JPH04193822A - Production of resin for hair dressing - Google Patents

Abstract

PURPOSE:To obtain a resin for hair dressing by producing a polymer containing a (meth)acrylic acid derivative such as 6-N,N-dimethylaminohexyl (meth)acrylate and another ethylenic unsaturated monomer, partially quaternizing N atom and then making the polymer amphiphatic. CONSTITUTION:A polymer containing 50-100wt.% monomer A shown by the formula (R<1> is H or CH3; R<2> is 4-6C alkylene) and 0-50wt.% other ethylenic unsaturated monomer B (e.g. styrene) is prepared in a hydrophilic solvent such as ethanol, allowed to react with a haloacetic ester, etc., to quaternize at least 50% N atom derived from the monomer A, hydrolyzed with about 5-20% solution of KOH in ethanol at room temperature to 80 deg.C for 2-6 hours in an inert gas atmosphere while stirring to produce an amphiphatic resin for hair dressing. The resin has excellent setting power and water solubility, is readily removable with a hair washing agent and is safe to the skin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing an amphoteric hair styling resin having excellent setting power and water solubility.

[Prior Art] Nonionic, anionic, cationic, and amphoteric ionic resins have been used as water-soluble hair styling resins. A hairdressing resin described in Japanese Patent Publication No. 32185/1985 is known as having little influence from the addition of anionic substances and cationic substances and having excellent adhesion to hair.

However, the film formed from the above-mentioned hair styling resin is still insufficient in terms of water solubility, and has the disadvantage that, for example, when it is used on hair and then washed, it is likely to be removed incompletely. Furthermore, in the method for producing hair styling resin J described in the above-mentioned publication, the physical properties of the resulting hair styling resin varied due to non-uniformity of copolymerization caused by free radical polymerization.

[Problems to be Solved by the Invention] Therefore, in view of the hair styling resin, the present inventors conducted extensive research to improve the water solubility and uniformity of physical properties of the hair styling resin, and found that An amine compound having a long chain alkylene group is used as the amine compound used in the resin, and in order to eliminate non-uniformity in monomer composition and copolymerization, it is made into two components with the above monomer component or other ethylenically unsaturated monomer. By quaternizing the resulting copolymer and then hydrolyzing it, we finally discovered that it was surprisingly possible to use it as a hair styling resin with excellent setting power and cleansing properties, as well as excellent uniformity of physical properties. He completed his invention.

[Means for Solving the Problems] That is, the present invention provides (A) general formula (I): (wherein R1
is a hydrogen atom or a methyl group, R2 is an alkylene group having 4 to 6 carbon atoms) Monomer A50-100
and (B) 80 to 50% by weight of an ethylenically unsaturated monomer other than monomer A, and at least 50 mol% of the nitrogen atoms derived from monomer A of the polymer are The present invention relates to a method for producing a resin for hair styling, which is characterized in that it is graded and then becomes amphoteric.

[Operations and Examples] According to the production method of the present invention, as described above, the general formula (I
): % formula % (wherein RI is a hydrogen atom or a methyl group, R2 is an alkylene group having 4 to 6 carbon atoms) 50 to 100% by weight of monomer A and ethylenically unsaturated monomers other than monomer A A hair styling resin can be obtained by preparing a copolymer containing 80 to 50% by weight, quaternizing at least 50 mol% of the nitrogen atoms derived from the monomer of the copolymer, and then making it amphoteric.

As described above, monomer A used in the present invention is an acrylic acid and/or methacrylic acid derivative represented by general formula (I). A major feature of the present invention is the use of monomer A. The polymer or copolymer of monomer A has good adhesion to hair, exhibits excellent setting power and moisture resistance, and is easy to wash. It exhibits excellent physical properties that allow it to be easily removed.

