WO2007061045A1

WO2007061045A1 - Hair treatment containing a powdery emulsifying and thickening agent

Info

Publication number: WO2007061045A1
Application number: PCT/JP2006/323435
Authority: WO
Inventors: Masato Yoshioka; Aiko Takidani; Keiichi Uehara; Yoshihito Kasahara
Original assignee: Seiwa Kasei Company, Limited
Priority date: 2005-11-28
Filing date: 2006-11-24
Publication date: 2007-05-31
Also published as: JP2009040686A

Abstract

A hair treatment which contains a powdery emulsifying and thickening agent containing a composition that comprises 88 to 99% by weight of either (A) a polymer of a monomer (i) having a strongly acid functional group which is partially or completely neutralized or a copolymer of the monomer (i) and other monomer (ii), 1 to 6% by weight of (B) at least one water-in-oil type emulsifying agent, and 0 to 6% by weight of (C) at least one oil-in-water type emulsifying agent and which has a proper viscosity, is excellent in stability and easy of preparation, and can treat the hair without imparting clamminess or bristliness thereto.

Description

Specification

Hair treatment agent containing powdery emulsifying thickener

Technical field

The present invention relates to a hair treatment agent used for hair dyes, hair dyes, permanent wave agents, hair creams, hair straighteners and the like. Specifically, it contains an emulsifying thickener that has an appropriate viscosity for hair treatment agents that require viscosity, is easy to prepare, has excellent stability, and does not give the treated hair stiff or sticky. The present invention relates to a hair treatment agent.

Background art

[0002] Xanthan gum, pectin, gum arabic, maltodextrin, starch, gelatin, which are natural or synthetic thickeners, are generally used to impart viscosity to hair treatment agents such as cream-like jelly cream. Ethyl cellulose, carboxybule polymer, polybulal alcohol, polyethylene oxide and the like are used.

[0003] However, when preparing a hair treatment agent using such a conventional thickener, it takes time to disperse the thickener in an aqueous phase or the like, and the pH is adjusted. In some cases, the preparation was complicated (Patent Document 1, Patent Document 2).

[0004] In addition, hair dyes and permanent wave agents are required to maintain a stable formulation in a wide range of pH 2 to 9 in order to fully exert the effect of the active ingredient. In addition, it is necessary to consider the affinity with water, the anti-dripping property, the effect on dyeing and permanent power, and the feel of the hair after treatment. However, hair treatment agents prepared using conventional thickeners do not always satisfy these requirements (Patent Document 3).

[0005] Further, since conventional thickeners do not have emulsifying ability alone or do not have sufficient emulsifying ability, a combination with other emulsifiers may be necessary.

Patent Document 1: JP 2002-80330

Patent Document 2: JP 2003-73237

Patent Document 3: JP 2003-95881

Disclosure of the invention Problems to be solved by the invention

[0006] The present invention has an appropriate effect such as a hair dye, a hair dye, a permanent hair agent, a hair cream, a hair straightener, etc. It is an object to provide a hair treatment agent that has no damage and is excellent in the feel of the hair after treatment, and does not give the hair any firmness or stickiness.

Means for solving the problem

[0007] As a result of studies conducted by the present inventors to solve the above-mentioned problems, a specific powdery emulsifying thickener can be easily thickened by adding water, and heating and pH adjustment can be performed. It is not necessary, and the hair treatment agent using this powdery emulsifying thickener has excellent stability and can solve the above-mentioned problems that do not give the hair stiffness and stickiness. It came.

[0008] The present invention is a hair treatment agent containing an emulsion thickener,

The emulsion thickener is

(A) a polymer of a monomer (i) having a partially or completely neutralized strong acid functional group, or a copolymer of the monomer (i) and another monomer (ii), which is branched or crosslinked Anionic polymer 88% -99% by weight,

(B) at least one water-in-oil (W / O) type emulsifier of 1% to 6% by weight, and

(C) At least one oil-in-water (O / W) type emulsifier 0 to 6% by weight

The present invention provides a hair treatment agent characterized by being a powdery emulsion thickener containing a powerful composition.

The invention's effect

[0009] The hair treatment agent of the present invention is easy to prepare and excellent in stability, and may impair the original effects of hair dyes, hair dyes, permanent wave agents, hair creams, hair straighteners and the like. And the touch of the hair after treatment is excellent, and the hair is not stiff or sticky. BEST MODE FOR CARRYING OUT THE INVENTION [0010] Examples of the (A) anionic polymer include the following (a) to (c).

(a) Monomeric homopolymers with branched or crosslinked, partially or fully neutralized strong acid functional groups.

(b) Copolymers of mono- and medium-grown monomers having branched or crosslinked, partially or fully neutralized strong acid functional groups.

(c) Monomers having branched or cross-linked partially or fully neutralized strong acid functional groups and monomers having partially or fully neutralized weak acid functional groups.

[0011] The hair treatment agent of the present invention comprises (A) anionic polymer 88 wt% to 99 wt%, (B) at least one water-in-oil (W / O) type emulsifier 1 wt% to 6 wt%. And (C) a powdery emulsion thickener containing a composition comprising 0 to 6% by weight of at least one oil-in-water (O / W) type emulsifier.

[0012] The anionic polymer of component (A) is branched or crosslinked. The expression branched polymer here means a non-linear polymer with pendant chains. By having pendant chains, very high viscosities can be obtained with low velocity gradients when the polymer is dissolved in water. The expression cross-linked polymer means a non-linear polymer that is insoluble in water but swells in water and thus in a three-dimensional network structure resulting in a chemical gel. (A) The anionic polymer contains a cross-linking unit (a cross-linked part) and a Z or branching unit (a part that is branched).

