JPH02223509A - Resin composition for hair dressing and aerosol foam type soap-free composition using same composition - Google Patents

Abstract

PURPOSE:To obtain the subject water-soluble composition excellent in smoothness and having setting effect by blending a polymer having a cationized repeating unit and an amphoteric repeating unit in a specified ratio with a water-soluble anionic polymer in a proper weight ratio. CONSTITUTION:An objective water-soluble resin composition for hair dressing prepared by blending a cationic/amphoteric polymer composed of 5-60mol% cationized repeating unit of formula I and 95-40mol% amphoteric repeating unit of formula II [R1 and R4 are H and CH3; R2, R5 and R6 are 1-4C alkylene; R3 is H, 1-4C alkyl, -CH2CH2OH, CH2H(OH)OCH3, CH2C(OH)HCH2, etc.; A1 and A2 are O or NH; X is Br, Cl, I, CH3SO4, etc.] with a water-soluble anionic polymer in (1:2)-(1:10) weight ratio. Using the resultant composition, an aerosol foam type soap-free composition is produced. The produced soap-free composition is free from stickiness and flaking and excellent in smoothness, setting properties and feeling.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a hair styling resin composition and an aerosol foam type soap-free composition using the same.

[Conventional technology]

Conventionally, nonionic, anionic, cationic, amphoteric resins and mixtures of these resins have been used as hair styling resins.

Polyvinylpyrrolidone, polyvinyl methyl ether, and the like are known as nonionic resins. The former has the disadvantage that the formed film is hard before it absorbs moisture, but when it absorbs moisture, it suddenly becomes soft and causes a blocking phenomenon, and the latter is more affected by humidity than the former.

Copolymer resins containing (meth)acrylic acid or the like as an ionic group are known as anionic resins, and there are some that are not so affected by humidity and others that are easily affected by humidity. These have weak affinity for hair, and because the formed film needs to be hard in order to enhance the hair styling effect, they tend to cause flaking and have drawbacks such as lack of smoothness.

Known examples of cationic resins include cationized cellulose, cationized vinylpyrrolidone/dimethylaminoethyl methacrylate copolymer, and polydimethylallylammonium chloride. These have a greater affinity for hair than the first two and also have antistatic properties, but
It is easily affected by humidity and has drawbacks such as precipitation caused by shampoo (anionic type) during hair washing.

Examples of amphoteric ionic resins include octylacrylamide/butylaminoethyl methacrylate/(meth)acrylic acid/(meth)acrylic acid ester copolymer, dialkylaminoethyl methacrylate/butyl methacrylate-1./
Other known examples include monochloroacetic acid amphoteric products of nonionic monomer copolymers. These have a high affinity for hair, and have fewer problems than nonionic and anionic resins, such as adhesion of dirt and dust, and hair entanglement, and their hygroscopicity is lower than nonionic and cationic resins. It has drawbacks such as insufficient setting force under high humidity.

Regarding the mixture system of the above resins, it is possible to combine each resin so that the drawbacks of each resin are compensated to some extent, but
On the other hand, there arises the problem of detracting from the advantages of each resin. Mixtures of anionic resins and cationic resins often become insolubilized due to their contradictory ionic properties, and the high hygroscopicity of cationic resins reduces their setting power under high humidity, and they also have poor affinity for hair. There are disadvantages such as a decrease in Furthermore, although a mixture of an anionic resin and an amphoteric resin has no problem in terms of compatibility, the current situation is that not only the advantages of each resin are diminished, but also the disadvantages are not compensated for.

In addition, regarding the air sole foam type composition, the foam is formed by blending various surfactants and/or foaming agents such as nonionic cellulose with the hair styling resin, which improves the performance of the hair styling resin. It is decreasing. In the above case,
Particularly under high humidity conditions, foaming agents such as surfactants absorb moisture, resulting in lower setting power and increased stickiness.

[Problem to be solved by the invention]

The object of the present invention is to provide a resin composition for hair styling that is free from adhesion and flaking, has excellent smoothness, exhibits excellent setting power under high temperature and high humidity conditions, and does not impair its feel, and an aerosol using the same. An object of the present invention is to provide a foam-type soap-free composition.

[Technical means for solving the problem and their effects] The hair styling resin composition according to the present invention contains 5 to 60 mol% of cationized repeating units represented by the following general formula [I] and the following general formula: The weight ratio of the cationic/amphoteric polymer consisting of 95 to 40 mol% of amphoteric repeating units represented by [II] and the water-soluble anionic polymer is 1:2 to 1:1.
It is characterized by being water-soluble and water-soluble.