Specific examples of the monomer A include 4-N, N
-dimethylaminobutyl (meth)acrylate, 5-N
, N-dimethylaminopentyl (meth)acrylate)
, B-'N', N-dimethylaminohexyl (meth)acrylate, etc. Among these, 6-N,N-dimethylaminohexyl (meth)acrylate is particularly preferred from the viewpoint of versatility.

The amount of monomer A used is 50 to 100% by weight, preferably 60 to 10% by weight based on the total monomers used for polymerization.
It is 0% by weight. If the amount of monomer A used is less than 50% by weight, the film formed with the resulting hair styling agent will be poorly soluble in water, making it difficult to wash and remove it during hair washing, and The affinity for hair, which is a characteristic due to its ionic nature, is reduced, and as a result,
This results in the occurrence of flaking, a decrease in the antistatic effect, and a decrease in the natural texture of the hair.

The ethylenically unsaturated monomer B other than the monomer A used in the present invention is a component that is appropriately used to impart flexibility and appropriate hardness to the film formed by the resulting hair styling agent and to change the texture. It is.

Specific examples of the ethylenically unsaturated monomer B include acrylonitrile, styrene, methylstyrene,
Chlorostyrene, vinyltoluene, vinyl acetate, etc., represented by the general formula (I+): ) acrylate; polypropylene glycol mono(meth)acrylate, vinyl trichlorosilane, methacryloxypropyltrimethoxysilane, acrylamide, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate; Examples include meth)acrylate, diaphragmacrylamide, etc.

The amount of the ethylenically unsaturated monomer B to be used is preferably adjusted to 0 to 50% by weight, preferably 0 to 40% by weight, based on the total monomers used for polymerization. If the amount of the ethylenically unsaturated monomer used exceeds the above range, the water solubility of the resin and the affinity with hair tend to decrease.

The polymer used in the present invention can be obtained by adjusting desired amounts of the monomer A or monomer A and ethylenically unsaturated monomer B, and copolymerizing them in a hydrophilic solvent.

Here, the hydrophilic solvent refers to an organic solvent having a solubility in water of 10 g/100 g of water (25° C.) or more. As a specific example of such a hydrophilic solvent, for example, one carbon number is 1.
-4 aliphatic mono- to tetrahydric alcohol, ethyl cellosolve,
Examples include butyl cellosolve, dioxane, methyl acetate, dimethylformamide, etc. Among these, 1
~Dihydric alcohols are particularly preferred when used as cosmetic raw materials.

Specific examples of the monohydric alcohol include methanol, ethanol, and isopropanol.

Further, specific examples of dihydric alcohols include propylene glycol. Note that, since the resulting hair styling resin may adhere to the skin, in consideration of its safety, ethanol and isopropanol are particularly preferred among the hydrophilic solvents.

The polymerization is performed by dissolving monomer A or monomer A and ethylenically unsaturated monomer B in the hydrophilic solvent, adding a polymerization initiator, and stirring while heating under a stream of inert gas such as nitrogen gas. This is done by

The polymerization initiator is not particularly limited as long as it is generally used in solution polymerization, and specific examples include peroxides such as benzoyl peroxide and lauroyl peroxide, and azobisisobutyroyl peroxide. Examples include azo compounds such as nitrile.

In addition, in the present invention, since acrylic ester and/or methacrylic ester are used as monomers to be subjected to polymerization, crosslinking gelation occurs when peroxide is used as a polymerization initiator. Therefore, it is preferable to use an azo compound.

Further, during polymerization, it is preferable to adjust the hydrophilic solvent so that the concentration of all monomers used in the copolymerization is about 30 to 70% by weight. If the concentration of all the monomers to be subjected to the copolymerization exceeds 50% by weight, it is recommended to divide all the monomers into portions and gradually add them to carry out the polymerization to avoid rapid generation of polymerization heat and safely carry out the polymerization. It is preferable to do so.