[0013] (A) The strong acid functional group of the monomer (i) forming the anionic polymer is particularly preferably a sulfonic acid functional group or a phosphonic acid functional group. A monomer containing a strong acid functional group is, for example, styrenesulfonic acid, and preferably 2_methyl_2 _ [(1_oxo_2_propenyl) amino] -1_propanesulfonic acid.

[0014] These strong acid functional groups are partially or completely neutralized in the (A) anionic polymer. Neutralization of the strong acid functional group of the monomer forming the anionic polymer is preferably carried out with an alkali metal, such as sodium or potassium, or ammonium, an alkaline alcohol, such as monoethanolamine, . Alternatively, basic amino acids such as lysine may be used. The degree of neutralization is preferably in the range where the pH of a 1% aqueous solution of the powdered emulsifying thickener is 3-9, more preferably in the range of 3.5-8. [0015] (A) Neutral monomers that form anionic polymers include (2-hydroxyethyl) phthalate, acrylamide, methacrylamide, dimethyl acrylamide, (2, 3-dihydroxypropyl) acrylate, (2 -Hydroxyethyl) metatalylate, (2,3-dihydroxypropyl) metatalylate, diacetone acrylamide, and polyoxyethylene ester of acrylic acid with 220 mol of polyoxyethylene group added. One or two selected from the above can be used.

[0016] (A) A monomer having a weakly acidic functional group that forms an anionic polymer is, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, or 3-methylolone 3- [(1-oxo 2 Propenyl) amino] butanoic acid and the like.

[0017] (A) As an anionic polymer, preferred, as a specific example,

Copolymer of 2-methyl 2 [(1 oxo-2-propenyl) amino] 1 propanesulfonic acid and 2-hydroxyethyl acrylate, cross-linked with methylene bis (acrylamide) and partially neutralized with sodium,

2-methyl 2 (1-oxo-2-propenyl) amino] cross-linked with methylenebis (acrylamide) and partially neutralized with sodium] 1 propanesulfonic acid and acrylamide copolymer,

2-Methyl-2-[(1_oxo_2_propenyl) amino] -1 partially crosslinked with methylenebis (acrylamide) and partially neutralized with sodium partially neutralized with propanesulfonic acid and sodium A copolymer of acrylic acid, and

2_Methyl _ 2-[(1 _Oxo _ 2_propenyl) amino]-1 _ propanesulfonic acid homopolymer cross-linked with methylenebis (acrylamide) and partially neutralized with sodium 1 type or 2 types selected from these can be used.

[0018] In particular, among the above (A) anionic polymers, 2-methyl-2-((1-oxo-2-propene) crosslinked with methylene bis (acrylamide) and partially neutralized with sodium. It is more preferable to use a copolymer of (nyl) amino] _1-propanesulfonic acid and 2-hydroxyethyl acrylate.

[0019] The content of the (A) anionic polymer in the composition constituting the powdered emulsion thickener is in the range of 88 wt% to 99 wt%. If this content is less than 88% by weight, sufficient If the content exceeds 99% by weight, it may not be possible to obtain a uniform hair treatment agent in which the anionic polymer is difficult to disperse in the aqueous phase. is there.

[0020] The content of the (B) water-in-oil type emulsifier in the composition constituting the powdered emulsion thickener ranges from 1% by weight to 6% by weight. When the content is less than 1% by weight, when the anionic polymer is synthesized by emulsion polymerization, a uniform reversed-phase microemulsion cannot be formed, and the anionic polymer is nonuniformly polymerized. The hair treatment agent that is uniform and easy to use cannot be obtained. On the other hand, when the content exceeds 6% by weight, the dispersibility of the anionic polymer in the aqueous phase is deteriorated, and there is a fear that a hair treatment agent having sufficient viscosity cannot be obtained.

[0021] The water-in-oil type emulsifier (B) means a surfactant having a sufficiently low HLB to give a water-in-oil emulsion. (B) Water-in-oil type emulsifiers include sorbitan esters such as sorbitan isostearate, sorbitan monooleate, sorbitan monooleate ethoxylated with 5 moles of ethylene oxide (5EO), and diethoxylated (2EO ) Oleocetyl alcohol, sorbitan sesquioleate, or polyethylene glycol poly (hydroxystearic acid) block copolymer.

[0022] The oil-in-water type emulsifier (C) means a surfactant having a sufficiently high HLB value to give an oil-in-water emulsion. (C) As an oil-in-water type emulsifier, ethoxylated sorbitan ester, for example, polyoxyethylene sorbitan monostearate or polyoxyethylene sorbitan monooleate mixed with 20 mol ethylene oxide (20EO), 25 mol Polyoxyethylene sorbitan trioleate ethoxylated with ethylene oxide (25EO), castor oil ethoxylated with 40 moles ethylene oxide (40EO), ethoxylated with 7 moles ethylene oxide (7E〇) Lauryl alcohol or decaethoxylated (10EO) oleocetyl alcohol.

[0023] (C) An oil-in-water type emulsifier constitutes a powdered emulsion thickener in order to improve the dispersibility of an anionic polymer in an aqueous phase and obtain a uniform and smooth hair treatment agent. Composition It can be blended in the range of 0 to 6% by weight. Therefore, the total amount of the (B) water-in-oil type emulsifier and the (C) oil-in-water type emulsifier is in the range of 1 wt% to 12 wt%.