(I) R+ (II) -CH2-C- CH, -C- (wherein, R+, R4 are H or CH3°R2, Rs
, R6 is a CH2 to C4H8 alkylene group.

R3 is H, an alkyl group of CH3 to C4H9.

CH2-0, CH2CH20H.

CH2H(OH)’ CCH3 or CH2' CH (OCH2CH2). Oh.

H (However, n = an integer from 1 to 9) A, , A2 is 0 or NH.

X is Br, C1, I, CH3SO4.

C2H1So4. CH3Coo or Cf1CH2Coo. ] The cationic/ampholytic polymer described in (g) can be produced by a method in which monomers corresponding to each repeating unit are polymerized and then cationized and amphoteric, a method in which each monomer is cationized and amphotericized, and then polymerized; A method in which amphoteric monomers are copolymerized with unmodified monomers and then amphotericization is carried out, or a method in which cationization is carried out after copolymerization between amphoteric monomers and unmodified monomers, etc. It can be obtained by

- Dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethyl Aminoethyl (meth)acrylamide and the like can be used in combination or in combination.

In the present invention, - when the repeating unit of formula [I] is less than 5 mol%, the bond between the cationic/ampholytic polymer and the water-soluble anionic polymer becomes weak, resulting in poor smoothness, which is a drawback of water-soluble anionic polymers. is not improved, the flaking phenomenon is not sufficiently reduced, and an aerosol foam type soap-free composition cannot be obtained. In addition, if the repeating unit exceeds 60 mol%, the mixing stability of the cationic/ampholytic polymer and the water-soluble anionic polymer will be poor, and the water solubility of the resin composition that is a mixture of them will also be poor, resulting in poor hair washing properties. It starts to cause problems.

Examples of cationizing agents include acids such as hydrochloric acid, hydrochloric acid, acetic acid, and chloroacetic acid; examples of quaternary cationizing agents include methyl chloride, methyl bromide, methyl iodo, ethyl chloride, ethyl chloride, propyl chloride, and propyl bromide. , ethylene chlorohydrin, ethylenezomuhydrin, epichlorohydrin, shrimp bromohydrin, propylene chlorohydrin, propylene bromohydrin, pencil chloride, benzyl bromide, polyethylene glycol monoepoxide, dimethyl sulfate, diethyl sulfate, and the like.

As the amphoteric agent, for example, sodium monochloroacetate,
Potassium monochloroacetate, lithium monochloropropionate, sodium monochloropropionate, potassium monochloropropionate, monochloroacetic acid and ammonia,
2-amino-2-methyl-1-propatol, monoethanolamine, jetanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-ethyl-1- There are neutralized products such as propatool and morpholine.

The above-mentioned cationizing agents and amphoteric agents are used stoichiometrically, ie, in equimolar amounts, with respect to each monomer.

The monomers corresponding to the respective squeezing units represented by formulas [I] and [H] may be copolymerized in a hydrophilic solvent. As the hydrophilic solvent, water, one or more water-soluble aliphatic alcohols having 1 to 4 carbon atoms, or mixtures thereof are suitable. Note that the solvent composition may need to be selected depending on the solubility of the monomer after modification. The copolymerization may be carried out by an ordinary solution polymerization method, for example, by dissolving the monomer in the above-mentioned solvent, adding a polymerization initiator, and heating and stirring under a nitrogen stream, by appropriately selecting polymerization conditions. Preferred examples of the polymerization initiator include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile.

The monomer is polymerized in a state in which the entire amount is present from the beginning of the polymerization, or by adding it in portions depending on the type and/or amount of the ridge member. It is preferable to use the hydrophilic solvent in such an amount that the concentration of the resulting polymer solution is approximately 30 to 70% by weight. The average molecular weight of the polymer is 10,000 to 5
Preferably, it is 00,000.

In the cationization reaction using an acid, a solution of the acid is added dropwise into a hydrophilic solvent solution of a monomer or polymer under a nitrogen stream while stirring, and the mixture is heated at 60 to 90°C for 0.5 to 2 hours. The quaternary cationization reaction is carried out by injecting a gas or dropping a solution of a quaternizing agent into a solution of a monomer or polymer in a hydrophilic solvent under a nitrogen stream while stirring.
This can be carried out by heating at 0 to 95°C for 2 to 10 hours.