The polymerization temperature cannot be determined unconditionally because it varies depending on the type of polymerization initiator used, or it is generally preferable to set it to the 10-hour half-life temperature of the polymerization initiator, especially depending on the reflux temperature of the hydrophilic solvent used. It is preferable that the values be close to each other because polymerization can be performed with higher reproducibility.

Further, if the polymerization time is shorter than 8 hours, the polymerization may be incomplete and unreacted monomer may remain, so it is desirable to set the polymerization time to 8 hours or more, preferably 12 to 36 hours. .

The presence or absence of residual monomers can be determined by confirming the presence or absence of double bonds by a standard method, such as the PSDB method.

The next obtained polymer is made by reacting it with, for example, a haloacetic acid ester in order to quaternize the nitrogen atoms derived from monomer A, and then hydrolyzing the ester portion of the copolymer to form an amphoteric copolymer. It is considered to be a combination.

Specific examples of the haloacetate include methyl chloroacetate, ethyl chloroacetate, methyl bromoacetate,
Examples include ethyl bromoacetate, and these haloacetic esters can be used alone or in combination of two or more. Among these haloacetic acid esters, haloacetic acid ethyl ester is particularly preferred since the resulting resin is used for hair styling.

The amount of the haloacetic acid ester used is a stoichiometric amount, that is, 50 to 100 mol per 00 mol of monomer Al,
Preferably it is 60 to 100 moles.

In addition, the quaternization rate of nitrogen atoms derived from monomer A is:
Since it depends on the amount of monomer A used, it cannot be determined unconditionally, but for example, if the amount of monomer A used is the smallest at 50 mol%, the quaternization rate is 100 mol%, and the amount of monomer A used is the highest. 100 mol%
In normal conditions, the quaternization rate is 50 mol% or more.

The reaction between the copolymer or homopolymer of monomer A and the haloacetic acid ester is usually carried out in the hydrophilic solvent used in preparing the polymer. In this case, the concentration of the polymer solution is preferably about 30 to 65% by weight. - The haloacetic acid ester is usually added as a solution to the polymer solution all at once or in portions. In this case, the reaction is carried out with stirring in an atmosphere of an inert gas such as nitrogen gas under normal pressure.
This can be carried out by heating to about 90° C. or by heating to about 90° C. for 8 to 20 hours under pressure.

The thus quaternized polymer is then hydrolyzed. Such hydrolysis is usually carried out by adding about 5 to 20% of potassium hydroxide, for example, so that the amount of potassium hydroxide is 105 to 1.20 mol per 100 mol of haloacetic acid ester contained in the reaction solution after completion of the reaction. This is carried out by adding an ethanol solution and keeping it at room temperature to about 80° C. for about 2 to 6 hours in an inert gas atmosphere such as nitrogen gas while stirring.

It is also possible to react with, for example, a haloacetate without going through an ester.

Typical examples of the haloacetate include sodium haloacetate, potassium haloacetate, etc., and specific examples thereof include sodium chloroacetate, sodium bromoacetate, potassium chloroacetate, potassium bromoacetate, etc. Potassium chloroacetate is particularly preferred from the viewpoint of reaction speed.

The amount of the haloacetate used is a stoichiometric amount, that is, 50 to 100 mol, preferably 60 to 100 mol, per 100 mol of monomer A.

In addition, the quaternization rate of nitrogen atoms derived from monomer A is:
It cannot be determined unconditionally because it varies depending on the amount of monomer A used, but for example, if the amount of monomer A used is the smallest at 50 mol%, the quaternization rate is 100 mol%, and the amount of monomer A used is the highest. 100 mol%
In normal conditions, the quaternization rate is 50 mol% or more.

The reaction between the polymer and the haloacetate is usually carried out in the same hydrophilic solvent used to prepare the polymer. In this case, the concentration of the polymer solution is preferably about 30 to 65% by weight. The haloacetate is 20 to 40% by weight.
It is added to the polymer all at once or in portions as a slurry solution. In this case, the solvent for the slurry solution is preferably the hydrophilic solvent used during the preparation of the polymer.