[0024] The preferred range of the amount of (C) the oil-in-water type emulsifier incorporated in the composition constituting the powdered emulsion thickener is (A) the dispersibility of the anionic polymer in the aqueous phase. Depends on. (A) The dispersibility of the anionic polymer in the aqueous phase varies depending on the HLB and amount of the (B) water-in-oil type emulsifier. For example, as long as the (B) water-in-oil type emulsifier does not interfere with the dispersion of the (A) anionic high molecular weight into the aqueous phase, the (C) oil-in-water type emulsifier may be blended. On the other hand, it is preferable that (C) the oil-in-water type emulsifier is appropriately blended so long as the dispersion of the anionic polymer in the aqueous phase is prevented and a non-uniform hair treatment agent can be formed. However, it is not preferable to add more than 6% by weight of (C) oil-in-water type emulsifier because it may interfere with the original performance of the hair treatment agent.

[0025] The powdery emulsifying thickener comprises an aqueous solution containing a monomer (i), a cross-linking agent or a branching agent, and, if necessary, another monomer (ii) and appropriate additives, and (B) at least one oil. (D) After emulsification in oil in the presence of a water-in-water emulsifier, an emulsion is obtained. Then, a polymerization initiator is added to the emulsion to start the polymerization reaction, and then the polymerization reaction is accelerated. After completion of the polymer emulsion, the polymer emulsion can be distilled and concentrated, and then dried by a method such as spray drying or freeze drying. According to this method, it is possible to obtain a powdery emulsifying thickener because it is pulverized during drying without providing a special pulverization step.

[0026] In the above production process, (C) the oil-in-water emulsifier can be added to, for example, the polymer emulsion immediately after the completion of the polymerization reaction. The powdery emulsified thickener obtained by the above manufacturing process, there may force ^s were used in the manufacturing process water and (D) oil slightly remained.

[0027] Examples of the oil (D) include liquid paraffin, squalane, hydrogenated polyisobutene, octyl palmitate, isostearinoreisostearate, isododecane and isohexadecane.

[0028] As a crosslinking agent or branching agent to be added, bifunctional or trifunctional or higher HC = CR- The compound which has group represented by these is illustrated preferably. More specifically, methylene bis (acrylamido), ethylene glycol dimetatalylate, diallyloxyacetic acid or a salt thereof, ethylene glycol ditalylate, diallylurea, trialinoleamine, or trimethylolpropane tritalylate and a mixture thereof. Examples thereof can be used, and those selected from these are preferably used.

[0029] The addition amount of the crosslinking agent or branching agent is preferably in the range of 0.005 mol% to 1 mol%, based on the total number of moles of the monomer (i) and the other monomer (ii). Preferably 0.01 mole ⁰ /. ~ In the range of 0 - 5 mole ^_0/0, more preferably 0 - 01 mole ⁰ /. ~ 0.5 in the range of 25 mole ^_0/0. When the addition amount of the crosslinking agent or branching agent is less than the above range, a three-dimensional network structure that provides sufficient emulsification and thickening power cannot be formed. On the other hand, when the amount of the crosslinking agent or branching agent added is larger than the above range, a strong three-dimensional network structure is formed, so that the swelling of the anionic polymer in the aqueous phase is inhibited and the hair treatment agent is used. There is a risk that an appropriate viscosity cannot be given.

[0030] As the powdery emulsifying thickener to be included in the hair treatment agent of the present invention, a commercial product sold under the trade name of SEPINOV EMT 10 from Sepic Co. can be used.

[0031] The content of the powdered emulsion thickener used in the hair treatment agent is preferably such that the ratio of the total amount of (A), (B) and (C) to the total amount of the hair treatment agent is 0.:! To 20% by weight, more preferably 0.5 to 10% by weight. If the content is less than 0.1% by weight, the viscosity imparted to the hair treatment agent may be insufficient, and if it exceeds 20% by weight, an effect commensurate with the increase in the content cannot be obtained. On the other hand, if the amount exceeds 20% by weight, the treated hair may tend to be stiff or sticky.

[0032] The hair treatment agent of the present invention includes (A) an anionic polymer compound, (B) a water-in-oil system, such as conventional hair dyes, hair dyes, permanent wave agents, hair creams and hair straighteners. It is prepared by adding a powdery emulsifying thickener containing a composition comprising an emulsifier of type C and an oil-in-water type emulsifier.

[0033] The hair treatment agent of the present invention can be appropriately mixed with other components as long as the effects of the present invention are not impaired. Such components include, for example, oily raw materials such as fats and oils, waxes, hydrocarbons, ester oils, silicone oils, fatty acids, lower alcohols, Class alcohols, polyhydric alcohols, surfactants, hydrolyzed proteins and their derivatives, amino acids, polypeptides, sugars, polymers, powders, colorants, UV protection agents, vitamins, animals and plants Extracts, antioxidants, disinfectants, antiseptics, acids, penetration enhancers, pH buffering agents, anti-inflammatory agents, sequestering agents, fragrances, hair growth agents, skin roughening agents, anti-aging agents and the like.

