JPS6232165B2 - - Google Patents

Description

[Detailed description of the invention]

[] BACKGROUND TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing a water-soluble amphoteric ionic resin that exhibits excellent hair styling effects. The hair styling resins obtained according to the invention are particularly suitable for use in aerosol form. PRIOR ART It is well known to fix hair with resin to give it a desired shape. Hair styling resins should be water-soluble so that they can be removed by washing the hair. Such hair styling resins include nonionic,
Anionic and cationic types have been used conventionally. However, conventional resins are not always fully satisfactory. In other words, nonionic resins include polyvinyl methyl ether and polyvinylpyrrolidone, but polyvinylpyrrolidone resins are easily affected by humidity conditions, and the film before absorbing moisture is hard and prone to flaking, whereas it Sometimes they become so flexible that a blocking phenomenon can occur, causing the hair to stick together and become impossible to comb or brush. 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 has better properties than nonionic resins, but due to its anionic nature 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 limited, and there is a concern that it may solidify due to rinse agents used 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 inventors of the present invention have already reported in JP-A-51-1999 that an excellent hair styling (hair fixing) resin composition can be obtained by using a resin containing amphoteric ions.
This is clarified in Publication No. 9732. However, in this case, if a sodium salt or potassium salt of haloacetic acid is used when ionizing the copolymer, a precipitate may be generated during denaturation. It is not very good and the container tends to corrode when used in aerosol form. [] 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 by removing the precipitate that occurs when denaturing haloacetic acid with sodium salt or potassium salt. The present invention was achieved by discovering that a resin (for hair fixation) can be obtained. That is, the method for producing hair styling resin according to the present invention is as follows:
The following monomer compositions (1) to (5) are copolymerized in a hydrophilic solvent, and the resulting copolymer is reacted with sodium or potassium haloacetate in a solution state in the hydrophilic solvent to form a precipitate. is removed, and the resulting copolymer solution is optionally treated with an ion exchange resin to remove ionic impurities.

[Table] Unsaturated monomers The total content of monomer (1) units and monomer (4) units is at least 35% by weight. Moreover, in the above formula, R ¹ to R ⁶ and A have the following meanings each and independently between each formula. R ¹ = hydrogen atom or methyl group R ² = alkylene group with 1 to 3 carbon atoms R ³ and R ⁴ = alkyl group with 1 to 4 carbon atoms R ⁵ = alkyl group with 1 to 3 carbon atoms R ⁶ = 4 carbon atoms -24 alkyl group or C4-24 cycloalkyl group A=O or NH Effect According to the present invention, a resin having properties particularly suitable for use as an aerosol hair styling agent is provided. That is, the present resin is soluble in water or a hydrophilic organic solvent, and solutions obtained using these solvents exhibit good solubility in common propellants. Furthermore, the resin obtained according to the present invention can be easily washed off with a hair detergent. In addition to the above-mentioned general features, this hair styling resin 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. [] Specific description of the invention 1 Monomer The resin obtained by the present invention contains essential monomer 2
It is an amphoteric product of a copolymer of seeds (monomers (1), (3)) and three arbitrary monomers (monomers (2), (4), (5)). These monomers can be used in combination within each group. 1 Monomer (1) Monomer (1) is a derivative of acrylic acid or methacrylic acid (hereinafter referred to as (meth)acrylic acid) represented by the general formula (). In the formula, each substituent has the meaning described above, R ¹ is methyl,
It is generally preferred that ^R2 is _C2 - _C3 , ^R3 and ^R4 are _C1 - _C2 , and A is 0. Specific examples of monomer (1) include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, and diethylaminopropyl (meth)acrylate. ) Contains acrylamide. The amount of monomer (1) used is 25 to 45% of the total monomers.
% by weight, preferably 30-40% by weight. twenty five%
If it is less than this, the film of the final amphoteric copolymer will be poorly soluble in water and will be difficult to remove during hair washing. Moreover, the affinity for hair, a characteristic due to the zwitterionic nature of this copolymer, is reduced;
As a result, problems such as occurrence of flaking phenomenon, decrease in antistatic effect, and decrease in hair's natural texture occur. On the other hand, when the amount of monomer (1) exceeds 45% by weight, the copolymer film exhibits a blocking feeling, has poor setting power, and also has reduced solubility in propellants when aerosolized. do. In the present invention, the amounts of monomers (1) to (5) relate to the monomer composition based on the weight of all monomers used, but the polymerization rate during copolymerization is substantially 100% ( (which is usually the case), this composition is substantially the same as the monomer unit composition of the copolymer before amphotericization. 2 Monomer (2) Monomer (2) is a (meth)acrylic ester represented by the general formula (). R ¹ is methyl,
It is generally preferred that R ⁵ is alkyl. Specific examples of monomer (2) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylates, and butyl (meth)acrylates. The amount of monomer (2) used is 0 to 50% of the total monomers.