The reaction can be carried out by heating at 70 to 80° C. for 8 to 16 hours under normal pressure in an inert gas atmosphere such as nitrogen gas while stirring. However, in this case, the haloacetate self-condenses during the reaction, producing polyester and producing insoluble matter, which causes turbidity. In addition, such a reaction solution causes clogging during filtration and purification, which significantly impairs workability in the purification process, so it is preferable to conduct the reaction via ester.

Next, after the amphoteric reaction is completed, inorganic salts are produced as by-products, so
For example, it is preferable to remove by-product inorganic salts by filtration or treatment with an ion exchange resin.

The hair styling resin thus obtained is used as a hair styling agent in the form of a solution or in a state with the solvent removed.

For example, to prepare a hair blow type hair conditioner,
For example, a solution of the hair styling resin in the hydrophilic solvent used as the polymerization solvent may be filled into a spray pump container together with other additives, auxiliary agents, and the like. It is generally desirable that the blending ratios of the various components filled into the spray pump container be adjusted as appropriate depending on the intended use.

Since the hair styling resin is amphoteric, the additives and auxiliary agents may be of any charge, and specific examples include alcohol esters of higher fatty acids, glycerin, plasticizers such as polyethylene glycol,
Examples include fragrances, coloring agents, and various hair nutrients.

The hair styling resin can be used alone or by blending with other anionic resins, nonionic resins, or cationic resins, for example, as setting lotions, hair lotions, hair liquids, hair gels, shampoos, conditioners, hair creams, etc. Suitably used.

Next, the method for producing the hair styling resin of the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples.

Example 1 A fifth flask equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen introduction tube, a charging tube and a stirring device was charged with 6-
60 parts (by weight, the same applies below) of N,N-dimethylamino-1-methylethyl methacrylate, 40 parts of tertiary-butyl methacrylate, and 150 parts of absolute ethanol were added, and 02 parts of 2,2°-azobisisobutyronitrile was added. The mixture was added, heated to 80° C. under a nitrogen gas stream, and a polymerization reaction was carried out under reflux for 12 hours.

Next, 6-N,N-dimethylaminohexylethyl methacrylate and equal molar amount of monochloroacetic acid ethyl ester were added dropwise into the flask using a dropping funnel.
A quaternized resin was obtained by heating at 80°C for 10 hours under a nitrogen gas stream.

The weight average molecular weight of the gill resin is about 50,000, and the quaternization rate is 0. It was determined to be 97% by potentiometric titration using an aqueous IN hydrochloric acid solution.

Next, a solution of potassium hydroxide (28.9 g), 1.1 times the mole of monochloroethyl acetate used for quaternization, dissolved in 9 times the amount of ethanol (242 g) was added dropwise into the flask using a dropping funnel. 80 minutes in a nitrogen gas stream.
℃ for 5 hours with stirring to hydrolyze the quaternized monochloroacetic ester (hydrolysis rate: 99.8%),
An amphoteric resin solution was obtained.

The resulting resin solution was filtered under pressure to remove by-product inorganic salts and excess potassium monochloroacetate. Further, the resin was purified by passing it through a column packed with an anionic exchange resin, and then through a column packed with a cationic exchange resin, to obtain a hair styling agent.

The resulting hair conditioner has an ash content of 1% or less, and chlorine (C4”-
) The concentration was 1100 pp or less.

Next, the appearance and water solubility of the obtained hair styling agent were examined according to the following methods. The results are shown in Table 1.

(Appearance) The resulting hair styling agent was prepared as an ethanol solution containing 30% of the resin component, and its appearance was visually observed.

(Water-soluble) The resulting hair styling agent was prepared into an ethanol solution containing 30% of the resin component, and while maintaining the liquid temperature at 25°C,
We investigated whether water could be diluted by adding water. The evaluation criteria are shown below.

(Evaluation criteria) ○: Diluted infinitely.

