel, thermometer, nitrogen purging glass tube, and stirring device.
40 parts and 200 parts of ethanol were added, 1.2 parts of α,α'-azobisisobutyronitrile was added, and the mixture was heated under reflux at 80°C under nitrogen atmosphere to carry out polymerization for 4 hours.

Next, add 32 parts of caustic potassium dissolved in 80 parts of ethanol to a solution of 50 parts of monochloroacetic acid dissolved in 30 parts of ethanol, and neutralize the resulting suspension of monochloroacetic potassium salt in ethanol using a dropping funnel. dripped into the flask. Furthermore, under a nitrogen stream,
The amphoteric reaction was carried out by keeping it at 80°C for 4 hours.

The resulting viscous suspension was filtered with a pressure filter (manufactured by Nippon Senzo Kikai Co., Ltd.) to remove the precipitate.

The liquid was a viscous transparent solution, and the ash content was 0.5% by weight.

Next, regenerated cation exchange resin (Diaion
PK-220 (after regeneration, the inside of the system was washed with ethanol) was filled with 300gr. The mixture was passed through a column, and then passed through a column filled with 300g of regenerated anion exchange resin (Diaion PA-416, the inside of which was washed with ethanol after regeneration). The ash content after the ion exchange resin treatment was less than 0.1% by weight, and the Cl ^- concentration was 50 ppm.

Add and dissolve 90 parts of ethanol to 6 parts of the solution obtained in this way, and add trichlorofluoromethane to this.
120 parts were added and filled into a sealed container to make a hair lacquer.

When you spray this hair lacquer on your hair,
No blocking occurred even under high temperature and high humidity, showing good setting power, and a natural texture was achieved without flaking due to brushing. Furthermore, even when stored in a tin can at 45°C for 6 months, no corrosion was observed on the inner surface of the can.

Comparative Example 1 Except for not performing filtration and ion exchange treatment,
A resin solution obtained in exactly the same manner as in Example 1 had an ash content of 2% and a Cl ^- concentration of 2000 ppm.

When this resin solution was used as a hair lacquer in the same manner as in Example 1, the resulting film lacked transparency and smoothness, and a blocking phenomenon occurred.

Furthermore, when the tin can was left at 45°C for two months, the inner surface of the can was corroded.

Example 2 In the same manner as in Example 1, 90 parts of diethylaminoethyl methacrylate, 70 parts of butyl methacrylate,
Example 40 parts of lauryl acrylate were copolymerized in ethanol, modified with potassium monochloroacetate, the resulting suspension was filtered under pressure, and further ion-exchanged with a cation exchange resin and an anion exchange resin. Similar to the product obtained in step 1, there was no blocking even under high temperature and high humidity, showing good setting power, and there was no flaking due to brushing, allowing a natural texture to be set.

Example 3 In the same manner as in Example 1, 90 parts of vinylpyridine,
70 parts of butyl methacrylate and 40 parts of lauryl methacrylate are polymerized in a 1/1 mixed solvent of ethanol/isopropanol, a modification reaction is carried out with monochloroacetic acid sodium salt, and the resulting suspension is filtered under pressure to obtain a product. This product showed good performance as a setting agent.

Example 4 In the same manner as in Example 1, 40 parts of dimethylaminoethyl methacrylate and 60 parts of methyl methacrylate were added.
100 parts of lauryl methacrylate were copolymerized in ethanol, subjected to a modification reaction with potassium monochloroacetate, and the resulting suspension was filtered under pressure.
Those treated with ion exchange using a cation exchange resin or an anion exchange resin showed good performance as a setting agent. Also, it was easily removed by washing with warm water and shampoo.

Example 5 In the same manner as in Example 1, 120 parts of dimethylaminoethyl methacrylate, 30 parts of cyclohexyl methacrylate, 20 parts of stearyl methacrylate, and 30 parts of butyl methacrylate were copolymerized in ethanol, and the mixture was modified with potassium monochloroacetate. The obtained suspension was subjected to pressure filtration and ion exchange treatment and showed good results as a setting agent.

Comparative Example 2 In the same manner as in Example 1, 20 parts of dimethylaminoethyl methacrylate and 60 parts of methyl methacrylate were added.
When 120 parts of butyl methacrylate were copolymerized in ethanol, denatured with potassium monochloroacetate, and the resulting suspension was subjected to pressure filtration and ion exchange treatment, there was a lot of flaking. It was also difficult to remove.

Comparative Example 3 In the same manner as in Example 1, 140 parts of dimethylaminoethyl methacrylate, 20 parts of 2-ethylhexyl methacrylate, and 40 parts of stearyl methacrylate were copolymerized in ethanol, and the resulting suspension was denatured with potassium monochloroacetate. Those that have been subjected to overpressurization and ion exchange treatment have a strong blocking force.
Furthermore, when 90 parts of ethanol was added to 6 parts of this solution to dissolve it, and 120 parts of trichlorofluoromethane was added thereto, the polymer precipitated at 5° C., resulting in insufficient stability.

Claims (1)

[Scope of Claims] 1 20 to 60% by weight of a polymerizable vinyl monomer having the following general formula or, 30 to 70% by weight of a polymerizable vinyl monomer having the following general formula, and other polymerizable vinyls. 0 to 50% by weight of monomers are copolymerized in a hydrophilic solvent and modified with sodium or potassium salts of halogenated acetic acid, the resulting precipitate is filtered and, if necessary, further treated with an ion exchange resin. A hair styling resin composition containing a treated copolymer resin. (In the above formula, R ₁ , R ₅ and R ₆ are each a hydrogen atom or a methyl group, R ₂ is an alkylene group having 1 to 4 carbon atoms, and R ₃ and R ₄ are each having 1 to 18 carbon atoms. Alkyl group, R ₇ is a saturated or unsaturated alkyl group or cycloalkyl group having 1 to 18 carbon atoms, A is an oxygen atom or NH group)