JP2002114802A - Method for producing cation-modified siloxane graft polysaccharide derivative and hair cosmetic formulated with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new and simple method for producing a cation-modified siloxane graft polysaccharide derivative. SOLUTION: This method for producing a cation-modified siloxane graft polysaccharide derivative comprises reacting a carboxy group-containing polysaccharide derivative with a single-terminated alicyclic epoxy modified organopolysiloxane compound represented by general formula (I) in an amount smaller than an equivalent of a carboxy group, reacting the obtained siloxane graft polysaccharide derivative with an epoxy group-containing cationizing agent represented by general formula (II) in an amount smaller than an equivalent of carboxy group and reacting the obtained siloxane graft polysaccharide derivative with the epoxy group-containing cationizing agent represented by general formula (II) in an amount smaller than an equivalent of the residual carboxy group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing a cation-modified siloxane-grafted polysaccharide derivative having a cationic group and an organosiloxane, and to provide a sustained set effect, gloss, feel, and combability of the hair surface by blending the derivative. The present invention relates to a hair cosmetic having excellent usability such as properties.

[0002]

2. Description of the Related Art Conventionally, vinyl polymers such as acrylic resin and polyvinylpyrrolidone have been generally used as a film-forming agent for blending hair cosmetics. None of them have yet to satisfy all the effects of the set effect, gloss, feel and combability. On the other hand, the cationized cellulose derivative has a good adsorbability to the hair and thus has an excellent conditioning effect, and is used for rinsing and blending a conditioner in combination with other film-forming agents. JP-A-7-702
No. 04 proposes a resin by a method of further grafting silicone to the cationized cellulose derivative. In this grafting method, a hydroxyl group of the cationized cellulose derivative is reacted with a glycidyl group-modified organopolysiloxane at one end. Therefore, there is a disadvantage that the graft efficiency is low and not practical. Therefore, at present, no film-forming agent that satisfies all the various properties for hair cosmetic formulations has emerged.

[0003]

An object of the present invention is to provide a novel and simple method for producing a cation-modified siloxane-grafted polysaccharide derivative, and to further provide a long-lasting set effect and a gloss on the hair surface by blending the same. An object of the present invention is to provide a hair cosmetic which is excellent in usability such as feel, feel and combability.

[0004]

That is, the present invention relates to a carboxyl group-containing polysaccharide derivative which is an alicyclic epoxy-modified organopolysiloxane compound represented by the following general formula (Chemical Formula 5).

[0005]

Embedded image (However, five R ¹ are the same or different from each other and have 1 to 10 carbon atoms.
Is reacted with an amount less than the equivalent of a carboxyl group, and the resulting siloxane-grafted polysaccharide derivative is reacted with an epoxy group-containing cation represented by the following general formula (Formula 6). Agent

[0006]

Embedded image (Where R ² is a divalent hydrocarbon group having 1 to 10 carbon atoms) is a method for producing a cation-modified siloxane-grafted polysaccharide derivative, which is characterized by reacting an amount less than the equivalent of the remaining carboxyl group; A cation-modified siloxane graft copolymer containing 1 to 60% by weight of an organopolysiloxane moiety represented by the following general formula (Chemical Formula 7) and 0.1 to 20% by weight of a cationic group moiety represented by the following general formula (Chemical Formula 8). This is a method for producing a saccharide derivative.

[0007]

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[0008]

Embedded image Furthermore, the present invention is a hair cosmetic comprising the cation-modified siloxane-grafted polysaccharide derivative.

The cation-modified siloxane-grafted polysaccharide derivative according to the production method of the present invention has a structure in which both a cation group and an organopolysiloxane are bonded to a polysaccharide derivative having excellent film-forming ability, so that the adsorptivity, water resistance,
A soft coating having excellent lubricating properties can be formed, and when used in hair, a hair cosmetic containing the same gives excellent set effect persistence, gloss, good feel, and combability.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing a cation-modified siloxane-grafted polysaccharide derivative of the present invention comprises a polysaccharide derivative having a carboxyl group and soluble in an organic solvent and a compound represented by the general formula (1).
This is a method of reacting an alicyclic epoxy-modified organopolysiloxane compound represented by the following formula with an epoxy group-containing cationizing agent represented by the general formula (Formula 2). The cation-modified siloxane-grafted polysaccharide derivative obtained by the production method of the present invention has an organopolysiloxane content of 1 to 6.
The content of the cationic group is 0.1 to 20% by weight at 0% by weight, and this content is preferable for hair cosmetics.
The content of the organopolysiloxane is represented by the weight percentage of the portion represented by the following general formula (Chemical Formula 9) with respect to the cation-modified siloxane-grafted polysaccharide derivative. If the content of the portion represented by the (Chemical Formula 9) is less than 1% by weight, The performance of the organopolysiloxane such as water resistance, moisture resistance, lubricity and the like becomes insufficient. If it exceeds 60% by weight, the film-forming ability is reduced, resulting in a film having insufficient durability.

