JP2596549B2 - Method for producing resin for hair styling - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a water-soluble zwitterionic resin exhibiting an excellent hair-styling effect. The hairdressing resin obtained by the method of the present invention is suitable for use in the form of an aerosol.

(Prior art)

It is well known that hair is fixed with resin to give a desired shape. The hairdressing resin should be water-soluble so that the resin can be removed by washing the hair.

As such a hairdressing resin, nonionic, anionic and cationic resins are conventionally used. However, conventional resins are not always fully satisfactory.

That is, the nonionic resin is easily affected by humidity conditions, the film is hard at low humidity and easily causes a flaking phenomenon. Phenomenon is likely to occur.

Anionic resins are less susceptible to humidity and exhibit better properties than nonionic resins.However, because they are anionic, their affinity for hair is weak. However, this may cause a flaking phenomenon and a sense of strangeness.

Cationic resins have excellent affinity for hair, but are more susceptible to humidity than nonionic resins, and are not generally used as hair styling resins.

The use of a resin having an amphoteric ion to obtain an excellent resin composition for hair styling has already been disclosed by the present inventors in JP-B-55-17009 and JP-B-61-57803.
No. in the publication. For example, Japanese Patent Publication No. 61-57803 discloses 20 to 60% by weight of a polymerizable vinyl monomer having the following general formula I or II, and 30 to 70% by weight of a polymerizable vinyl monomer having the following general formula III. , And 0-50% by weight of other polymerizable vinyl monomers are copolymerized in a hydrophilic solvent and modified with a sodium or potassium salt of a halogenated acetic acid, and the resulting precipitate is removed, if necessary. Furthermore, a hair styling resin composition containing a copolymer resin treated with an ion exchange resin has been proposed.

(Wherein 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, R ₃
And R ₄ represents an alkyl group having 1 to 18 carbon atoms, R ₇ represents a saturated or unsaturated alkyl group or cycloalkyl group having 1 to 18 carbon atoms, and A represents an oxygen atom or an NH group. [Problems of the prior art] The nitrogen (N) atom of the unit of the amphoteric copolymer resin based on the monomer represented by the above formula I or II is amphoteric with an equimolar modifier according to the examples. Therefore, it is impossible to arbitrarily control the water solubility to water resistance of a film obtained by blending a pair of components, such as a cationic resin or an anionic resin, with the copolymer resin. However, the materials to be treated were limited, and the resulting film was somewhat soft.

[Specific means to solve the problem]

In the present invention, when producing an amphoteric ionic resin, an ethylenically unsaturated monomer having an acidic group is present as a constituent component of the amphoteric ionic copolymer resin.

[Constitution of the Invention] In the present invention, the following monomer compositions (I) to (IV) are copolymerized in a hydrophilic solvent, and the resulting copolymer is equimolar to the monomer of (I). And a method for producing a hairdressing resin having a weight average molecular weight of 5,000 to 200,000, which is modified with an alkali metal salt, an ammonium salt or an amine salt of a halogenated acetic acid.

(III) Ethylenically unsaturated monomer having an acidic group 3 to 25
% By weight (IV) Ethylenically unsaturated monomer other than the above (I) to (III) 0 to 25% [However, the total of the monomer composition of (I) to (IV) is 100% by weight. In the above formulas, R ^{1 to} R ⁵ and A each independently represent the following meanings between the formulas.

R ¹ = hydrogen atom or methyl group R ² = alkylene group having 1 to 4 carbon atoms R ³ and R ⁴ = hydrogen atom or alkyl group having 1 to 4 carbon atoms R ⁵ = alkyl group or alkenyl group having 1 to 24 carbon atoms A = O or NH. Monomer (I) The monomer (I) is an acrylic acid or methacrylic acid represented by the general formula (I) (hereinafter referred to as (meth) acrylic acid or methacrylic acid (hereinafter referred to as (meth) acrylic acid))
Is a derivative of In the formula, each of the substituents has the meaning described above, but R ¹ is methyl, R ² is C _{2 to} C ₃ , R ³ and R ⁴ are C ₁ to
It is generally preferred that C ₂ and A are 0.

Specific examples of the monomer (1) include, for example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminoethyl (meth)
There are acrylamide and diethylaminopropyl (meth) acrylamide.