The amphoteric reaction uses an amphoteric agent with a relatively high boiling point, and similarly to the quaternary cationization reaction described above, the amphoteric reaction is carried out in a hydrophilic solvent solution of a monomer or polymer under a nitrogen stream while stirring. This is carried out by dropping an aqueous solution, wood-philic solvent solution or suspension of the curing agent and heating at 70 to 95°C for 2 to 10 hours. If the amphoteric agent is an alkali metal salt such as sodium, potassium, or lithium, the inorganic salt will precipitate as the amphoteric reaction progresses in the aliphatic alcohol. Remove it by means and make it available for use.

On the other hand, when the amphoteric agent is an amine salt or an ammonium salt, the organic salt does not precipitate as the amphoteric reaction progresses, so it can be used as is as a homogeneous solution.

The polymer obtained as described above can be used as it is as a solution in a hydrophilic solvent, or after removing the solvent and replacing it with water. The cationic/ampholytic polymer is in a weight ratio of 1:2 to 1:10 with the water-soluble anionic polymer.
to prepare a hair styling resin composition. If the weight ratio of the cationic/ampholytic polymer exceeds 1:2, the formed film of the anionic polymer and resin composition will become sticky.
When applied to hair, the setting power decreases under high humidity,
- On the other hand, if the blending amount does not reach a weight ratio of 1:10, the formed film will be hard and will not have smoothness when applied to hair.
The feel becomes poor and flaking occurs.

As the water-soluble anionic polymer, the above composition (a)
-- Monomer represented by the general formula % formula % 5 to 40% by weight C In the formula, R
7 is H or CH3, R8 is Cl5HI7~Cl8H37
is an alkyl group. ] (b) At least one monomer selected from the group consisting of acrylic acid, methacrylic acid, and itaconic acid
Use a polymer obtained by solution polymerizing a monomer mixture consisting of 6 to 35% by weight (C) and 25 to 89% by weight of other vinyl monomers in a water-soluble solvent, and adding a water-soluble organic basic substance. Can be done.

In the above, when the blending amount of monomer (a) is less than 5% by weight, the mutual solubility between the anionic polymer and the halogenated hydrocarbon, liquefied petroleum gas, etc. becomes insufficient, and the anionic polymer and resin composition The formed film lacks flexibility, resulting in flaking. On the other hand, when the blending amount exceeds 40% by weight, the anionic polymer becomes poorly soluble in water and the formed film becomes sticky. As intermediate (a),
For example, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, etc. can be used alone or in combination.

Moreover, when the blending amount of monomer (b) is less than 6% by weight, the anionic polymer becomes poorly soluble in water, and the blending amount is 35% by weight.
If the weight percentage is exceeded, the formed film becomes hygroscopic and becomes sticky. As the monomer (b), acrylic acid,
Methacrylic acid and itaconic acid can be used alone or in combination.

Furthermore, the monomer (C) imparts appropriate hardness, flexibility, water solubility, etc. to the formed film, if necessary. Monomer<
Examples of CI include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate,
Tert-butyl (meth)acrylate, acrylonitrile, (meth)acrylamide, styrene, vinyltoluene, vinyl acetate, etc. can be used alone or in combination.

In addition, as another water-soluble anionic polymer, the following composition (d) diacetone acrylamide 5 to 88% by weight (e) 5 to 40% by weight of a monomer represented by the formula % [in the formula, R
9 is H or CH3, and Rto is an alkyl group of C4H9 to C,8H3. ] (f) At least one monomer selected from the group consisting of acrylic acid, methacrylic acid, and itaconic acid.
6 to 35% by weight (g) - 1 to 84% by weight of the monomer represented by the formula % [in the formula, R
1 is H or CR3, and RI2 is an alkyl group of CH3 to C3H7. ] A polymer obtained by solution polymerizing a monomer mixture consisting of the following in a water-soluble solvent and adding a water-soluble organic basic substance can be used.

The above monomer (d) is water-soluble in itself, but has the unique property of becoming a water-insoluble and hygroscopic polymer when homopolymerized. When the amount of monomer (d) is less than 5% by weight, the hydrophilicity of the anionic polymer is insufficient, the affinity for hair is lost, and the solution spreads poorly to hair. On the other hand, if the blending amount exceeds 88% by weight, the formed film of the anionic polymer and resin composition becomes brittle, and the monomer (f), which is a component for improving hair washability, and the hardness of the formed film are reduced. It is also unfavorable in terms of balance with monomer (e), which is a component that maintains compatibility with the agent.