% by weight, preferably from 5 to 40% by weight. If it exceeds 50% by weight, the flexibility of the copolymer film deteriorates and its solubility in propellants decreases. 3 Monomer (3) Monomer (3) is a (meth)acrylic acid ester represented by the above general formula (), and has a longer chain length of the alcohol moiety than monomer (2). R ¹ is methyl,
Those in which R ⁶ is C ₄ to C ₁₈ are generally preferred. To give a specific example of monomer (3), for example, 2-
There are ethylhexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, isobutyl (meth)acrylate, and cyclohexyl (meth)acrylate. The amount of monomer (3) used is 5 to 65% of the total monomers.
% by weight, preferably 10-50% by weight. 5%
If it is less than that, the moisture resistance (setting power at high humidity) will decrease.
The flexibility of the film deteriorates and its solubility in propellants decreases, and when the content exceeds 65% by weight, the film of the same copolymer begins to exhibit a blocking feeling, and the smoothness and transparency of the film deteriorate. It also becomes poorly soluble in water, making it difficult to remove it when washing hair. 4 Monomer (4) N-vinylpyrrolidone (4) can be further copolymerized to improve the water solubility of the final amphoteric copolymer and facilitate washing removal during hair washing. The amount of monomer (4) used is 0 to 20 based on the total monomers.
% by weight, preferably 0 to 15% by weight, and the total amount with monomer (1) is 35% by weight or more, preferably 35% by weight.
The amount is ~50% by weight. When the amount of monomer (4) itself exceeds 20%, the hydrophilicity improves, the setting power at high humidity decreases, the film begins to exhibit a blocking feeling, and the relationship between monomer (1) and monomer (1) increases. If the total amount is less than 35%, the water solubility of the amphoteric copolymer is insufficient. 5 Monomer (5) Ethylenically unsaturated other than the above monomers (1) to (4) in order to give the final amphoteric copolymer film appropriate flexibility and hardness to change the feel. The monomers can be further copolymerized. Specific examples of monomer (5) include acrylonitrile, styrene, chlorostyrene, vinyltoluene, vinyl acetate, polypropylene glycol mono(meth)acrylate, vinyltrichlorosilane, methacryloxypropyltrimethoxysilane, acrylamide, hydroxy These include ethyl to propyl (meth)acrylate, polyethylene to propylene glycol mono(meth)acrylate, and diacetone acrylamide. The amount of monomer (5) used is 0 to 0 based on all monomers.
20% by weight, preferably 0-10% by weight. 2 Polymerization The above three to five types of monomers are copolymerized in a hydrophilic solvent. The term "hydrophilic solvent" as used herein means an organic solvent having a solubility in water of 10 [g/100g water/25°C] or more. Specific examples of hydrophilic organic solvents suitable for use in the present invention include, for example, aliphatic mono- to tetrahydric alcohols having 1 to 4 carbon atoms, especially mono- to dihydric alcohols, especially monohydric alcohols, e.g. methanol,
Ethanol, isopropanol, etc., dihydric alcohols include ethylene glycol, ethyl cellosolve, butyl cellosolve, dioxane, methyl acetate, dimethyl formamide, etc. The "hydrophilic solvent" may be in a water-containing state.