[0011]

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The cationic group content in the cation-modified siloxane-grafted polysaccharide derivative obtained by the production method of the present invention is determined by the weight of the portion represented by the following general formula (Chem. 10) with respect to the cation-modified siloxane-grafted polysaccharide derivative.
%, When the cation-modified siloxane-grafted polysaccharide derivative is incorporated into cosmetics, if the content of the chemical formula (10) is less than 0.1% by weight, the adsorptivity of the cosmetics to the hair is reduced. If it is inferior, and if it exceeds 20% by weight, the coating will be inferior in water resistance and moisture resistance, and the durability of the setting effect will be insufficient.

[0013]

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Examples of the carboxyl group-containing polysaccharide derivative in the present invention include hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose acetate succinate, carboxymethylethylcellulose, pullulan acetate phthalate and the like. Examples thereof include hydroxypropylmethylcellulose phthalate and hydroxypropylmethylcellulose acetate succinate. Nate is commercially available as an enteric coating for pharmaceuticals and is particularly safe because it is safe, easily available, inexpensive, and provides excellent set effect persistence, gloss, feel, and combability. preferable.

The one-terminal alicyclic epoxy-modified organopolysiloxane compound in the present invention is represented by the following general formula (Formula 1). Wherein the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R ^1, a methyl group, an ethyl group, a propyl group, an alkyl group such as butyl group; a cyclopentyl group, cycloalkyl groups such as cyclohexyl group; phenyl Aryl groups such as a benzyl group; alkenyl groups such as a vinyl group and an allyl group; and halogen-substituted hydrocarbon groups such as a chloromethyl group and a 3,3,3-trifluoropropyl group.
Five R ¹ may also be different ones the same as each other.
Further, n is from 3 to 200, and when n is less than 3, the properties as an organopolysiloxane are insufficient, and when it exceeds 200, the graft reaction rate to the polysaccharide derivative becomes slow, which is not practical.

The epoxy group-containing cationizing agent in the present invention is represented by the general formula (Formula 2). Where R ² has 1 to 10 carbon atoms
A methylene group, an ethylene group, a propylene group, a butylene group, a decylene group, etc. are exemplified, but those in which R ² is a methylene group are commercially available in the form of an aqueous solution and are easily available. It is.

Hereinafter, an example of the method for producing the cation-modified siloxane-grafted polysaccharide derivative of the present invention will be described in detail. The method for producing the cation-modified siloxane-grafted polysaccharide derivative of the present invention is described in claims 1 to 3. Although the method described in detail below is part 1
By way of example, the manufacturing method of the present invention is not limited by this method. The cationized siloxane-grafted polysaccharide derivative obtained by the production method of the present invention is obtained by reacting a carboxyl group-containing polysaccharide derivative with a hydrophobic organopolysiloxane compound and a water-soluble cationizing agent. Since both the siloxane compound and the cationizing agent are completely incompatible with each other, it is difficult to react them at the same time.

In the first step, a carboxyl group-containing polysaccharide derivative is reacted with an alicyclic epoxy-modified organopolysiloxane compound at one end. First, a carboxyl group-containing polysaccharide derivative is dissolved in an organic solvent such as acetone, methyl ethyl ketone, ketones such as cyclohexanone, dioxane, ethers such as butyl cellosolve acetate, and the like, and then the desired cation-modified siloxane-grafted polysaccharide derivative is dissolved. An alicyclic epoxy-modified organopolysiloxane compound at one end is added in an amount such that the portion represented by the above formula (1) becomes 1 to 60% by weight, and the mixture is stirred.
By heating at 60 to 200 ° C. for 2 to 5 hours, the reaction can be performed almost quantitatively without using a catalyst. After completion of the reaction, a poor solvent such as n-hexane may be added to precipitate and separate the generated siloxane-grafted polysaccharide derivative, but the organic solvent is evaporated from the reaction solution,
It may be removed and separated.