When the amount of monomer (e) is less than 5% by weight, the formed film will lack flexibility, causing flaking. On the other hand, if the blending amount exceeds 40% by weight, the anionic polymer becomes poorly soluble in water and hair washing becomes difficult, and the formed film becomes sticky. As the monomer (e), for example, butyl (meth)acrylate,
Isobutyl (meth)acrylate, tertiary-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, etc. can be used alone or in combination.

When the blending amount of the monomer (f> is less than 5% by weight, the formed film becomes poorly soluble in water; on the other hand, when the blending amount exceeds 35% by weight, the formed film has high hygroscopicity, Significant tackiness.As the monomer (f), acrylic acid, methacrylic acid and itaconic acid can be used alone or in combination.

Furthermore, the monomer (g) provides appropriate flexibility and adhesive strength to the formed film. As the monomer (g), for example, methyl (meth)acrylate, ethyl (meth)acrylate,
Propyl (meth)acrylate, isopropyl (meth)
Acrylate etc. can be used alone or in combination.

It is disclosed in Japanese Patent Publication No. 31238/1983 and Japanese Patent Publication No. 6538/1989 that water-soluble anionic polymers are useful as air seal type or non-gas type setting agents. The above polymer can be produced by using, for example, an aliphatic alcohol having 1 to 4 carbon atoms as a solvent, and using a peroxide such as benzoyl peroxide or an azo compound such as azobisisobutyronitrile as a polymerization initiator. Polymerization is carried out under stirring at or near the boiling point of
It is obtained by neutralizing the polymer solution after polymerization with a water-soluble organic basic substance to make it water-soluble.

Furthermore, as another water-soluble anionic polymer, a polymer obtained by adding a water-soluble organic basic substance to a butyl alcohol and/or isopropyl alcohol ester of vinyl methyl ether and maleic anhydride copolymer can be used. . This polymer is, for example, commercially available r
G A N'rRE Zlis, (USA, G
It can be obtained by adding a water-soluble organic basic substance to A.I. Co., Ltd.).

Although the above-mentioned cationic/ampholytic polymer and water-soluble anionic polymer cannot form a good aerosol foam when used alone, the resin composition according to the present invention made by blending them together can be used in combination with a surfactant. without doing anything,
A good aerosol form can be formed.

For example, the above resin composition has a solid content of 0.5 to 10% by weight.
The resulting aqueous resin solution 80-9
An aerosol form can be obtained by pressurizing 5% by weight of the propellant and 20-5% by weight of the propellant into a resin-coated aluminum can. As the propellant, for example, chlorofluorocarbon gas, liquefied petroleum gas (LPG), solid carbon dioxide, etc. are used alone or in combination. In addition, as additives, higher alcohol esters of higher fatty acids, glycerin,
Plasticizers such as polyethylene glycol, fragrances, polishing agents,
Coloring agents, hair nutrients, etc. are used as appropriate.

For example, by dissolving the above resin composition in water and/or a water-soluble solvent and adding additives for hair styling products, it is possible to create hair styling products such as hair lotions, hair creams, and Hair Miss 1 to (non-gas aerosols). It can be used as a component of ingredients.

Note that the above (meth)acrylic acid means acrylic acid or methacrylic acid, (meth)acrylate means acrylate or methacrylate, and (meth)acrylamide means acrylamide or methacrylamide.

(Examples 1 to 12) Hereinafter, the present invention will be described based on Examples and in comparison with Comparative Examples. In addition, both "%" and "part" described below are weight units.

Table 1 shows the compositions of the cationic/amphoteric polymers used in Examples 1 to 12 and Comparative Examples 1 to 12 (including some that were not cationized or amphoteric).
The monomer composition) is shown together with the composition of the cationizing agent and the amphoteric agent, the average molecular weight of the polymer, and the molar ratio of each repeating unit. In the table, the polymers indicated by "rCA1-4" are within the limited range of claim 1, and the polymers indicated by "rc8-11-14" are outside the limited range of claim 1.

Tables 2 and 3 also include Examples 1 to 10 and Comparative Example 1.
The composition (monomer composition) of the water-soluble anionic polymer used in Examples 1 to 10 is shown together with the composition of the water-soluble organic basic substance.

