JPH0495017A - New polymer and hair cosmetic containing the same - Google Patents

Abstract

PURPOSE:To provide a hair cosmetic having good hair-conditioning and arranging effects by compounding a specific cationic/amphoteric polymer. CONSTITUTION:A hair cosmetic especially contains a cationic/amphoteric polymer comprising 5-40mol% of quaternary repeating units of formula I [R<1> is H, methyl; R<2> is 1-4C alkylene; R<3> is 1-4C alkyl, benzyl, 2-hydroxyethyl, 2,3- epoxypropyl, 2-hydroxypropyl), group of formula II (n us 1-9); A<1> is O, NH; X is halogen, alkyl sulfuric acid residue], 40-90mol% of amphoteric repeating units of formula III (R<4> is R<1>; R<5>, R<6> are R<2>; A<2> is A<1>), and 5-40mol% of repeating units of formula IV. The polymer is prepared e.g. by a method wherein monomers corresponding to the respective repeating units are copolymerized and subsequently subjected to a quaternization reaction and an amphoteric reaction, or by a method wherein the respective monomers are subjected to quaternization reactions and amphoteric reactions and subsequently copolymerizing the reacted monomers.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel cationic/ampholytic polymer and a hair cosmetic containing the same that has a hair conditioning effect and a hair styling effect.

[Prior art and problems to be solved by the invention] Conventionally,
Cationic polymers as hair conditioning agents,
Although oils and fats have been used, there has been no one that satisfies both the conditioning effect of making the hair easy to comb and feel good after drying, and the hair styling effect of maintaining the hair style.

[Means for Solving the Problems] Under these circumstances, the present inventors conducted intensive research and found that a hair cosmetic that satisfies the above requirements can be obtained by blending a specific new cationic/ampholytic polymer. The invention has been completed.

That is, the present invention comprises 5 to 40 mol% of quaternized repeating units represented by the following general formula (I), 40 to 90 mol% of amphoteric repeating units represented by general formula (n),
and a cationic/amphoteric polymer comprising 5 to 40 mol% of repeating units represented by general formula (m), and a hair cosmetic containing the same.

(Left below) R'R'
CH3-CH2-C--CH2-C--CH2-Cc
=o c=o
c=.

A' A20R2R5CH2 Cloudy x-coo- (I) (n)
(m) [In the formula, R1 and R4 are hydrogen atoms or methyl groups, R11, R5 and R6 are alkylene groups having 1 to 4 carbon atoms, and R3 is an alkyl group having 1 to 4 carbon atoms, benzyl group, 2- A1 and A2 are oxygen atom or NH, and X represents a halogen atom or an alkyl sulfate residue. ] In the above formula, R1 and R4 are methyl groups, R2 and R5 are ethylene, R6 is methylene, R
Particularly preferred is a methyl group as 3, an oxygen atom as A1 and A2, and a chlorine atom as X. Further, the molar ratios of the repeating units of general formulas (I), (n), and (III) are 5 to 40 mol%, 40 to 90 mol%, and 5 to 5 mol%, respectively.
40 mol%, and if it deviates from this range, sufficient effects will not be achieved when it is blended into hair cosmetics. In addition, when considering compatibility, it is preferable that the degree of cationization is low.

The method for producing the cationic/ampholytic polymer of the present invention includes: ■ A method in which unmodified monomers corresponding to each repeating unit are polymerized, and then quaternized and amphotericized. ■ Quaternized and amphotericized each monomer. ■ Method of copolymerizing the quaternized monomer and unmodified monomer and then performing amphotericization ■ Copolymerizing the monomer after amphotericization with the unmodified monomer Examples include a method in which quaternization is performed after polymerization.

Copolymerization of each monomer is performed in a hydrophilic solvent.

As the hydrophilic solvent, one or more water-soluble aliphatic alcohols having 1 to 4 carbon atoms or a mixture thereof with water is preferable, and the concentration of the resulting polymer is 30 to 70% by weight.
It is preferable to use an amount that satisfies the following.