[0034] Specific examples of the oil-based raw material include olive oil, macadamia nut oil, cocoon oil, medow ohm oil, hyoretic sunflower oil, hyorek safflower oil, castor oil, jojoba oil, power lunauba wax, candelilla wax, lanolin, rice bran wax, Liquid paraffin, isoparaffin, squalane, petrolatum, ceresin, glycerol tri-2-ethylhexanoate, glycerol triisostearate, glycerol triisopalmitate, tetra-2-ethylhexanoate pentaerythritol, tri-2-ethylhexanoic acid Trimethylolpropane, diisostearyl malate, 2-ethylhexyl palmitate, cetyl 2-ethylhexanoate, isostearyl isostearate, dimethylpolysiloxane, methylphenylpolysiloxane, decame Examples include tilcyclopentasiloxane, ceramides, and silicone oils.

[0035] Examples of fatty acids include octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, isostearic acid, isopalmitic acid, 12-hydroxystearic acid, Examples include ricinoleic acid, resin acid, hydrogenated resin acid, abietic acid, rosin, disproportionated rosin, hydrogenated rosin, and tetrahydroabietic acid.

[0036] Examples of lower and higher alcohols include ethanol, propyl alcohol, octanore, laurinorenoreconole, myristinoleanoreconole, nonremitinoleanoreconole, stearyl alcohol, isostearyl alcohol. , 2-Otaclide decanol, Oleira Noreco Nore, Beheninore Noreco Nore, Nochinore T Reco Nore, Quiminole T Reco Nore, Cholesterol Nore, Phytosterol, etc. , For example, glycerin, diglycerin, propylene glycol, dipropylene glycol, polypropylene glycol

, Diethylene glycolol, triethylene glycolol, polyethylene glycolol, 1,3-butylene glycol, sonorebitol, erythritol, maltitol and the like.

[0037] Hydrolyzed proteins and their derivatives include protein partial strength silk, coller , Keratin, casein, concholine, soy protein, wheat protein, rice protein, sesame protein, pea protein, etc., and hydrolyzed protein derivatives are cationized, acylated, Examples include esterification and chilled silk.

[0038] Nonionic surfactants for the surfactant include, for example, polyoxyethylene alkenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, Examples thereof include oxyethylene hydrogenated castor oil, polyoxyethylene sorbitol tetrafatty acid ester, glycerin fatty acid ester, sorbitan fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, alkylpolyglycoside, and polyether-modified silicone.

[0039] Examples of the anionic surfactant include fatty acid sarcophagus, alkane sulfonate, alkyl sulfate, polyoxyethylene alkyl ether sulfate, fatty acid alcohol amide sulfate, fatty acid monoglyceride sulfate, alkyl phosphate Salts, polyoxyethylene alkyl ether phosphate, N-acyl glutamate, and acyl N-methyl taurate. Examples of cationic surfactants include tetraalkyl ammonium salts and fatty acid amidoamine salts.

[0040] Examples of amphoteric surfactants include alkyl glycine salts, N-acylaminoethyl-N-2-hydroxyethylidaricin salts, fatty acid amidopropyl betaines, N-alkyl-N, N-dimethylammonites. Examples thereof include N-propyl sulfonate, phosphatidylcholine, phosphatidylinositol, phosphatidylethanolamine, phosphatidinole glycerol, lysolecithin, and lecithin. In addition, high molecular type and natural surfactants are also included.

[0041] Examples of the polymers include sodium polyacrylate, carboxybulle polymer, vinylpyrrolidone polymer, polybulal alcohol, polyacrylolamide, amino-modified silicone, methinoresenorelose, and ethinorescenole. Loin, hydroxy ethenorescenellose, canoleboxy methylcellulose, sodium alginate, sodium hyaluronate, carrageenan, xanthan gum, agar, guar gum, quince seed gum, tamarind gum, starch, dex Examples include trin, locust bean gum, chitosan, cationized cellulose, cationized guar gum, and polyethylene glycol.

[0042] Examples of UV protection agents include 2-methoxyhexyl paramethoxyketiate, 4-t-butyl_4-methoxybenzoylmethane, paradimethylaminobenzoic acid, homomentinolic salicylate, diparamethoxykeido. Octyl arsenate, hydroxymethoxybenzophenone, hydroxymethoxybenzophenone sulfonate, 2, 4, 6 trianilino p- (carbo-2-ethylhexyl _ 1 _oxy) _ 1, 3, 5_triazine Etc.

[0043] Examples of vitamins include vitamin A, vitamin C, vitamin E, and derivatives thereof, and examples of plant extracts include peonies extract and button peel extract.

Example

[0044] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to these examples. In the following examples and comparative examples, the amount of each component is based on parts by weight.If the amount is not a solid content, the solid content is indicated in parentheses after the component name. Indicates the concentration. The concentration of the solution or dispersion is% by weight.

[0045] Production Example 1

The following were put in a beaker and mixed to prepare an aqueous phase.

2_Methyl _ 2_ [(1 _Oxo _ 2_propenyl) amino] — 1 _50% aqueous solution of sodium salt of propanesulfonic acid; 608.8 g

2 Hydroxyethyl acrylate: 72.6 g

Methylenebis (acrylamide); 0 · 301g

Furthermore, the pH of the aqueous phase was adjusted to 3.5 by adding 0.7 g of 2-methyl-2-[(1-oxo-2-propenyl) amino] -1-propanesulfonic acid.

[0046] In parallel, the organic phase was prepared by mixing the following components in a beaker.

Isohexadecane; 220g

Sorbitan oleate; 22g Azobis (isobutyronitrile); 0.2 g

[0047] The aqueous phase was gradually introduced into the organic phase, and strong mechanical stirring was performed with an Ultra_turrax (IKA, trade name) machine commercially available from IKA to obtain an emulsion. Next, the obtained emulsion was transferred to a polymerization reactor. A large amount of nitrogen was bubbled through the emulsion to remove oxygen and cooled to about 5-6 ° C.