In the table, the bozu polymer in rAN-]~4'' is within the limited range of claim 2 or 3, and rAN-11~1
The polymers indicated by "4" are outside the scope of claims 2 and 3.

In addition, in Examples 11-12 and Comparative Examples 11-12, rGAN'rRE7, which is another water-soluble anionic polymer, was used.
．． -ES4 was used.

Production method of cationic/amphoteric polymer used in each example and comparative example (polymerization, cationization, amphotericization, and purification method)
The method for producing the water-soluble anionic polymer (polymerization and preparation method) is as follows.

Polymerization method for cationic/amphoteric polymers> Into a fourth flask equipped with a reflux condenser, thermometer, dropping funnel, glass tube for nitrogen substitution, and stirrer, add 100 parts of the monomer corresponding to each repeating unit and 50 parts of ethyl alcohol. 1 part, add 0.6 part of azobisin butyronitrile, and heat at 80°C under nitrogen stream.
The mixture was heated under reflux and polymerization was carried out for 4 hours.

<Method for cationizing a cationic/ampholytic polymer> Following the above polymerization reaction, an ethyl alcohol solution of a cationizing agent is added dropwise from the dropping funnel. If the cationizing agent is an acid,
After the above dropwise addition, the mixture is heated at 70 to 80° C. for 1 hour under a nitrogen stream. When using a quaternary cationizing agent, inject a gaseous body of the quaternary cationizing agent or drop its ethyl alcohol solution in a dropping row F.
The mixture was heated at ℃ for 6 hours to carry out the quaternization reaction.

<Method for Amphotericization of Cationic/Amphoteric Polymer> After the above cationization, an amphotericization reaction is carried out. A 30% ethyl alcohol suspension of sodium monochloroacetate or potassium monochloroacetate as an amphoteric agent is added dropwise from a dropping funnel, and heated at 70 to 80° C. for 6 hours under a nitrogen stream to carry out an amphoteric reaction.

<Purification method for cationic/amphoteric polymers> The polymer solution obtained by the following amphoteric conversion method becomes a viscous suspension with the precipitation of inorganic salts. After diluting this with ethyl alcohol, it is filtered using a pressure filtration machine. The precipitate was filtered out and diluted with ethyl alcohol to give a solid content of 30%.

<Polymerization and preparation method of water-soluble anionic polymer> In a fourth flask similar to the one used in the polymerization described above for cationic/amphoteric polymers, 100 parts of each monomer mixture was added.
, 50 parts of ethyl alcohol, and 1.0 part of benzoyl peroxide were added, and the mixture was heated under reflux at 80° C. under a nitrogen stream to carry out polymerization for 4 hours. Next, an ethyl alcohol solution of a water-soluble organic basic substance is dropped using a dropping funnel, stirring is performed, and ethyl alcohol is added so that the solid content becomes 40%.

Note that r GAN, another water-soluble anionic polymer
TREZ-ESJ is commercially available (7) r GANTREZ
-ES-425J (solid content 50%) was prepared by neutralizing 30% with aminomethyl propatool as described below.

GANTREZ-ES-425 (solid content 50%) 00
g aminomethyl propatool 1.

(Hereinafter referred to as the following margin) Next, each cationic/ampholytic polymer obtained by the recipe L and the water-soluble anionic polymer were mixed in various combinations and blending ratios, and Examples 1 to 12 and Comparative Examples 1 to Each hair styling resin composition according to No. 12 is manufactured.

Regarding the above resin composition, an aerosol foam was prepared according to the recipe F, and each performance was evaluated using the following test and evaluation method. Table 4 shows the results.

<Composition of aerosol foam> Resin composition (solid content) 4 parts Cetyl trimethylammonium chloride fragrance PG Freon-12 0.2 parts 0.05 parts 7 parts 1 part Total 100 parts (Test and evaluation method) (1) Setting power (curl retention) After washing with a commercially available shampoo, treating with a commercially available rinse and air drying length: 22
cm, weighing approximately 2 g, apply an amount of aerosol foam about the size of a quail egg, smooth the foam with your fingers, and then apply a 1. cm diameter hair.
Wrap it around a 2cm curler, dry it at 55-60°C for 30 minutes, cool it in a desiccator, and then unwind it into a spiral.
The test piece was attached to a vertical glass plate (marked with a scale every 0.5 cm) and left in a constant temperature and humidity dryer at 30°C and 90% RH for 10 hours. The position of the tip was recorded, and curl retention was measured based on the following formula.