×: Turbidity occurs when water is added.

Example 2 A hair styling resin was prepared in the same manner as in Example except that the monomer composition was changed as shown in Table 1.

The weight average molecular weight of the obtained resin was 48,000, and 4
The grading rate was 98%.

Next, the physical properties of the obtained resin were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 3 A hair styling resin was prepared in the same manner as in Example 1, except that the monomer composition was changed as shown in Table 1.

The weight average molecular weight of the obtained resin was 40,000.
9- The quaternization rate was 98%.

Next, the physical properties of the obtained resin were investigated in the same manner as in Example]. The results are shown in Table 1.

Example 4 A copolymer was prepared in the same manner as in Example 1 except that the monomer composition was changed as shown in Table 1.

The weight average molecular weight of the resulting resin was 40,000. The quaternization rate was 96%.

Next, the obtained resin solution was purified in the same manner as in Example 1.

The ash content of the resulting resin is less than 0.1%, and the chlorine (CI) content is less than 0.1%.
The content was below 1100 pp.

The physical properties of the obtained resin were investigated in the same manner as in Example 1. The results are shown in Table 1.

Example 5 Except for changing the monomer composition as shown in Table 1,
A hair styling resin was prepared in the same manner as in Example 1. The weight average molecular weight of the resulting resin was 41,000. Moreover, the quaternization rate was 97%.

20 The physical properties of the resin obtained were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 6 Except for changing the monomer composition as shown in Table 1,
A hair styling resin was prepared in the same manner as in Example 1. The weight average molecular weight of the obtained resin was 43,000. Also, 4
The grading rate was 96%.

Next, the physical properties of the obtained resin were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 7 A hair styling resin was prepared in the same manner as in Example 1, except that the monomer composition was changed as shown in Table 1. The weight average molecular weight of the obtained resin was 49,000. Moreover, the quaternization rate was 94%.

Next, the physical properties of the obtained resin were examined in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 A copolymer was prepared in the same manner as in Example 1 except that the monomer composition was changed as shown in Table 1.

Next, 1.5 times the mole of 3-N,N-dimethylaminopropyl methacrylate of ethyl monochloroacetate was added dropwise into the flask using a dropping funnel, and heated at 80°C for 24 hours under a nitrogen gas stream. A quaternized resin was obtained.

The weight average molecular weight of the obtained resin was 40,000, and 4
The grading rate was 96%.

Next, 1.1 of ethyl monochloroacetate used for quaternization
A hair styling agent was obtained in the same manner as in Example 1, except that a solution prepared by dissolving twice the amount of potassium hydroxide in 9 times the amount of ethanol was used.

The physical properties of the obtained hair styling agent were investigated in the same manner as in Example 1.

The results are shown in Table 1.

[Margin below] From the results shown in Table 1, it can be seen that the hair styling resins obtained in Examples 1 to 7 of the present invention were all excellent in both appearance and water solubility.

Formulation Examples 1 to 7 and Comparative Formulation Example 1 The hair styling resins obtained in Examples 1 to 7 and Comparative Example 1 were
9 g of purified water was added to 21 g of a 0% ethanol solution, and the mixture was filled into a spray pump to create a hair blower.

Using the resulting hair blower, the setting force and physical properties of the formed film were examined in accordance with the following methods. The results are shown in Table 2.

(Set power) After spraying 2 g of hair with a length of 25 cm for 10 seconds from a distance of 20 cm, the hair was wrapped in curlers with an outer diameter of 1.2 cm and dried with warm air at 40°C for 60 minutes. After that, remove the hair from the curler and hang it vertically in an atmosphere with a temperature of 30°C and a relative humidity of 8096°C to determine the length (L).
, ) and the length (L2) after being left for 1 hour were measured, and the curl retention was calculated from the following formula.

5-L [Curl Retention] e= 2x 100
(%)25-1. .