[0048] After the emulsion solution was sufficiently stirred and homogenized well, 30 ml of a 0.002% aqueous sodium metabisulfite solution was added at a flow rate of 0.5 ml / min. During this addition, the temperature of the polymerization reactor was raised to the final polymerization temperature, maintained at this temperature for 90 minutes, and then cooled to a temperature of 35 ° C.

[0049] Next, 22 g of polyoxyethylene sorbitan monostearate (20EO) was slowly added. Thereafter, the reaction medium was spray-dried to obtain a powdery emulsifying thickener 1.

[0050] Production Example 2

The following were put in a beaker and mixed to prepare an aqueous phase.

Deionized water; 80. Og

48% by weight aqueous sodium hydroxide solution; 95. Og

2-Methyl-2-[[(1-Oxo-2-propenyl) amino]-1-propanesulfonic acid; 246.7 g

50% by weight acrylamide aqueous solution; 253.8 g

Sodium diethylenetriaminepentaacetate; 0.18g

Trialinolamin; 0. 61g

Ammonium persulfate; 0.34 g

[0051] The amount of the aqueous phase was adjusted to 682 g by adjusting the pH of the aqueous phase described above to 5.2 and collecting deionized water.

[0052] In parallel, the organic phase was prepared by mixing the following in a beaker.

Isohexadecane; 220g

Sorbitan isostearate; 7.5g

[0053] Gradually introducing the aqueous phase into the organic phase, the Ultra- turrax (IKA) available from IKA A powerful mechanical agitation was carried out using a machine (trade name, company name) to obtain an emulsion. Next, the obtained emulsion was transferred to a polymerization reactor. In order to remove oxygen, a large amount of nitrogen was bubbled through the emulsion and cooled to about 5-6 ° C.

[0054] After the emulsion solution was sufficiently stirred and homogenized well, 30 ml of a 002% aqueous solution of sodium metabisulfite was added at a flow rate of 0.5 ml / min. During this addition, the temperature of the polymerization reactor was raised to the final polymerization temperature, maintained at this temperature for 90 minutes, and then cooled to a temperature of 35 ° C. Thereafter, this reaction medium was spray-dried to obtain a powdery emulsion thickener 2.

[0055] Production Example 3

The following were put in a beaker and mixed to prepare an aqueous phase.

200g deionized water

48% by weight aqueous sodium hydroxide solution; 112. lg

2-Methyl-2-[[(1-Oxo-2-propenyl) amino]-1-propanesulfonic acid; 278. 4g

Acrylic acid; 73. lg

Sodium diethylene polyamine pentaacetate; 0.18g

Methylenebis (acrylamide) 0 · 182g

The pH of the above aqueous phase was adjusted to 4.0 and deionized water was added to bring the amount of aqueous phase to 682 g.

[0056] In parallel, the organic phase was prepared by mixing the following components in a beaker.

Isohexadecane; 220g

Sorbitan oleate; 22g

Azobis (isobutyronitrile) 0.2 g

[0057] The aqueous phase was gradually introduced into the organic phase, and strong mechanical stirring was performed with an Ultra_turrax (IKA, trade name) machine commercially available from IKA to obtain an emulsion. Next, the obtained emulsion was transferred to a polymerization reactor. A large amount of nitrogen was bubbled through the emulsion to remove oxygen and cooled to about 5-6 ° C.

[0058] After the emulsion solution was sufficiently stirred and homogenized well, 30 ml of a 002% aqueous solution of sodium metabisulfite was added at a flow rate of 0.5 ml / min. During this addition, the polymerization reactor The temperature was raised to the final polymerization temperature and maintained at this temperature for 90 minutes before cooling to a temperature of 35 ° C.

[0059] Next, 20 g of polyoxyethylene sorbitan monooleate (20E0) was slowly added. Thereafter, this reaction medium was spray-dried to obtain a powdery emulsion thickener 3.

[0060] Next, the usefulness of various hair treatment agents containing the above-described production examples:! To 3 in the form of powdered emulsion thickeners:! To 3 will be described.

[0061] Example 1, Comparative Example 1

Acid hair dyes were prepared with the compositions shown in Table 1 below, and were comparatively evaluated.

[0062] [Table 1]

* Seiwa Kasei Co., Ltd., Promois Silk A (trade name)

[0063] The acid hair dyes of Example 1 and Comparative Example 1 shown in Table 1 were evaluated for ease of preparation, thickening property, and operability when applied to hair (smooth adhesion, but softness of application). . The evaluation results are shown in Table 2. The evaluation criteria are as shown below. The evaluation of thickening was made based on the appearance of the hair dye when the hair dye was put on a hair comb.

[0064] [Evaluation Criteria]

Ease of preparation;

◯: Can be prepared in a short time

Δ: takes time but can be prepared X: Cannot be prepared

Thickening;

○: There is viscosity and there is no dripping when taken in a comb.

△: Force with viscosity Dripping from comb

X: falls from the comb

Operability during application;

◯: Can be applied smoothly to hair and has good adhesion

Δ: Force that can be applied to hair Adhesion is poor

X: Feeling friction when applied to hair

[Table 2]

[0066] The acidic hair dye of Example 1 blended with the powdered emulsifying thickener 1 of Production Example 1 can be easily prepared as compared with the acidic hair dye of Comparative Example 1, has an appropriate viscosity, and is suitable for hair. The hair dye had good adhesion when applied and immediately.