Note that the solvent composition may need to be selected depending on the solubility of the monomer after modification. Copolymerization is carried out using the usual solution polymerization method, for example, by dissolving the monomer in the above solvent, adding a polymerization initiator,
Polymerization is carried out by appropriately selecting polymerization conditions, such as 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. Even if the entire amount of monomer is present from the beginning of polymerization,
It may be added separately for each type of monomer or in small portions.

The average molecular weight of the polymer thus obtained is approximately 10,000 to 70
Preferably, it is 10,000.

The quaternization reaction is carried out by injecting a gaseous amount of a quaternizing agent in an equimolar amount to the monomer to be quaternized into a solution of a monomer or polymer in a hydrophilic solvent under a nitrogen stream with stirring. Drop the solution,
This is carried out by heating at 70 to 95°C for 2 to 10 hours.

Examples of the quaternizing agent include methyl chloride, methyl bromide, methyl iodo, ethyl chloride, ethyl bromide, propyl chloride, ethylene chlorohydrin, ethylene bromohydrin, epichlorohydrin, epibromhydrin, propylene chlorohydrin, and propylene bromhydrin. Phosphorus, benzyl chloride, benzyl bromide, polyethylene glycol monoepoxide, dimethyl sulfate, diethyl sulfate, etc. are used.

The amphoteric reaction is carried out by adding an amphoteric agent in an aqueous solution, a hydrophilic solvent solution, or a suspension in a hydrophilic solvent solution of a monomer or polymer in an equimolar amount to the monomer to be amphoteric while stirring under a nitrogen stream. The suspension is added dropwise and heated at 70-95°C for 2-10 hours.

Examples of amphoteric agents include sodium monobromoacetate,
Sodium monochloroacetate, potassium monochloroacetate,
Monohalogenated fatty acid alkali metal salts such as lithium monochloropropionate; monohalogenated fatty acids and ammonia, 2-amino-2-methyl-1-propatur, monoethanolamine, jetanolamine, triethanolamine, 2-amino- Neutralized products with 2-methyl-1,3-propanediol, 2-amino-2-ethyl-1-propatol, morpholine, etc. are used.

If the amphoteric agent is an alkali metal salt such as sodium, potassium, or lithium, inorganic salts will precipitate as the amphoteric reaction progresses, so if salt becomes an obstacle in the formulation,
It is preferable to remove this by solid-liquid separation operations such as centrifugation and filtration. On the other hand, when the amphoteric agent is an amine salt or an ammonium salt, the organic salt does not precipitate even as the amphoteric reaction progresses, so there is no need to perform such a separation operation and the solution can be used as it is as a homogeneous solution.

The cationic/ampholytic polymer of the present invention thus obtained can be left as a solution in a hydrophilic solvent, or subjected to operations such as diluting with water, ethanol, etc. as necessary, or removing the solvent and replacing it with water. After that, it can be used as an ingredient in hair cosmetics such as shampoos, conditioners, and treatments.

The amount of the polymer of the present invention incorporated into the hair cosmetic is preferably in the range of 0.01 to 5% by weight as a pure polymer content.

The hair cosmetic composition of the present invention is produced by blending, in addition to the above-mentioned polymer of the present invention, other components that are usually included in hair cosmetic compositions, such as a surfactant, an oil agent, a diluting solvent, and the like.

For example, as surfactants, anionic surfactants include EO/PO addition type alkyl/alkenyl ether sulfates, alkyl/alkenyl sulfates, olefin sulfonates, alkanesulfonates, and saturated/unsaturated fatty acids. Salt, EO/PO addition type alkyl/alkenyl ether carboxylate, α-sulfo fatty acid salt/ester, sulfosuccinic acid type surfactant, phosphate ester type surfactant, amino acid type surfactant, carboxylic acid type surfactant As nonionic surfactants, EO/PO/BO adduct type nonionic surfactants, higher fatty acid alkanolamides/alkylene oxide adducts thereof, sugar group nonionic surfactants, etc. are used as cationic surfactants. Long chain alkyl quaternary ammonium salt, mono long chain alkyl quaternary ammonium salt, di long chain alkyl polyoxyethylene quaternary ammonium salt, mono long chain alkyl polyoxyethylene quaternary ammonium salt, bis(hydroxyalkyl) quaternary ammonium salt Examples of amphoteric surfactants include betaine type (carbo, amide, sulfo, hydroxysulfo, amidosulfo), imidacilline type, amidoamino type, etc.