L-L.

L: Length when the test piece is stretched (L = 22 cm) Lo = Position of the tip of the test piece before placing it in the constant temperature/humidity dryer Lt: 10 hours have passed after being left in the constant temperature/humidity dryer Later position of the tip of the test piece (2) When hair prepared in the same manner as in the evaluation of flaking setting force was combed, the amount of resin that fell off was evaluated as follows.

O: almost no shedding, Δ: little shedding, ×: large shedding (3) The difficulty of combing when evaluating smoothness and flaking was evaluated as follows.

Q: Easy to comb, △: Slightly difficult to comb, ×: Difficult to comb (4) Film properties (cleanability and blocking) Take a certain amount of the aerosol foam solution before adding the propellant onto a glass plate and apply it to the same area. Spread the solution with a crowbar etc. so that The glass plate is left in an atmosphere of 20° C. and 60% RH day and night, and then dried at 60° C. for 1 hour.

Regarding cleanability, the glass plate was immersed in an aqueous solution containing 0.5% commercially available shampoo at 40°C, and the state of dissolution of the film was evaluated as follows.

Dissolved within 0.1 hour, small amount remaining after △ knee time, large amount remaining after X knee time Regarding blocking (adhesiveness), the glass plate was
After being left day and night in a constant temperature/humidity dryer adjusted to 0° C. and 90% RH, it was evaluated by touch as follows.

○: No stickiness, △: Slight stickiness, X: High stickiness (5) Spray a quail egg-sized amount of foamy aerosol foam onto a glass plate, press the foam with your finger, and adjust the elasticity of the foam as shown below. evaluated.

O: Elasticity, △: Slightly lacking in elasticity, ×: No elasticity 6) Spray an amount of foamable aerosol foam about the size of a quail egg onto a filter paper and observe the persistence of the foam state. It was evaluated as follows.

○: Almost no change for 30 seconds or more, △: There is a tendency to shrink after 10 to 30 seconds, X: Defoaming at the same time as injection (A) Feeling Feeling when touching the hair prepared in the same way as in the flaking evaluation was evaluated as above.

○: Flexible and soft to the touch, slightly sticky feeling, ×: Strong feeling of stickiness △: Stiff or sticky feeling or stickiness Performance evaluation of aerosol foam (hereinafter referred to as the following margin) [Effects of the invention] As described above, this book The hair styling resin composition and the aerosol foam type soap-free composition using the same according to the invention are as follows:
It is free from adhesion and flaking, has excellent smoothness, exhibits excellent setting power under high temperature and high humidity conditions, and can produce a hair styling effect without impairing its feel.

2. Procedural amendment to the name of the invention (voluntary) June 1999 02E1 1999 Patent Application No. 044334 and thereafter - Resin composition for hair styling and air sole foam type soap-free composition using the same 3. Amendments are made. Relationship with the patent case Patent applicant address Kyoto prefecture
)'j, 58 Address Name: mbVY Trading Five Type Company Representative Director-2Y V Elbow 4, Agent 603 Patent Applicant Goo Chemical Industry Co., Ltd. Agent Patent Attorney Atsushi Ando 5, Date of Amendment Order (Spontaneous) ) 6. Subject of amendment Contents of amendments to each column of "Claims" and "Detailed Description of the Invention" of the specification (Attachment) (1) The scope of claims shall be amended as shown in the Attachment.

(2) Page 9, lines 4 to 11 of the specification '(I) RI OR2-C- C=0 H3C--N-CH3 X of, r(I) RI CH2--C- -O H3C-N-CH3 X and correct it.

<3) r--CH2CH(OCH2CH2) nOHH" in lines 1 and 2 of page 10 of the specification is replaced with r-CR2CHCH2(OCH2CH2) n 0H
Correct with OHJ.

(4) “Description M, page 18, lines 15-17”
R R2C=CCOORI2 0'' is corrected as r R, □ HzC=CCOR12 ■ 0''.

(Attachment) Amended Claims (1) The cationized repeat represented by the following general formula [II + 5 to 60 mol% of the 3rd position] and the following formula [I
I ] amphisexualized repeat low 95-40
A hair styling resin composition characterized in that it is water-soluble and is made by mixing a cationic/amphoteric polymer and a water-soluble anionic polymer in a weight ratio of 1.2 to 1:10 by mole%.

(Hereinafter referred to as Motoyama Margin) -O -O x co.