[0067] Example 2, Comparative Example 2

After preparing the first oxidized hair dye having the composition shown in Table 3, each was mixed with two oxidized hair dyes having the composition shown in Table 4 at 1: 1 (weight ratio) for comparative evaluation.

[0068] [Table 3] Oxidative hair dye 1st agent Example 2 Comparative example 2 Powdered emulsification thickener of production example 1 1 3.2

Carboxypropyl polymer 3.2

Parafini Nilemin 0. 5 0. 5

Paraaminophenol 0. 2 0. 2

Ortoaminophenol 0. 2 0. 2

Metaaminophenol 0. 3 0. 3

Resorcin 0. 6 0. 6

Propylene glycol 10 0 10 0 Isopropanol 10 0 10 0 Ninatrime edetate 0.3.0.3

Monoethanolamine (80%) 6. 0 6. 0

Ammonia water (28%) 5. 0 5. 0

S-L'Fenoki Shetano paraoxybenzoate 0. 2 0. 2

Mixture *

Dimethylpolysiloxane 0.5 0.5 0.5

20% aqueous solution of hydrolyzed keratin * * 5. 0 5. 0

Purified water Total 100 Total 100

* Seiwa Kasei Secepto H Co., Ltd. (trade name)

* * Seiwa Kasei Co., Ltd., Promois WK—GB (trade name) [Table 4]

* Monyu Nobu 68 (trade name) manufactured by Sepic Co., Ltd. About the first oxidation hair dye of Example 2 and Comparative Example 2 above, the mixing of the hair with the second oxidation hair dye (easy mixing) ), Uniformity of the mixture, viscosity of the mixture, and operability when applied to hair (smooth adherence and softness of application). The evaluation results are shown in Table 5. The evaluation criteria are as shown below. In addition, evaluation of viscosity Judgment was made based on the appearance of the hair dye when taken into a hair dye comb.

[0071] [Evaluation Criteria]

Ease of mixing;

○: Can be mixed in a short time

Δ: Time is required but mixing is possible

X: Cannot be mixed

Homogeneity of the mixture;

○: Uniform

Δ: Lumps are formed during mixing, but uniform if mixed well

X: lump remains

Viscosity;

○: There is viscosity and there is no dripping when taken in a comb.

△: Force with viscosity Dripping from comb

X: falls from the comb

Operability during application;

◯: Can be applied smoothly to hair and has good adhesion

Δ: Force that can be applied to hair Adhesion is poor

X: Feeling friction when applied to hair

[0072] [Table 5]

[0073] Both the oxidized hair dye first agent of Example 2 and Comparative Example 2 kept an appropriate viscosity stably when mixed with the second agent. However, when the first part of the oxidized hair dye of Comparative Example 2 was mixed with the second part, it took time, and the lump remained in the mixture and did not become uniform. On the other hand, when the first oxidation hair dye of Example 2 is used, it can be easily prepared, and the average A uniform mixture was obtained. In addition, when applied to the hair, when the first oxidized hair dye of Comparative Example 2 was used, it could not be applied smoothly, whereas the oxidized hair dye of Example 2 When one agent was used, it could be applied smoothly.

[0074] Example 3, Comparative Example 3

A cold two-bath hair straightener 1st agent having the composition shown in Table 6 and a 2nd agent having the composition shown in Table 7 were prepared for comparative evaluation.

[0075] [Table 6]

* Seiwa Kasei Co., Ltd. Seiseto H (trade name)

* * Seiwa Kasei Co., Ltd., Promois WK— G B (trade name)

[0076] [Table 7]

Cold double bath hair straightener 2nd agent Example 3 Comparative example 3 Powdered emulsifying thickener of production example 1 1 3.2-Carboxyvinyl polymer 1 3.2 Propylene glycol 10. 0 10. 0 Isopropanol 10. 0 10. 0 Disodium edetate 0. 3 0. 3 Hydrogen peroxide solution (35%) 6. 0 6. 0 Cyanic anhydride 0. 05 0. 05 Trisodium trihydrate of citrate 0. 15 0 15 S-Phenoxyeta paraoxybenzoate 0. 2 0. 2 Nord mixture *

Dimethylpolysiloxane 0.5 0.5 0.5 Hydrolyzed keratin 20% aqueous solution * * 5. 0 5. 0 Purified water Total 100 Total 100

* Seiwa Chemical Co., Ltd., Secepto H (trade name)

* * Seiwa Kasei Co., Ltd., Promois WK—GB (trade name)

[0077] Regarding the first and second cold two-bath hair straighteners of Example 3 and Comparative Example 3 above, ease of preparation, viscosity, operability when applied to hair (smooth adhesion, etc.) The applicability was evaluated. The evaluation results are shown in Table 8. The evaluation criteria are as shown below. The evaluation of the viscosity was made based on the appearance of the hair straightener when the mixture was taken into a comb.

[0078] [Evaluation Criteria]

Ease of preparation;

◯: Can be prepared in a short time

Δ: takes time but can be prepared

X: Cannot be prepared

Viscosity;

○: There is viscosity and there is no dripping when taken in a comb.