Examples of the oil agent include ester oil, wax, wax ester, hydrocarbon, silicone, silicone derivative, polyoxyalkylene derivative, polyoxyalkylene alkyl ether derivative, higher alcohol, and the like.

Further, examples of the diluting solvent include volatile carriers such as water and lower alcohols.

The hair cosmetics of the present invention may further include other ingredients that are usually added to hair cosmetics, such as protein derivatives, plant extracts such as crude drugs, water-soluble polymer substances, sequestering agents, and preservatives. , disinfectants, humectants such as glycerin, pH
regulator, ultraviolet absorber, antioxidant, oxidizing agent, reducing agent,
Colorants, fragrances, etc. may be added within the range that does not impair the effects of the present invention.

[Examples] Hereinafter, the present invention will be explained in more detail by giving examples, but the present invention is not limited thereto.

Example 1 162.5 g of dimethylaminopropyl methacrylate (0,95
mole), 2-hydroxyethyl methacrylate 6.5g
(0.05 mol), 169 g of ethyl alcohol, and 14 g of azobisisobutyronitrile were added, and the mixture was heated under a nitrogen stream and refluxed for 4 hours to polymerize.

After the polymerization was completed, 5.5 g (0.05 mol) of ethyl bromide was added dropwise from the dropping funnel with care at a temperature below its boiling point, maintained at the addition temperature for 1 hour, and then heated to reflux for 6 hours. A grading reaction was performed.

After the completion of the quaternization reaction, potassium monochloroacetate 119.3
A suspension of 40 wt. After completion of the reaction, the precipitated inorganic salts were filtered out from the obtained viscous suspension using a pressure filter, and the ratio of repeating units of general formulas (I), (n) and (m) was 5/9015. A polymer having an average molecular weight of 120,000 was obtained. Next, this was diluted with water so that the polymer pure concentration was 30% by weight.

Comparative Example 1 General formulas (I), (II) and (I
A polymer having an average molecular weight of 120,000 and having a repeating unit ratio of 0/9515 in II) was obtained, and an aqueous solution having a polymer purity of 30% by weight was obtained.

Example 2 141.3 g (0.90 mol) of dimethylaminoethyl methacrylate and 13.0 g of 2-hydroxyethyl methacrylate were placed in a four-way flask equipped with a reflux condenser, a thermometer, a dropping funnel, a glass tube for nitrogen substitution, and a stirrer.
(0.10 mol), 154 g of ethyl alcohol, and 12 g of azobisisobutyronitrile were added, and the mixture was heated under a nitrogen stream and refluxed for 4 hours to polymerize.

After completion of polymerization, 31.4 g of propyl chloride (0,4
0 mol) was added dropwise from the dropping funnel with care at a temperature below its boiling point, maintained at the addition temperature for 1 hour, and then heated to reflux to carry out a quaternization reaction for 6 hours.

After the completion of the quaternization reaction, 66.3 g of potassium monochloroacetate
A 40% by weight suspension of ethyl alcohol (0.50 mol) was added dropwise from the dropping funnel, and the mixture was further heated under reflux for 6 hours to carry out an amphoteric reaction. After completion of the reaction, the precipitated inorganic salt was filtered out from the obtained viscous suspension using a pressure filter, and the ratio of repeating units of general formulas (1), (II) and (III) was 40150/10. A polymer having an average molecular weight of 150,000 was obtained. Next, this was adjusted to a polymer purity concentration of 30
It was diluted with water to give a weight percent.

Comparative Example 2 The amount of propyl chloride used was 39.3g (0,50
mole), the amount of potassium monochloroacetate used was 53.0g.
A polymer having an average molecular weight of 150,000 and having a ratio of repeating units of general formulas (I), (II), and (III) of 50/40/10 was obtained in the same manner as in Example 2 except that (040 mol) was used. , an aqueous solution with a polymer purity of 30% by weight.