[In the formula, R+, R4 are H or CH3゜R2, R5,
RI is an alkylene group of CH2=C,H8.

R3 is H, CH3~C4H! ] Alkyl group.

CH2-0, -CH2CH20H.

〇 -CH2H(OH)CCH3 or CH2CHCH2 (OCH2CH2) OH (However, n = an integer from 1 to 9) A1. A2 is O or NH.

Oh.

X&'iBr　, Cfl, I　, CH35o, .

C2R5SO,I, CH3Coo or Cf1CH2C
It is oo. ] (2) The water-soluble anionic polymer has a composition (a) of -F - 5 to 40% by weight of an immediate polymer represented by the formula % [wherein R
7 is H or CH3, R is an alkyl group of C3HI7 to Cl8837. ] (b) At least one monomer selected from the group consisting of acrylic acid, methacrylic acid, and itaconic acid
A polymer obtained by solution polymerizing a monomer mixture consisting of 6 to 35% by weight (C) and 25 to 89% by weight of other vinyl monomers in a water-soluble solvent, and adding a water-soluble organic basic substance. The hair styling resin composition according to claim 1.

(3) The water-soluble anionic polymer has the following composition (
d) Diacetone acrylamide 5-88% by weight (c) Monomer represented by the formula % 5-40% by weight [in the formula, R
9 is H or CH3, R,. is an alkyl group of C4H9 to Cl8H37. ) (f) at least one monomer selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid
6 to 35% by weight (g) = - Formula % Formula % Monomer 1 to 84% by weight [In the formula, R
1 is H or CH3, and R+2 is an alkyl group of CH3 to C3H7. ] The resin composition for hair styling according to claim 1, which is a polymer obtained by solution polymerizing a monomer mixture consisting of the following in a water-soluble solvent and adding a water-soluble organic basic substance.

(4) An aerosol foam soap-free composition comprising the hair styling resin composition according to claim 1.2 or 3.

that's all

Claims (4)

[Claims] (1) 5 to 60 mol% of cationized repeating units represented by the following general formula [I] and the following general formula [II]
95 to 40 mol% of amphoteric repeating units represented by
1. A resin composition for hair styling, characterized in that it is water-soluble and is made by mixing a cationic/ampholytic polymer consisting of the following and a water-soluble anionic polymer in a weight ratio of 1:2 to 1:10. [I]▲There are mathematical formulas, chemical formulas, tables, etc.▼[II]▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_4 are H or CH_3, R_2, R
_5, R_6 is an alkylene group of CH_2 to C_4H_8, R_3 is H, an alkyl group of CH_3 to C_4H_9, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, -CH_2CH_2
OH, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CH_2H(OH)CCH_3 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, (However, n = integer from 1 to 9) A_1, A_2 are O or NH, X is Br, Cl, I, CH_3SO_4, C_2H_5SO_4, CH_3COO or ClCH_
It is 2COO. ] (2) The water-soluble anionic polymer has the following composition (a)
Monomer represented by general formula ▲ Numerical formula, chemical formula, table, etc. ▼ 5 to 40% by weight [In the formula, R_7 is H or CH_3, R_8 is C_8H_
It is an alkyl group of 1_7 to C_1_8H_3_7. ]
(b) A monomer mixture consisting of 6 to 35% by weight of at least one monomer selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid (c) 25 to 89% by weight of other vinyl monomers The hair styling resin composition according to claim 1, which is a polymer obtained by solution polymerizing in a water-soluble solvent and adding a water-soluble organic basic substance. (3) The water-soluble anionic polymer has the following composition (d)
Diacetone acrylamide 5-88% by weight (e) Monomer represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ 5-40% by weight [In the formula, R_9 is H or CH_3, R_1_0 is C_4
It is an alkyl group of H_9 to C_1_8H_3_7. ]
(f) At least one monomer selected from the group consisting of acrylic acid, methacrylic acid, and itaconic acid 6 to 35% by weight (g) Monomer amount represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ Body 1-84% by weight [In the formula, R_1_1 is H or CH_3, R_1_2 is C
It is an alkyl group of H_3 to C_3H_7. ] The resin composition for hair styling according to claim 1, which is a polymer obtained by solution polymerizing a monomer mixture consisting of the following in a water-soluble solvent and adding a water-soluble organic basic substance. (4) An aerosol foam soap-free composition comprising the hair styling resin composition according to claim 1, 2 or 3.