△: Force with viscosity Dripping from comb

X: falls from the comb

1: Cannot be determined because preparation is not possible

Operability during application;

◯: Can be applied smoothly to hair and has good adhesion Δ: Power that can be applied to hair Adhesion is poor

X: Feeling friction when applied to hair

1: Cannot be determined because preparation is not possible

[0079] [Table 8]

[0080] The cold two-bath hair straightener No. 1 of Example 3 was good and evaluated in all items.

On the other hand, the lj of Comparative Example 3 had viscosity, but was not easy to prepare and had a problem in operability during coating. Furthermore, in the second agent, which is an acidic formulation, the preparation of Comparative Example 3 was impossible, whereas in Example 3, there were problems in all items. In other words, the acidic formulation of the second agent using hydrogen peroxide as the oxidizing agent showed the excellent characteristics of the powdered emulsion thickener 1.

[0081] Example 4

A hair cream having the following composition was prepared, and the feeling of use when applied to the hair and hair was evaluated.

[0082] [Table 9]

Hair cream Example 4

Powdered emulsion thickener of production example 2 2 0.1

Cetostearyl glucoside · cetostearyl alcohol * 3.0

Coconut oil fatty acid hydrolyzed collagen strength aqueous solution (36%) * * 0. 3

Hydrolyzed collagen aqueous solution (30%) * * * 3. 0 2_Hexyldecyl stearate 8.0

Isopropyl myristate 2.0

Phenylmethyl polysiloxane 0.5

Polyoxyethylene (25) Cetyl ether 0.7 Stearic acid 1.0 Triethanolamine 0.1

Preservative ¾ amount Purified water Total 100

* Made by Sepic, Mon Yunobu 68 (trade name)

* * Seiwa Kasei Co., Ltd. Promo ECP (Product Name)]

* * * Promose WU-32R (trade name) manufactured by Seiwa Kasei Co., Ltd.]

[0083] The hair cream of Example 4 can be easily prepared by simply mixing the respective raw materials at room temperature. When the hair cream is picked up and applied to the hair, it is easy to apply to the hand and is easy to spread. Immediately after the treatment, the hair was smooth and well-organized.

[0084] Example 5

A permanent wave first liquid having the following composition was prepared, and the viscosity of the preparation and the finished state of the wave and hair after permanent-to-wave treatment were evaluated.

[0085] [Table 10]

Permanent liquid 1st Example 5

Powdered emulsifying thickener in Production Example 3 3 0. 3 Ammonium thioglycolate (50%) 12. 0

Monoethanolamine (80%) 1. 0 Isopropanol 5. 0 Polyoxyethylene (5) Alkylphenyl ether 3.0 Sodium edetate 0.1 Sodium water 3.0

(Hydrolyzed silk / PG-propylmethylsilanediol) 0.1

Spiromer mono-aqueous dispersion (75%) *

Coconut «ΚΙ«!) [1 Hydrolysis aqueous collagen sodium solution (36%) * * 0.5 Sodium hydroxide 0.63 Preservative Suitable weight Purified water meter 100

* Seiwa Kasei Co., Ltd. PROTES I L LH (trade name)

* * Seiwa Kasei Co., Ltd. Promose ECS (trade name)

[0086] Permanent wave treatment was performed on the hair using the first liquid of the permanent wave agent of Example 5 and a 6% aqueous solution of sodium bromate as the second liquid, and the prepared first liquid was applied to the hair. The hair that was easy to clean was kept stable, and the hair after the permanent wave treatment had a uniform wave and a smooth, moist feeling.

[0087] Example 6, Comparative Example 4

Acid hair dyes having the compositions shown in Table 11 below were prepared and subjected to comparative evaluation.

[0088] [Table 11]

[0089] Ease of preparation and thickening of the acidic hair dyes of Example 6 and Comparative Example 4 shown in Table 11 And operability during application to hair (smooth adherence and applicability) were evaluated based on the same evaluation criteria as in Example 1. Table 12 shows the results of the evaluation.

[Table 12]

[0091] The acidic hair dye of Example 6 blended with a powdery emulsifying thickener can be prepared more easily than the acidic hair dye of Comparative Example 4, has an appropriate viscosity, and is easily applied to hair. The adhesion of the hair dye was good.

[0092] Example 7

Prepare the first and second oxidized hair dyes with the following composition, the stability of their respective viscosities, the mixing of the first and second agents, the operability when applied to the hair, The hair dyeing property was evaluated.

[0093] [Table 13]

Oxidative hair dye 1st agent Example 7

(Ingredient)

SEP I NOV EMT 1 0 氺 1 3.5

Palaf Enirangeamin 0.5

Paraaminophenol 0.2

Ortominophenol 0.2

Metaaminophenol 0.3

Resorcin 0.6

Dimethylpolysiloxane 0.5

Propylene glycol 10.0

Isopropanol 10.0

Edetate disodium 0.3

Monoethanolamine solution (80%) 6.0

Ammonia water (28%) 5. 0

PROTES I L LH * 3 0. 1

Promois WK * 4 5. 0

Preservative weekly dose

Purified water total 100

[0094] [Table 14]

[0095] The first and second oxidation hair dyes of Example 7 were each kept at a suitable viscosity stably, and the first and second agents were mixed at 1: 1 (weight ratio). When evenly mixed and immediately applied to the hair, it can be applied smoothly, without affecting the hair dyeing power inherent to the oxidized hair dye, and without causing the hair after hair coloring to be smooth. Added.

[0096] Example 8 Prepare the 1st and 2nd hair straighteners with the following composition, evaluate the stability of each viscosity, evaluate the operability when applied to the hair, and evaluate the function of the hair after treatment. Went.