The amount of the monomer (I) used is 15 to 65% by weight, preferably 20 to 50% by weight, based on all monomers. If it is less than 15%, the film of the final amphoteric copolymer is hardly soluble in water, and it is difficult to wash and remove it during hair washing. In addition, the affinity for hair, which is characteristic of the copolymer being zwitterionic, is reduced, resulting in the occurrence of flaking phenomena, reduced antistatic effects and reduced natural hand of hair. And the like. On the other hand, if the amount of the monomer (I) exceeds 65% by weight, the film of the copolymer will exhibit a blocking feeling, the set power will be inferior, and the solubility of the propellant in aerosolization will decrease. I do.

In the present invention, the amounts of the monomers (I) to (IV) relate to the monomer composition based on the weight of all the monomers used, but the polymerization rate during copolymerization is substantially 100% ( If so, this composition is substantially the same as the monomer unit composition of the copolymer before amphoteric.

Monomer (II) The monomer (II) is an acrylate or methacrylate represented by the general formula (II) (hereinafter, both are collectively referred to as “(meth) acrylate”), Preferably, R ¹ is methyl; R ⁵ is C ₁ -C ₁₈ .

Specific examples of the monomer (II) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and oleyl (meth) acrylate.

The amount of the monomer (II) used is 10 to 80% by weight, preferably 20 to 65% by weight, based on all monomers. If the amount is less than 10%, the strength of the obtained film is insufficient, and the It will not be able to withstand the use as. If it exceeds 80% by weight, the film becomes hardly soluble in water, making it difficult to remove the film during washing.

Monomer (III) Specific examples of the ethylenically unsaturated monomer having an acidic group include methacrylic acid, acrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, vinyl acetic acid, crotonic acid and the like. Examples include carboxylic acid monomers and phosphoric acid monomers such as acid phosphooxyethyl (meth) acrylate and acid phosphooxypropyl (meth) acrylate.

The amount of the monomer (III) used is 3 to 25
% By weight, preferably 5 to 20% by weight. If the amount is less than 3% by weight, the water solubility and water resistance of the obtained resin film cannot be arbitrarily adjusted, and the amphoteric resin obtained cannot have the above-mentioned properties as an anionic resin. If the content exceeds 25% by weight, the obtained resin cannot have the general characteristics as the above-mentioned zwitterionic resin.

The monomer (III) may be partially or completely neutralized with a basic compound corresponding to each of them in advance at the monomer stage, and the neutralization may be carried out after the copolymerization and after the modification reaction. The resin may be partially or completely neutralized with a basic compound.

Specific examples of the basic compound include, for example, lithium hydroxide,
Potassium hydroxide, ammonia, ethanolamine, 2-
Amino-2-methyl-1-propanol, 2-amino-
2-ethyl-1,3-propanediol, laurylamine and the like.

Monomer (IV) An ethylene monomer other than the above monomers (I) to (III) in order to give the final amphoteric copolymer film appropriate flexibility and moderate hardness to change the feel. Can be copolymerized.

Specific examples of the monomer (IV) include, for example, styrene, chlorostyrene, vinyltoluene, acrylonitrile, vinyl acetate, (meth) acryloxypropyltrimethoxysilane, N-vinylpyrrolidone, hydroxyethyl or propyl (meth) Examples include acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and acrylamide.

The amount of the monomer (IV) used is 0 to 25 with respect to all the monomers.
% By weight, preferably 0 to 15% by weight.

The monomers (I) to (IV) can be used in each of these groups.

Polymerization Each of the above monomers is copolymerized in a hydrophilic solvent.

Here, “hydrophilic solvent” means that the solubility in water is 10
[G / 100 g water / 25 ° C.] or more means an organic solvent.

Specific examples of hydrophilic organic solvents suitable for use in the present invention include, for example, aliphatic mono- to tetra-hydric alcohols having 1 to 4 carbon atoms, especially mono- to di-hydric alcohols, especially monohydric alcohols, for example. Methanol, ethanol, isopropanol and the like, and dihydric alcohols such as ethylene glycol and the like, as well as ethyl cellosolve, butyl cellosolve, dioxane, methyl acetate, dimethylformamide and the like.