In the second stage reaction, the remaining carboxyl groups of the siloxane-grafted polysaccharide derivative are reacted with an epoxy group-containing cationizing agent represented by the following chemical formula (2). The moiety represented by the above formula (1) for the polysaccharide derivative is 1 to 20
It is the amount that becomes weight%. First, a predetermined amount of the siloxane-grafted polysaccharide derivative obtained above is dissolved in a mixed solvent of methanol or ethanol and water, then a predetermined amount of an epoxy group-containing cationizing agent is added, and the mixture is stirred at 40 to 80 ° C.
By heating for 3 to 10 hours, the reaction can be sufficiently performed without using a catalyst. After completion of the reaction, the desired cation-modified siloxane-grafted polysaccharide derivative can be precipitated and separated by adding a poor solvent, but the unreacted cationizing agent is extracted and used as the solvent.
Acetone, IPA (isopropyl alcohol) that can be removed
Hydrophilic solvents such as are preferred.

The amount of the cationically modified siloxane-grafted polysaccharide derivative in the hair cosmetic composition of the present invention is not particularly limited because it varies depending on the type of the hair cosmetic composition.
It is 0.01 to 50% by weight, preferably 0.1 to 10% by weight. If the amount is less than 0.01% by weight, the hair cosmetic composition of the present invention will not have a sufficient effect, and if it exceeds 50% by weight, the viscosity of the hair cosmetic composition will be too high or the feel will be heavy. Is not preferred.

In the hair cosmetic of the present invention, oils, deionized water, alcohols, water-soluble polymer compounds, which are usually added to the hair cosmetic, as long as the effects of the present invention are not impaired,
Film forming agents, surfactants, defoamers, powders, oil-soluble gelling agents, organically modified clay minerals, resins, ultraviolet absorbers, humectants, wetting agents, preservatives, bactericides, fragrances, salts, oxidation Inhibitors, antidandruff agents, antifreeze agents, refreshing agents, anti-inflammatory agents, chelating agents, beautiful skin ingredients, vitamins, amino acids,
Nucleic acids, hormones, inclusion compounds and the like can be added.

Although these additives are not particularly limited, oils such as avocado oil, linseed oil, almond oil, ibotaro, eno oil, olive oil as natural animal and vegetable oils and fats and semi-synthetic oils, Cocoa butter, kapok wax, kaya oil, carnauba wax, liver oil, candelilla wax, tallow, beef tallow, beef bone fat, hardened tallow, kyonin oil, whale wax, hardened oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil , Sugarcane wax, sasanqua oil,
Safflower oil, shea putter, cinnamon oil, cinnamon oil,
Jojoba wax, shellac wax, turtle oil, soybean oil,
Teaseed oil, camellia oil, evening primrose oil, corn oil, lard,
Rapeseed oil, Japanese drill oil, bran wax, horse fat, persic oil, palm oil, palm kernel oil, castor oil, hydrogenated castor oil,
Castor oil fatty acid methyl ester, sunflower oil, grape oil, bayberry wax, jojoba oil, macadamia nut oil,
Beeswax, mink oil, cottonseed oil, cotton wax, mokuro, mokuro kernel oil, montan wax, coconut oil, hydrogenated coconut oil, triglyceride fatty acid glyceride, sheep fat, peanut oil, lanolin,
Examples include liquid lanolin, reduced lanolin, lanolin alcohol, hard lanolin, lanolin acetate, lanolin fatty acid isopropyl, POE lanolin alcohol ether, POE lanolin alcohol acetate, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, and egg yolk oil.

Hydrocarbon oils include ozokerite, squalane, squalene, ceresin, paraffin, paraffin wax, liquid paraffin, pristane, polyisobutylene, microcrystalline wax, and petrolatum; higher fatty acids include lauric acid, myristic acid, palmitic acid, Stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linoleic acid, arachidonic acid,
Eicosapentaenoic acid, docosahexaenoic acid, isostearic acid, 12-hydroxystearic acid; higher alcohols such as lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyl Dodecanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecinol, cholesterol, phytosterol; POE cholesterol ether, monostearyl glycerin ether as ether
(Bacyl alcohol), monooleyl glycerin ether
(Serakyl alcohol).