From the viewpoint of a polymerization solvent, the degree of water content is free within a range in which all the monomers used are dissolved in a predetermined concentration (restrictions on the water content from the viewpoint of a solvent for amphotericization reaction will be described later). A specific example of a water-containing hydrophilic organic solvent is 95% ethanol. Polymerization is carried out by a conventional solution polymerization method, for example, a method consisting of 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. Generally, all types and amounts of monomers are present from the beginning of polymerization, but the types and/or amounts of monomers may be added in portions. The amount of solvent used is preferably such that the concentration of the resulting copolymer solution is about 30 to 65% by weight. 3 Amphoterization The 3- to 5-component copolymer thus obtained is reacted with sodium or potassium haloacetate. The "reaction" in this case is understood to be zwitterionic ionization consisting of introducing an acetate group into the amino group of monomer (1). As a result of this reaction, sodium or potassium halide derived from the sodium or potassium haloacetate used is produced as a by-product. The amphoteric reaction is carried out on a solution of the copolymer obtained as described above in a hydrophilic solvent. The definition of the hydrophilic solvent in this case is the same as that for the polymerization solvent described above. However, from the viewpoint of removing the amphoteric reaction by-product inorganic salt as a precipitate according to one of the features of the present invention, the amphoteric reaction solvent should have a sufficiently low solubility of this by-product inorganic salt,
Therefore, it is preferable that the hydrophilic solvent has a sufficiently low water content. If this point is taken into consideration, it is convenient to carry out the amphotericization reaction on the copolymerization reaction product, that is, on the copolymer solution. The halogen in sodium or potassium haloacetate, which is an amphoteric agent, is chlorine, bromine or iodine, with chlorine being typical. The salt can also be formed "in situ" by reacting the haloacetic acid with sodium or potassium hydroxide in an amphoteric reaction solvent. In the amphoteric reaction, sodium or potassium haloacetate is added as it is or as a solution or suspension to a copolymer solution (preferably the copolymer concentration is about 30 to 65% by weight), all at once or in portions, and then inactivated. This can be carried out by heating at a temperature of about 70 to 80° C. for about 4 to 8 hours under an atmosphere, for example, a nitrogen stream, with appropriate stirring. The amount of sodium or potassium haloacetate to be used is the stoichiometric amount, i.e. relative to monomer (1) (and monomer (5) if monomer (5) contains a nitrogen atom to be ampholyzed). equimolar, 70-130% of
It is usually about 80 to 120%, preferably. 4 By carefully selecting the solvent for the peramphoterization reaction, the by-product inorganic salt, i.e., sodium or potassium halide, precipitates (but does not necessarily precipitate) in the amphoterized copolymer solution. This is removed as it precipitates. The precipitate may be removed by centrifugation, filtration, or any other means available for solid-liquid separation. If the solvent is removed after precipitation (or after treatment with an ion exchange resin as described below), the objective resin of the present invention can be obtained as a solid. 5 Ion Exchange Resin Treatment The amphoteric copolymer solution from which the precipitate has been separated in this manner may still contain a small amount (about 0.1 to 1% by weight) of a by-product inorganic salt. If it is desired to sufficiently remove such inorganic salts, the ash content can be reduced to 0.1% by weight or less by treating the amphoteric copolymer solution after precipitation with an ion exchange resin, for example, in a batch or flow system. can do. 6 Usage form The thus obtained hair styling resin can be used as it is when it is obtained as a solution, or as a hair styling agent or a hair styling agent resin component after removing the solvent. A preferred mode of use of the hair styling resin is to apply the solution to the hair in the form of an aerosol by sealing the solution together as a propellant under pressure in a container and injecting it into the atmosphere through a valve. It is known to apply a hair styling resin to hair in the form of an aerosol, and the resin of the present invention may be similarly used by being encapsulated in an aerosol dispenser.
Therefore, solvents for the amphoteric copolymers, preferably hydrophilic solvents (as defined above), such as aliphatic alcohols, ethers such as dioxane, ketones such as methyl ethyl ketone, acetone, ether alcohols, as defined above as solvents for polymerization. such as methyl cellulosolve, ethyl cellosolve, etc., propellants such as those commonly used, such as fluoro or fluorochloroalkanes (known as "freons"),
It is sealed under pressure in a conventional aerosol dispenser together with other halogenated hydrocarbons, hydrocarbons such as butane gas, other petroleum-based liquefied gases, etc., and with appropriate additives or auxiliaries. Since the resin obtained by the present invention is amphoteric, the additive or auxiliary agent in this case may be of any charge, such as a plasticizer such as a higher alcohol ester of a higher fatty acid, glycerin, or polyethylene glycol. By adding appropriate fragrances, polishing agents, coloring agents, hair nutrients, etc., the additives or the resin itself will not be altered in quality. 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 amphoteric ionic resin in the present invention can be used for setting lotions, hair lotions, hair liquids, shampoos, etc. , conditioner, hair creel, etc. In the present invention, the expression "for hair styling" refers to such hair-related uses. 7 Experimental Examples Example 1 30 parts of dimethylaminoethyl methacrylate, 30 parts of methyl methacrylate, and 15 parts of 2-ethylhexyl methacrylate were placed in a five-necked flask equipped with a reflux condenser, dropping funnel, thermometer, glass tube for nitrogen substitution, and stirring device. , dodecyl methacrylate 15
10 parts of N-vinylpyrrolidone and 100 parts of absolute ethanol, 0.6 part of α,α'-azobisisobutyronitrile was added, and the mixture was heated under reflux at 80°C under a nitrogen stream to carry out polymerization for 4 hours. Next, a 50% by weight ethanol suspension of dimethylaminoethyl methacrylate and equimolar potassium monochloroacetate was added dropwise into the flask using a dropping funnel, and the mixture was further heated at 80°C for 6 hours under a nitrogen stream to undergo an amphoteric reaction. Do this. The resulting viscous suspension is separated from the precipitate using a pressure filter (manufactured by Nippon Sensei Kikai Co., Ltd.). The liquid is passed through a column packed with a regenerated cation exchange resin (Diaion PK-220, the system was replaced with anhydrous ethanol after regeneration), and then a column filled with a regenerated anion exchange resin (Diaion PA-220).