[0097] [Table 15]

[Table 16] Hair straightener 2nd liquid Example 8

(Ingredient)

S E P I NOV EMT 1 0 * 1 2. 4

Liquid paraffin # 7 0 1 0. 0

Behenyl alcohol 0.6

Cetostearyl alcohol 4.5

POE (40) Setiljetel 2.0

POE (30) Setilje Itel 0.5

Dimethicone (1 00 c s) 1.0

Sodium bromate 7.0

Edetate tetrasodium 0.2

Chenic anhydride 0. 0 5

Cenaic acid trisodium trihydrate 0. 1 5

Alkyltrimethylammonium chloride (80%) 0.6

Promois S _CAQ * 5 1. 0

Seyce 卜 H 0.5

Purified water total 100 [0099] When the first and second liquids for straightening of the hair straightener of Example 8 were prepared, they had a suitable viscosity for treating the hair, had excellent stability, and had good adhesion to the hair. The hair after hair straightening did not become stiff and had a moist feeling.

[0100] Example 9

[0101] [Table 17]

[0102] The hair cream of Example 9 can be easily prepared by simply mixing the respective raw materials at room temperature. When the hair cream is picked up and applied to the hair, it can be easily applied to the hand and easily applied. Immediately after the treatment, the hair was smooth and well-organized.

[0103] Example 10

[0104] [Table 18] Ingredients of the first liquid of the permanent agent Example 10

S EP I NOV EMT 10 * 1 0. 3

Ammonium thioglycolate (50%) 12. 0

Monoethanolamine (80%) 1. 0

Isopropanol 5.0

Polyoxyethylene (5) Alkyl phenyl ether 3.0

Edetic acid disodium 0.1

Ammonia water 3.0

P ROTE S I L LH * 3 0. 1

Promois ECS * 9 0. 5

Sodium hydroxide 0.63

Preservative appropriate amount

Purified water total 100

[0105] Permanent wave treatment was performed on the hair using the first liquid of the permanent wave agent of Example 10 and a 6% aqueous solution of sodium bromate as the second liquid, and the prepared first liquid was applied to the hair. The easy viscosity was kept stable, and the hair after the permanent wave treatment had a uniform wave and a smooth, moist feeling.

[0106] Among the components used in the above Examples, the details of those marked with * 1 to * 9 are as follows.

* 1: 2-Methyl 2-[((1-Oxo 2-propenyl) amino] —powder emulsifying thickener containing a copolymer of 1-propanesulfonic acid and 2-hydroxyethyl acrylate (Sepic) Made)

* 2: Hydrolyzed silk ethyl 20% ethanol solution (manufactured by Seiwa Kasei Co., Ltd.)

* 3: (Hydrolyzed silk / PG-propylmethylsilanediol) Crosspolymer 75% aqueous dispersion (Seiwa Kasei Co., Ltd.)

* 4: Hydrolysis keratin 25% aqueous solution (manufactured by Seiwa Kasei)

* 5: 20% aqueous solution of cocodimonium hydroxypropyl hydrolyzed synolec (manufactured by Seiwa Kasei Co., Ltd.)

* 6: A mixture of cetearyl darcoside and cetearyl alcohol (manufactured by Sepic)

* 7: Palm oil fatty acid hydrolyzed collagen potassium 36. /. Aqueous solution (manufactured by Seiwa Kasei Co., Ltd.) * 8: Hydrolyzed collagen 30% aqueous solution (manufactured by Seiwa Kasei)

* 9: Palm oil fatty acid hydrolyzed collagen sodium 36. /. Aqueous solution (manufactured by Seiwa Kasei)

Claims

The scope of the claims

[1] A hair treatment agent containing an emulsifying thickener,

The emulsion thickener is

(A) A polymer of a monomer (i) having a strong acid functional group partially or completely neutralized, or a copolymer of the monomer (i) and another monomer (ii), which is branched or crosslinked. Re, ruanion polymer 88% -99% by weight,

(B) at least one water-in-oil (W / O) type emulsifier 1 wt% to 6 wt%, and

(C) At least one oil-in-water (O / W) type emulsifier 0 6% by weight

A hair treatment agent characterized by being a powdery emulsifying thickener containing a powerful composition

[2] The anionic polymer of (A) is based on the total number of moles of the monomer (i) and the other monomer (ii). It is crosslinked and Z or branched by an agent, and the crosslinking agent or branching agent is methylene bis (acrylamide), ethylene glycol dimetatalylate, diallyloxyacetic acid or a salt thereof, ethylene glycol ditalylate, diallylurea, The hair treatment agent according to claim 1, wherein the hair treatment agent is selected from allylamine, trimethylolpropane tritalylate, or a mixture thereof.

[3] The anionic polymer (A)

2_methyl _ 2 [(1 oxo-2-propenyl) amino] 1 propanesulfonic acid and 2-hydroxyethyl acrylate copolymer crosslinked with methylenebis (acrylamide) and partially neutralized with sodium,

2-Methyl-2-[(1-oxo-2-propenyl) amino] -1-crosslinked with methylenebis (acrylamide) and partially neutralized with sodium Partially neutralized with sodium and propanesulfonic acid A copolymer of acrylic acid, and 2_Methyl _ 2-[(1-oxo-2-propenyl) amino]-1 monopropanesulfonic acid homopolymer cross-linked with methylene bis (acrylamide) and partially neutralized with sodium The hair treatment agent according to claim 1 or 2, which is selected.