The “hydrophilic solvent” may be in a water-containing state. The degree of water content is free from the viewpoint of the solvent for polymerization, as long as all the monomers used are dissolved at a predetermined concentration. A specific example of the water-containing hydrophilic organic solvent is 95% ethanol.

The polymerization is carried out by a usual solution polymerization method, for example, a method comprising dissolving each monomer in the solvent, adding a polymerization initiator, and heating and stirring under a nitrogen stream. As the polymerization initiator, for example, peroxides such as benzoyl peroxide and lauroyl peroxide, and azo compounds such as azobisisobutyronitrile are preferable. Usually, all kinds and total amounts of the monomers are present from the beginning of the polymerization, but it is also possible to carry out divided additions with respect to the kind and / or the amount of the monomers. The amount of the solvent used was such that the concentration of the produced copolymer solution was 20%.
Preferably, it is about 65% by weight.

Amphoterization Halogenated acetate is added to the copolymer thus obtained in one or more portions, and the mixture is heated at a temperature of about 70 to 90 ° C. under an inert atmosphere, for example, with appropriate stirring under a nitrogen stream. Denaturation by heating for about 4 to 10 hours,
That is, an amphoteric reaction is performed.

As the halogenated acetate of the amphoteric agent, the halogenated acetic acid is converted to a basic compound such as ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, mono- or /
And di- or / and / or triethanolamine, mono-
Or / and / or di- or / and tripropanolamine, 2-amino-2-methyl-1-propanol, 2-
It is a salt obtained by neutralization using amino-2-methyl-1,3-propanediol, benzylamine, morpholine, laurylamine, cyclohexylamine or the like alone or in combination. The halogen of the halogenated acetic acid is chlorine, bromine, or iodine, with chlorine being typical.

The amount of the halogenated acetate to be used is the theoretically necessary amount for the monomer (I), ie, an equimolar amount of 95 to the monomer (I).
Used in the range of ~ 110%.

Post-treatment When the amphoteric agent is an alkali metal salt of halogenated acetic acid,
With the progress of the amphoteric ionization reaction, inorganic salts such as alkali halides (specifically, for example, potassium chloride, sodium bromide, etc.) are precipitated. If necessary, this by-product inorganic salt is centrifuged. Separation is carried out by any means available for separation, filtration or other solid-liquid separation. Further, if necessary, the inorganic salt remaining after dissolution is removed by treating with an ion exchange resin.

Usage Form The copolymer resin thus obtained can be used as a hair styling agent or a hair styling resin component as it is when obtained as a solution or after removing the solvent.

A preferred mode of use of the resin obtained by the method of the present invention is that the solution is pressurized and sealed in a container together with a propellant, injected into the atmosphere from a valve, and applied to the hair in the form of an aerosol.

It is known to apply a hairdressing resin to hair in the form of an aerosol, and the resin of the present invention may be similarly used by being enclosed in an aerosol dispenser. Accordingly, a solvent for an amphoteric copolymer, preferably a hydrophilic solvent (as defined above), for example, an aliphatic alcohol, an ether such as dioxane, a ketone such as methyl ethyl ketone, acetone or ether alcohol as described above as a solvent for polymerization. Such as methyl cellosolve, ethyl cellosolve and others, and propellants such as those commonly used, such as fluoro or fluorochloroalkanes (known as "Freon"), other halogenated hydrocarbons, hydrocarbons such as Butane gas, propane gas,
Pressurized in a conventional aerosol dispenser with other petroleum liquefied gases and the like, and with appropriate additives or auxiliaries.

In this case, known additives such as higher alcohol esters of higher fatty acids, plasticizers such as glycerin and polyethylene glycol (PEG), and appropriate additives such as fragrances, polishes, coloring agents, and hair nourishes are required. Can be added accordingly.

An example of a general hair spray composition is as follows.

Weight% propellant (CFC) Approx. 60 Resin 2-10 Ethanol 37-34 Polishing agent (PEG-based compound) Approx. , Shampoo, rinse, hair cream, hair treatment and the like. The term "for hair styling" in the present invention means such hair-related applications.