Example 3 146 g of ethyl alcohol and 0.7 g of azobisisobutyronitrile were placed in a four-way flask equipped with a reflux condenser, a thermometer, a dropping funnel, a glass tube for nitrogen substitution, and a stirrer.
936 g (0.60 mol) of dimethylaminoethyl methacrylamide and 52.0 g (0.40 mol) of 2-hydroxyethyl methacrylate were added under reflux under a nitrogen atmosphere.
mol) was added dropwise over 2 hours. After the dropwise addition was completed, 0.7 g of azobis-isobutyronitrile was further added and the mixture was refluxed for 2 hours to polymerize.

After the polymerization, 12.5 g of ethylene bromohydrin (0,
10 mol) was added dropwise from the dropping funnel with care at a temperature below its boiling point, and after maintaining the addition temperature for 1 hour,
The mixture was heated under reflux to perform a quaternization reaction for 6 hours.

After the completion of the quaternization reaction, sodium monochloroacetate 53.3
A 40% by weight aqueous solution of g (0.50 mol) was added dropwise from the dropping funnel and heated under reflux for 6 hours under a nitrogen stream to carry out an amphoteric reaction, resulting in compounds of general formulas (I), (n) and (III). A polymer with an average molecular weight of 500,000 and a repeating unit ratio of 10150/40 was obtained. After the reaction was completed, the mixture was diluted with water so that the solid content including the precipitated inorganic salt was 40% by weight.

Comparative example 3 The amount of each ingredient used was 143g for ethyl alcohol.

Dimethylaminoethylmethacrylamide is 78.0g (
The general formula ( I), (II) and (I
A polymer having an average molecular weight of 600,000 and having a ratio of repeating units of II) of 10/40150 was obtained, and an aqueous solution containing the precipitated inorganic salt and having a solid concentration of 40% by weight was prepared.

Example 4 169 g of ethyl alcohol and 0.8 g of azobisisobutyronitrile were placed in a four-way flask equipped with a reflux condenser, a thermometer, a dropping funnel, a glass tube for nitrogen substitution, and a stirrer.
129.5 g (0.70 mol) of diethylaminoethyl methacrylate) and 2
-Hydroxyethyl methacrylate 39.0g (0,
30 mol) was added dropwise over 2 hours. After the dropwise addition was completed, 0.8 g of azobisisobutyronitrile was further added and the mixture was refluxed for 2 hours to polymerize.

After the polymerization, 32.7 g of ethyl bromide (0,30
mol) was added dropwise from the dropping funnel with care at a temperature below its boiling point, maintained at the addition temperature for 1 hour, and then heated to reflux to carry out a quaternization reaction for 6 hours.

After the completion of the quaternization reaction, the 2-amino-2-
A 40 wt% aqueous solution of 73.4 g (0.40 mol) of methyl-1-propatur salt was added dropwise from the dropping funnel, and heated under reflux for 6 hours under a nitrogen stream to carry out an amphoteric reaction, resulting in a compound of general formula (I). A polymer having an average molecular weight of 300,000 in which the ratio of repeating units of , (II) and (I[[) was 30/40/30 was obtained.

After the reaction was completed, the mixture was diluted with water so that the solid content including the precipitated inorganic salt was 40% by weight.

Comparative Example 4 The amount of each component used was 43.6g (0
General formula (I),
The ratio of repeating units of (n) and (III) is 40/30
/30 and an average molecular weight of 300,000 was obtained, and an aqueous solution containing the precipitated inorganic salt and having a solid concentration of 40% by weight was prepared.

Example 5 136.8 g (0.8 mol) of dimethylaminopropyl methacrylate and 26.0 g of 2-hydroxyethyl methacrylate were placed in a four-way flask equipped with a reflux condenser, a thermometer, a dropping funnel, a glass tube for nitrogen substitution, and a stirrer.
(0.2 mol), 169 g of ethyl alcohol, and 1.4 g of azobisisobutyronitrile were added, and the mixture was heated under a nitrogen stream and refluxed for 4 hours to polymerize.