Examples of ester oils include diisobutyl adipate, 2-hexyldecyl adipate, and di-2-adipate.
Heptylundecyl, N-alkyl glycol monoisostearate, isocetyl isostearate, trimethylolpropane triisostearate, ethylene glycol di-2-ethylhexanoate, neopentyl glycol di-2-ethylhexanoate, 2-ethylhexane Cetyl acid, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl octanoate, octyl dodecyl gum ester, oleyl oleate, octyl dodecyl oleate, decyl oleate, neodicabate neo Pentyl glycol, triethyl citrate, 2-ethylhexyl succinate, amyl acetate, ethyl acetate, butyl acetate, isocetyl stearate, butyl stearate, diisopropyl sebacate, di-2 sebacate Ethylhexyl, cetyl lactate, myristyl lactate, isopropyl palmitate,
2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, 12
Cholesteryl hydroxystearate, dipentaerythritol fatty acid ester, isopropyl myristate, 2-octyldodecyl myristate, myristic acid 2
-Hexyldecyl, myristyl myristate, hexyldecyl dimethyloctanoate, ethyl laurate, hexyl laurate, N-lauroyl-L-glutamic acid-2-
Examples include octyldodecyl ester, diisostearyl malate, dextrin palmitate, dextrin stearate, dextrin 2-ethylhexanoate palmitate, sucrose palmitate, and sucrose stearate.

Glyceride oils include acetoglyceryl, glyceryl diisooctanoate, glyceryl triisostearate, glyceryl triisopalmitate, glyceryl tri-2-ethylhexanoate, glyceryl monostearate, glyceryl di-2-heptylundecanoate, Glyceryl trimyristate is mentioned.

Examples of silicone oils include dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and tetramethyltetrahydrogencyclotetrasiloxane. , Higher alkoxy-modified silicone such as stearoxy silicone, higher fatty acid-modified silicone, fluorine-modified silicone, amino-modified silicone, alkyl-modified silicone, higher fatty acid ester-modified silicone, silicone resin, silicone rubber, silicone resin; Fluoropolyether, perfluorodecalin, perfluorooctane and the like, and these are one kind as necessary,
Alternatively, two or more kinds can be used.

The alcohols include lower alcohols such as ethanol and isopropanol; sugar alcohols such as sorbitol, monobenzylidene sorbitol, dibenzylidene sorbitol and maltose; and the sterols include cholesterol, sitosterol, phytosterol and lanosterol. As the water-soluble polymer compound, plant-based polymer compounds such as gum arabic, tragacanth, galactan, carob gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed (quince), starch, alge colloid, tranto gum, locust bean gum, etc. A microbial polymer compound such as xanthan gum, dextran, succinoglucan, pullulan; an animal polymer compound such as carboxymethyl starch and methylhydroxypropyl starch; methylcellulose, ethylcellulose, methylhydroxypropylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxy Propyl cellulose, nitrocellulose, cellulose sodium sulfate, sodium carboxymethyl cellulose, crystalline cellulose, etc. Cellulose polymer compound; sodium alginate, alginic acid-based polymer compounds such as propylene glycol alginate.

Vinyl polymer compounds such as polyvinyl methyl ether and carboxyvinyl polymer; polyoxyethylene polymer compounds; polyoxyethylene polyoxypropylene copolymer polymer compounds; sodium polyacrylate, polyethyl acrylate; Acrylic polymer compounds such as polyacrylamide; inorganic polymer compounds such as polyethyleneimine, cationic polymer, bentonite, aluminum magnesium silicate, laponite, hectorite, and silicic anhydride; and polyvinyl alcohol; And a film-forming agent such as polyvinylpyrrolidone.