〔Example〕

Example 1 In a five-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen glass tube, and a stirrer, 35 parts of dimethylaminoethyl methacrylate and methyl methacrylate were added.
30 parts, 30 parts of lauryl methacrylate, 5 parts of lithium methacrylate and 100 parts of ethanol were added, and 0.6 part of α, α'-azobisisobutyronitrile was added.
Polymerization was carried out by refluxing at 4 ° C. for 4 hours. Next, a solution prepared by dissolving 21 parts of monochloroacetic acid in 122 parts of ethanol was added to 2-solution.
After adding 27 parts of amino-2-ethyl-1,3-propanediol to neutralize monochloroacetic acid, this solution was added to the flask using a dropping funnel. Furthermore, under nitrogen stream for 6 hours,
After the amphoteric reaction was carried out at 80 ° C., ethanol was added to prepare a resin solution containing 30% by weight of the active ingredient.

The molecular weight of the copolymer was 61,000. Next, 6 parts of the solution thus obtained was dissolved by adding 24 parts of ethanol, and then 45 parts of dichlorodifluoromethane was added, and the mixture was filled in a closed container to form a spray.

When these sprays were sprayed on the hair, blocking and flaking did not occur, a good setting force of a natural texture was observed, and compatibility with the propellant and film performance were excellent (see Table 1). 2 In the same five-necked flask as in Example 1, 30 parts of diethylaminoethyl methacrylate and 30 parts of methyl methacrylate were added.
Parts, tridecyl methacrylate 30 parts, 4-vinylpyridine 5 parts, potassium acrylate 5 parts, and ethanol 50
Add α, α'-azobisisobutyronitrile 0.3
The mixture was refluxed and heated at 80 ° C. under a nitrogen atmosphere to carry out polymerization for 6 hours.

Next, 14.5 parts of 2-amino-2-methyl-1-propanol was added to a solution obtained by dissolving 15 parts of monochloroacetic acid (equimolar amount to 30 parts of diethylaminoethyl methacrylate) in 140 parts of ethanol. This solution was added dropwise to the flask using a dropping funnel, and a denaturation reaction was performed in the same manner as in Example 1 to obtain an ethanol solution containing 30% by weight of the active ingredient.

 The molecular weight of the copolymer was 120,000.

When the solution thus obtained was evaluated as a spray in the same manner as in Example 1, good performance was exhibited (see Table 1).

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 (however, dimethylaminoethyl methacrylate was 10 parts as monomer (I),
30 parts of monomer (III)) and then 6 parts of monochloroacetic acid (equimolar amount to 10 parts of dimethylaminoethyl methacrylate) dissolved in 65 parts of ethanol were added with 2-amino-
After 5.7 parts of 2-methyl-1-propanol was added to neutralize monochloroacetic acid, the solution was dropped into a flask with a dropping funnel, and amphoteric reaction was carried out in the same manner as in Example 1. Then, ethanol was added. The active ingredient was adjusted to 30% by weight. The molecular weight of the copolymer was 52,000.

50 parts of the solution thus obtained was taken, and 0.4 part of lactic acid and 0.9 part of ethanol were added.

This solution was operated in the same manner as in Example 1, and a spray was prepared and evaluated. As a result, it was found that the detergency was insufficient, the set force was insufficient, and there was also a problem with flaking (see Table 1).

Comparative Example 2 As in Example 1, the initial monomer composition was 95 parts of dimethylaminoethyl methacrylate (80 parts as monomer (I) and 15 parts as monomer (III)) and 5 parts of methyl methacrylate. The polymerization was carried out, and then 45 parts of 2-amino-2-methyl-1-propanol were added to a solution of 48 parts of monochloroacetic acid (equimolar amount to 80 parts of dimethylaminoethyl methacrylate) in 190 parts of ethanol, and 45 parts of monochloroacetic acid were added. After neutralizing the acetic acid, this solution was dropped into the flask with a dropping funnel, and subjected to an amphoteric reaction in the same manner as in Example 1.
Ethanol was added to adjust the active ingredient to 30% by weight. The molecular weight of the copolymer was 79,000.

50 parts of the resin solution thus obtained was added, and 0.65 part of lactic acid and 1.5 parts of ethanol were added.

This solution was operated in the same manner as in Example 1 to prepare and evaluate a spray. As a result, it was found that the compatibility with the propellant and the setting force were insufficient, and there were also problems with blocking and the like (Table 1). reference).