After the polymerization was completed, 22.0 g (0.2 mol) of ethyl bromide was added dropwise from the dropping funnel with care at a temperature below its boiling point, maintained at the addition temperature for 1 hour, and then heated to reflux for 6 hours. A grading reaction was performed.

After the completion of the quaternization reaction, 79.6 g of potassium monochloroacetate
A suspension of 40% by weight ethyl alcohol (0.6 mol) was added dropwise from the dropping funnel, and the mixture was further heated under reflux for 6 hours to carry out an amphoteric reaction. After the reaction is completed, the precipitated inorganic salts are filtered from the resulting viscous suspension using a pressure filter,
A polymer having an average molecular weight of 200,000 and having a ratio of repeating units of general formulas (I), (II) and (III) of 20760720 was obtained. Next, this was diluted with water so that the polymer pure concentration was 30% by weight.

Example 6 Using the polymer aqueous solution obtained in Example 2 or Comparative Example 2, a shampoo having the following composition was prepared.

Coconut oil fatty acid jetanolamide 5.0 Ethylene glycol distearate 2.0 Example 2
Or polymer aqueous solution of Comparative Example 2 1.0 fragrance
0.5 ethanol
10 purified water
Remaining Amount The above shampoo was subjected to a combing test and a hair styling test based on sensory evaluation using the following method.

The results of each test are shown in Table 1.

(<Street test and hair styling test) Each sample was applied to a 20 g hair bundle, and after shampooing, rinsing, and drying, evaluation was made according to the following criteria.

The comb/brush goes through well. O The comb/brush goes through well. △ The comb/brush goes through poorly. Margin) Table 1 Example 7 Using the polymer aqueous solution obtained in Example 3 or Comparative Example 3, a conditioner having the following composition was prepared.

Hydroxyethylcellulose 0.5 Polymer aqueous solution of Example 3 or Comparative Example 3 05 Propylene glycol 5.0 Cetanol
3.0 fragrance
0.3 Purified water
Regarding the remaining amount of the conditioner above,
The combing test and hair styling test were conducted in the same manner as in Example 6, except that the hair strands were shampooed with a regular shampoo, each sample was applied, rinsed, and evaluated after drying.

The results of each test are shown in Table 2.

Table 2 Example 8 Using the polymer aqueous solution obtained in Example 4 or Comparative Example 4, a shampoo having the following composition was prepared.

A hair test was conducted as in Example 6. In addition, a compatibility test of the polymer with the shampoo system was also conducted by the following method.

The results of each test are shown in Table 3.

(Compatibility test) Appearance was observed with the naked eye and evaluated according to the following criteria: Transparent and dissolved ○ Slightly cloudy △ Cloudy × Table 3 Cocoamidopropyl betaine (30% aqueous solution) Coconut oil fatty acid jetanol Polymer aqueous solution of Amide Example 4 or Comparative Example 4 Fragrance ethanol Purified water Regarding the above shampoo, the remaining amount was tested and adjusted [Effects of the invention] As described above. Furthermore, by using the cationic/ampholytic polymer of the present invention as a component of hair cosmetics such as shampoo rinses, hair cosmetics with good conditioning and hair styling effects can be obtained.

Claims (2)

[Claims] (1) 5 to 40 mol% of quaternized repeating units represented by general formula (I) below, 40 to 90 mol% of amphoteric repeating units represented by general formula (II), and general formula ( A cationic/ampholytic polymer comprising 5 to 40 mol% of repeating units represented by III). ▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (II) (III) [In the formula, R^1 and R^4 is a hydrogen atom or a methyl group,
R^2, R^5 and R^6 are alkylene groups having 1 to 4 carbon atoms, R^3 is an alkyl group having 1 to 4 carbon atoms, benzyl group, 2-hydroxyethyl group, 2,3-epoxypropyl group group, 2-hydroxypropyl group or the following formula -CH_2CH
A^1 and A^2 are oxygen atoms or N
H and X represent a halogen atom or an alkyl sulfate residue. ] (2) A hair cosmetic containing the cationic/ampholytic polymer according to claim 1.