As the surfactant, if it is a cationic, nonionic or amphoteric surfactant other than anionic,
There is no particular limitation, and any one can be used as long as it is used for ordinary cosmetics. Illustrating specific examples below, examples of cationic surfactants include alkylamine salts, amine salts such as polyamines and amino alcohol fatty acid derivatives, alkyl quaternary ammonium salts, aromatic quaternary ammonium salts, pyridium salts, imidazolium salts Nonionic surfactants include sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, Polyoxyethylene alkyl phenyl ether,
Polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor oil,
Polyoxyethylene hydrogenated castor oil, polyoxyethylene phytostanol ether, polyoxyethylene phytosterol ether, polyoxyethylene cholesterol ether, polyoxyethylene cholesteryl ether, polyoxyalkylene-modified organopolysiloxane, polyoxyalkylene / alkyl co-modified organopoly Siloxane, polyoxyalkylene / fluoroalkyl co-modified organopolysiloxane, polyoxyalkylene / organopolysiloxane block copolymer, alkanolamide, sugar ether, sugar amide; amphoteric surfactants include betaine, aminocarboxylate, imidazoline Derivatives and the like.

As the powder, if used in ordinary cosmetics, the shape of the particles (spherical, needle-like, plate-like, etc.),
And particle structure (porous, non-porous, etc.), particle size (fume class, fine particle class, pigment class, etc.), for example, moisture-resistant pigments, white pigments, colored pigments, organic powders, pearlescent agents, organic dyes, etc. Specific examples include talc, mica, kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, red iron oxide, yellow iron oxide, black iron oxide, nylon powder, silk powder, urethane powder, silicone resin powder,
Examples include silicone rubber powder, mica titanium, and tar dyes. In addition, these powders can be combined with powders, general oils, silicone oil,
Those treated with a fluorine compound, a surfactant or the like can also be used.

Examples of the oil-soluble gelling agent include metal soaps such as aluminum stearate, magnesium stearate and zinc myristate; amino acid derivatives such as N-lauroyl-L-glutamic acid, α, γ-di-n-butylamine;
Dextrin fatty acid esters such as dextrin palmitate, dextrin stearate, and dextrin 2-ethylhexanoate palmitate; sucrose fatty acid esters such as sucrose palmitate and sucrose stearate; monobenzylidene sorbitol, dibenzylidene sorbitol Benzylidene derivatives of sorbitol and the like, and also organically modified clay minerals such as dimethylbenzyldodecylammonium montmorillonite clay and dimethyldioctadecyl ammonium montmorillonite clay.

Examples of the ultraviolet absorber include benzoic acid-based ultraviolet absorbers such as para-aminobenzoic acid; anthranilic acid-based ultraviolet absorbers such as methyl anthranilate; salicylic acid-based ultraviolet absorbers such as methyl salicylate; octyl paramethoxycinnamate; Cinnamic acid ultraviolet absorbers; benzophenone ultraviolet absorbers such as 2,4-dihydroxybenzophenone; and urocanic acid ultraviolet absorbers such as ethyl urocanate. As humectants, sorbitol, xylitol, polyethylene glycol, hyaluronic acid,
Chondroitin sulfate, pyrrolidone carboxylate; preservatives include alkyl paraoxybenzoate, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol; antibacterial agents include benzoic acid, salicylic acid, phenolic acid, sorbic acid, Examples include paraoxybenzoate, parachloromethcresol, hexachlorophen, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, photosensitizer, and phenoxyethanol.

Examples of the antioxidant include tocopherol, butylhydroxyanisole, and dibutylhydroxytoluene. Examples of the chelating agent include alanine, edetate sodium salt, sodium polyphosphate, sodium metaphosphate, and phosphoric acid; Menthol, camphor; anti-inflammatory agents include allantoin, glycyrrhetinic acid, tranixamic acid, azulene and the like. Examples of the anti-dandruff agent include selenium disulfide, alkylisoquinolinium bromide, zinc pyridione, biphenamine, thianthol, octopirox and the like. Amino acids include arginine, aspartic acid, cystine, cysteine, methionine, serine, leucine, tryptophan; nucleic acids include deoxyribonucleic acids; hormones include estradiol and ethenyl estradiol.

The hair cosmetics of the present invention include shampoos, rinses, rinse-in shampoos, treatments,
Includes all products applied externally to hair, such as conditioners, hair creams, hair oils, brushing agents, setting agents, and hair tonics. The dosage form can be selected from various forms such as semi-solid, liquid, emulsion, cream, mousse, paste, and spray.

[0035]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. The percentages in the examples and the numbers in the columns of the components in Tables 1 and 2 all indicate% by weight.