Comparative Example 3 Polymerization was carried out in the same manner as in Example 1 except that the initial monomer composition was changed to 10 parts of dimethylaminoethyl methacrylate, 60 parts of methyl methacrylate, and 30 parts of stearyl methacrylate, and then 7.5 parts of sodium monochloroacetate (dimethylaminoethyl methacrylate) (Equimolar amount to 10 parts) in 80 parts of ethanol was dropped into the flask using a dropping funnel.

Further, an amphoteric reaction was carried out at 80 ° C. for 8 hours under a nitrogen stream.

The obtained viscous liquid was subjected to excess and ion exchange treatments in the same manner as in Example 2 to obtain a 30% ethanol solution of the active ingredient. The molecular weight of the copolymer was 74,000.

This solution was operated in the same manner as in Example 1 to prepare a spray, which was evaluated. As a result, it was found that the cleaning property and the set force were insufficient, and there was a problem in flaking. Also, no change in detergency was observed by addition of an acid.

In addition, the performance of the resin shown in the table was evaluated as follows. ◎ indicates extremely good, は indicates good, Δ indicates insufficient, and × indicates poor.

(1) Compatibility with propellant In a pressurized container, 60 parts of F ₁₁ / F ₁₂ = 20/80 (weight ratio) freon gas is added to 40 parts of an alcohol solution containing 5% by weight (dry basis) of a resin. The polymer precipitation temperature when cooled is measured.

(2) Film properties The above solution is sprayed on a glass plate, left in the atmosphere at 20 ° C. and 60% RH for 24 hours, and evaluated visually and by finger.

The detergency is evaluated from the state of film dissolution at each time when the glass plate is immersed in warm water containing 0.2% shampoo at 40 ° C.

(3) Set force: The solution was sprayed on hair of 23 cm and 2 g for 10 seconds, wound around a curler having a diameter of 1.2 cm, dried, hung under an atmosphere of 30 ° C. and 90% RH, and measured for curl retention.

(4) Flaking Evaluate the amount of release resin when combing the prepared hair in the same manner as in the evaluation of the set force.

(Effects) According to the present invention, an amphoteric resin having properties suitable for use as an aerosol hair styling agent is provided. In other words, the copolymer resin obtained by the method of the present invention can be used to neutralize an acidic group portion derived from an ethylenically unsaturated monomer having an acidic group, which is present as a constituent component, with a basic compound at an arbitrary ratio. By doing so, the water solubility and water resistance of the resulting copolymer resin film can be arbitrarily adjusted.

Further, by neutralizing an acidic group present as a constituent component by an arbitrary ratio with a basic compound, the resulting amphoteric ionic resin can also have properties as an anionic resin and improve the hardness of the film. And so on.

The hairdressing resin obtained by the method of the present invention has the following general characteristics as amphoteric ion resin in addition to the above characteristics.

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

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

(3) Despite the film's hygroscopicity, it has an excellent hair styling effect under high temperature and high humidity. In addition, due to the moisture absorbing effect, an antistatic effect on the hair is generated, and adhesion of rubber or the like hardly occurs.

(4) No shock phenomenon is caused by the addition of any charged substance, and no solidification is caused by an anionic or cationic activator during hair washing.

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

(6) Very low toxicity and skin irritation.

(7) It feels good and feels very natural.

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

Claims (1)

(57) [Claims] 1. A monomer composition of the following (I) to (IV) is copolymerized in a hydrophilic solvent, and the resulting copolymer is equimolar to the monomer of (I) in an equimolar amount. A method for producing a hairdressing resin having a weight-average molecular weight of 5,000 to 200,000, wherein the resin is modified with an alkali metal salt, an ammonium salt, or an amine salt. (III) Ethylenically unsaturated monomer having an acidic group 3 to 25
% By weight (IV) Ethylenically unsaturated monomer other than the above (I) to (III) 0 to 25% by weight [However, the total of the monomer compositions of (I) to (IV) is 100% by weight. In the above formulas, R ^{1 to} R ⁵ and A each independently represent the following meanings between the formulas. R ¹ = hydrogen atom or methyl group R ² = alkylene group having 1 to 4 carbon atoms R ³ and R ⁴ = hydrogen atom or alkyl group having 1 to 4 carbon atoms R ⁵ = alkyl group or alkenyl group having 1 to 24 carbon atoms A = O or NH. ]