(Physical properties of the film) (a) Cleanability After spraying the hair blower 10 times from a distance of 20 cm onto a glass plate measuring 2.5 cm (vertical) and 7.5 cm (horizontal), a film was formed by air drying at 20°C for 3 hours. did. This glass plate was left standing and immersed in warm water containing 0.2% shampoo at 40°C, and the change in the dissolution state of the film over time was examined and evaluated according to the evaluation criteria shown below.

(Evaluation criteria) ○: Completely dissolved within 10 minutes.

Δ: Completely dissolved within 20 minutes.

×: Film remains even after 20 minutes have passed.

(b) Water Resistance After spraying the hair plow 10 times from a distance of 20 cm onto a horn glass plate measuring 2.5 cm in length and 7 cm in width, a film was formed by air drying at 20° C. for 3 hours. This glass plate was left standing and immersed in warm water at 40° C., and the change over time in the dissolution state of the film was examined and evaluated according to the evaluation criteria shown below.

(Evaluation criteria) ○: No dissolution at all even for 60 minutes or more.

Δ: Partial dissolution is observed within 40 to 60 minutes.

×: Partial dissolution is observed within 40 minutes.

(c) Blocking resistance 3 g of hair styling agent was uniformly applied to 2 g of hair having a length of 25 cIII using a spray pump. The hair was dried with warm air at 40° C. for 60 minutes, and the condition of the hair when combed was evaluated using a commercially available comb based on the following evaluation criteria.

(Evaluation criteria) O: There is no catch and the comb passes through smoothly.

△: There is some catch, but it can be combed through.

×: The comb does not go through.

(d) Smoothness After spraying the hair blow 10 times from a distance of 2 cm on a 2.5 cm + 7.5 cm glass plate,
A film was formed by air drying at 20° C. for 3 hours.

Next, the tactile sensation of the formed film surface was examined with fingers, and the smoothness was evaluated based on the evaluation criteria shown below.

(Evaluation criteria) O: Completely smooth.

△: Slightly rough.

×: Considerably rough.

(E) Transparency After spraying the hair styling product 10 times from a distance of 20 cm on a glass plate measuring 2.5 cm vertically and 7.5 cm horizontally,
A film was formed by air drying at 20° C. for 3 hours. Next, the state of the formed film was visually observed and evaluated based on the following evaluation criteria.

(Evaluation criteria) Q: It is completely transparent.

Δ: Partially whitened.

×: The entire surface is whitened.

(f) Flaking resistance 3 g of hair blow was applied uniformly to 2 g of hair with a length of 25 cm by spraying. The hair was dried with warm air at 40° C. for 60 minutes, combed through the hair 10 times using a commercially available comb, and then the peeling state of the resin was evaluated based on the following evaluation criteria.

(Evaluation criteria) ○: No peeling observed at all.

Δ: Partial peeling is observed.

×: Peeling is observed throughout.

[Margins below] = 27 - From the results shown in Table 2, the hair styling products obtained in Examples 1 to 7 of the present invention all had good setting power, cleansing properties, blocking resistance, smoothness, transparency, and resistance. It can be seen that it has excellent flaking properties.

[Effects of the Invention] The hair styling resin obtained in the present invention is water-soluble and can be easily removed with a hair wash, so it has excellent setting power and excellent blocking resistance even under high temperature and humidity. It is something.

Furthermore, the hair styling resin obtained according to the present invention has a high affinity for hair, has an excellent hair styling effect, does not cause flaking, and has very little irritation to the skin.

Furthermore, since the hair styling resin according to the present invention is not solidified by anionic or cationic substances, various additives can be appropriately added thereto.

Claims (1)

[Claims] 1 (A) General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 is a hydrogen atom or a methyl group, R^2 is a carbon number of 4 A polymer containing 50 to 100% by weight of a monomer A (representing an alkylene group of At least 50 nitrogen atoms derived from monomer A
Quaternizing mole percent and then amphoteric