Example 1 (Production of Cation-Modified Siloxane-Grafted Polysaccharide Derivative a) Hydroxypropylmethylcellulose phthalate [trade name: HP manufactured by Shin-Etsu Chemical Co., Ltd.] was placed in a glass flask equipped with a stirrer, a thermometer, and a cooler. -55, a carboxybenzoyl group content of 33.4%, a COOH content of 168.2 mmo1] of 75 g, and an alicyclic epoxy-modified dimethylpolysiloxane at one end represented by the following formula (Chemical formula 11) (epoxy equivalent: 2,270 g / mo1) , 25 g of epoxy content 11.0 mmol) and 400 g of cyclohexanone were reacted at 150 ° C. for 5 hours under a nitrogen stream to obtain a pale yellow, slightly turbid liquid.

[0037]

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Next, the reaction solution was cooled to 30 ° C., 1 liter of n-hexane was added with stirring to precipitate a polymer, and cyclohexanone and n-hexane were separated by filtration. Drying yielded 92 g of a pale yellow powder. When the infrared absorption spectrum of this powder was measured, the following characteristic absorption of dimethylpolysiloxane was observed in addition to the characteristic absorption of hydroxypropylmethylcellulose phthalate. 1,262 cm ^-1 (Si-CH ₃ ) 1,071; 1,123 cm ^-1 (Si-O-Si) 801 cm ^-1 [(CH ₃ ) ₂ -Si-O] Also, the carboxybenzoyl group The content was quantified to be 23.5%, confirming that the reaction proceeded almost quantitatively. The acid value of this powder was 88.5 mgKOH / g, and the organopolysiloxane content determined from the reaction rate was 24.5% by weight. Next, 50 g of this siloxane-grafted polysaccharide derivative, 200 g of ethanol and 20 g of water were placed in a glass flask equipped with the same equipment as above, and dissolved by stirring at room temperature.
Cation agent represented by 2) (trade name: S
7.5 g of Y-GTA80 (80% aqueous solution) was added and reacted at 75 ° C. for 8 hours. After the completion of the reaction, the reaction solution is cooled to 30 ° C. and stirred.
One liter of acetone was added to precipitate a white rice cake-like polymer. Next, the polymer was vacuum dried at 60 ° C. for 5 hours to obtain 45 g of a pale yellow transparent resin.

[0039]

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When the obtained resin was quantified for Si, N and Cl (chlorine), they were 8.47%, 0.81% and 2.0, respectively.
5%, and the organopolysiloxane content and the cationic group content determined from these values were 22.4% and 8.8%, respectively.
Met. This is designated as a cation-modified siloxane graft polysaccharide derivative a.

(Example 2) (Preparation of cation-modified siloxane-grafted polysaccharide derivative b) 50 g of hydroxypropylmethylcellulose phthalate of Example 1 (COOH content: 112.1 mmol) and 50 g of alicyclic epoxy-modified dimethylpolysiloxane at one end were prepared. (Epoxy content 2
Except having changed to 2.0 mmol1), it carried out similarly to Example 1, and obtained 91 g of pale yellow powder. When the infrared absorption spectrum of this powder was measured, the following characteristic absorption of dimethylpolysiloxane was observed in addition to the characteristic absorption of hydroxypropylmethylcellulose phthalate. 1,264 cm ^-1 (Si-CH ₃ ) 1,073; 1,125 cm ^-1 (Si-O-Si) 801 cm ^-1 [(CH ₃ ) ₂ -Si-O] When the amount was quantified, it was 13.6%, and it was confirmed that the reaction proceeded almost quantitatively. The acid value of this powder was 51.2 mgKOH / g, and the organopolysiloxane content determined from the reaction rate was 49.5% by weight. Next, this siloxane graft polysaccharide derivative 50 g, ethanol 200 g, water 2
Using 0 g and 1.7 g of the same cationizing agent as in Example 1, 43 g of a pale yellow transparent resin was obtained in the same manner as in Example 1. When S, N and C1 (chlorine) of the obtained resin were quantified, they were 18.3%, 0.22%, and 0.57%, respectively. The contents were 48.3% and 2.4%, respectively. This is designated as a cation-modified siloxane graft polysaccharide derivative b.