416". After regeneration, the system is passed through a column filled with anhydrous ethanol. The pale yellow transparent solution obtained in this way is used as the active ingredient.
Adjust to 30% by weight with absolute ethanol. 24 parts of absolute ethanol was added to 6 parts of this solution to dissolve it, and 45 parts of dichlorodifluoromethane was added thereto, and the mixture was filled into a closed container to prepare a spray. When this hair lacquer was sprayed on hair, no blocking or flaking occurred, a natural texture and good setting power were observed, and the compatibility with propellants and film properties were also excellent. Further, even when this solution was left in a tin can at 45°C for 6 months, no corrosion was observed on the inner surface of the can. Note that the molecular weight of the obtained resin was 52,000. Examples 2 to 6 (See Table 1) Resin solutions obtained by operating in the same manner as in Example 1 except that the initial monomer composition was changed to the composition shown in Table 1 were the same as the resin solutions obtained in Example 1. Similarly, blotzking,
Shows good setting power without raking,
It also showed excellent performance in terms of compatibility with propellants and film properties. The molecular weights of the resins obtained in these Examples are as follows. Example 2: 62500, Example 3: 75000, Example 4: 62000, Example 5: 68000, Example 6:
53000. Comparative Examples 1 to 8 (See Table 2) Resin solutions obtained by operating in the same manner as in Example 1 except that the initial monomer composition was as shown in Table 2 had good compatibility with propellants, cleanability, There was a problem with at least one of the film properties such as blocking, smoothness, and transparency, and there was a problem with the performance of the setting agent. The sample of Comparative Example 8 also had a problem in setting power. The performance of the resins shown in the table was evaluated as follows. ○ indicates good, △ indicates insufficient, and × indicates poor. (1) Compatibility with propellant F ₁₁ /F ₁₂ = 20/80 (weight ratio) in a pressurized container with 40 parts of alcoholic liquid containing 5% by weight of resin (dry basis)
Add 60 parts of Freon gas, cool it, and measure the polymer precipitation temperature. (2) Film properties Spray the above solution onto a glass plate and heat at 20℃, 60%
Leave it in an RH atmosphere day and night and evaluate visually and with your finger. The cleanability is evaluated based on the state of film dissolution at each time point when the glass plate is left standing and immersed in warm water containing 0.2% shampoo at 40°C. (3) Setting power Spray the above solution on 23 cm, 2 g hair for 10 seconds, wrap it around a 1.2 cm diameter curler, and after drying,
℃, hang under 90% RH atmosphere and measure curl retention. (4) Flaking When hair prepared in the same manner as the setting force evaluation is combed, the amount of peeling resin is evaluated.

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Claims (1)

[Scope of Claims] 1 The following monomer compositions (1) to (5) are copolymerized in a hydrophilic solvent, and the resulting copolymer is mixed with sodium or potassium haloacetate in a solution state in the hydrophilic solvent. 1. A method for producing a hair styling resin, which comprises reacting, removing precipitates formed as by-products, and treating the resulting copolymer solution with an ion exchange resin to remove ionic impurities, if necessary. (1) 25-45% by weight (2) 0-50% by weight (3) 5 to 65% by weight (4) N-vinylpyrrolidone 0 to 20% by weight (5) Ethylenically unsaturated monomers other than the above (1) to (4)
0 to 20% by weight, and the total content of monomer (1) units and monomer (4) units is at least 35% by weight. Moreover, in the above formula, R ¹ to R ⁶ and A have the following meanings each and independently between each formula. R ¹ = hydrogen atom or methyl group R ² = alkylene group having 1 to 3 carbon atoms R ³ and R ⁴ = alkyl group having 1 to 4 carbon atoms R ⁵ = alkyl group having 1 to 3 carbon atoms R ⁶ = 4 carbon atoms -24 alkyl group or C4-24 cycloalkyl group A=O or NH