Example 3 (Production of Cation-Modified Siloxane-Grafted Polysaccharide Derivative c) The hydroxypropylmethylcellulose phthalate of Example 1 was replaced with hydroxypropylmethylcellulose acetate succinate (trade name: AS-LG, content of succinoyl group, manufactured by Shin-Etsu Chemical Co., Ltd.). 93 g of a pale yellow powder was obtained in the same manner as in Example 1 except that the amount was changed to 75 g (15.6%, COOH content: 115.6 mmol). When the infrared absorption spectrum of this powder was measured, the following characteristic absorption of dimethylpolysiloxane was observed in addition to the characteristic absorption of hydroxypropylmethylcellulose acetate succinate. 1,238 cm ^-1 (Si-CH ₃ ) 1,057; 1,122 cm ^-1 (Si-O-Si) 803 cm ^-1 [(CH ₃ ) ₂ -Si-O] When the succinoyl group content was quantified, it was 10.8. %, And it was confirmed that the reaction proceeded almost quantitatively. The acid value of this powder was 60.0 mgKOH / g, and the organopolysiloxane content determined from the reaction rate was 23.8% by weight. Next, 50 g of this siloxane-grafted polysaccharide derivative,
200 g of ethanol, 20 g of water, the same cationizing agent as in Example 1
In a similar manner to Example 1 using 2.4 g, 46 g of a pale yellow transparent resin was obtained. When the obtained resin was quantified for Si, N and C1 (chlorine), it was 8.66%, 0.37% and 0.9, respectively.
4%, and the organopolysiloxane content and the cationic group content determined from these values were 22.8% and 4.0%, respectively.
Met. This is designated as a cation-modified siloxane-grafted polysaccharide derivative c.

(Examples 4 to 6 and Comparative Example 1) (Preparation and evaluation of cream rinse) A cream rinse was prepared according to the following procedure using each component (% by weight) shown in Table 1. For the cream rinses of Examples 4, 5, and 6, cation-modified siloxane-grafted polysaccharide derivatives a, b, and c were used in this order. A: Add components 1, 5, 6, and 7 and dissolve by heating. B: Components 2, 3, and 4 are heated and dissolved, and then added to A and emulsified. C: (A + B) is cooled to obtain a cream rinse. [Evaluation and judgment method] Perform a use test by a professional panel of 20 women, and evaluate the smoothness after use on the hair, the smoothness of the hair after drying, the dry feeling, the refreshing feeling according to the following criteria, respectively. The average score was determined as follows. (Evaluation criteria) 5 points: Very good 4 points: Good 3 points: Normal 2 points: Somewhat poor 1 point: Poor (Judgment) ◎: Average score of 4.5 or more ○: Average score of 3.5 or more and less than 4.5 △: Average score of 2.5 or more and less than 3.5 ×: Average score of less than 2.5

[0044]

【table 1】

As is evident from the results in Table 1, the cosmetics of Examples 4 to 6 containing the cation-modified siloxane-grafted polysaccharide derivative according to the production method of the present invention showed a smooth, smooth and refreshing feeling on the back skin. Was excellent in sustainability.

(Examples 7 to 9) (Preparation and evaluation of hair setting agent) Using each component (% by weight) shown in Table 2, a hair setting agent was prepared in the following procedure. Examples 7, 8, and 9
The cation-modified siloxane-grafted polysaccharide derivatives a, b, and c were used in this order. A. Mix and dissolve 1-4. B. Fill A with a liquefied gas into a spray container to obtain a hair setting agent. When the hair setting agent obtained as described above was used for hair, the hair setting agent was excellent in persistence of the setting effect, gloss on the surface of the hair, feel of the hair, and combability of the hair.

[0047]

[Table 2]

[0048]

According to the production method of the present invention, a cation-modified siloxane-grafted polysaccharide derivative can be easily produced, and its coating is excellent in adsorptivity, water resistance, moisture resistance and lubricity. It can be used as a compounding agent, as a treatment agent for fibers and papers, etc., especially when it is added to hair cosmetics, it exhibits the best effect, lasting effect of set effect, gloss of hair surface, feel, A hair cosmetic having excellent usability such as combability can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08G77 / 42 C08G77 / 42 F-term (Reference) 4C083 AC072 AC102 AC122 AC352 AC692 AD162 AD211 AD212 BB34 CC32 CC39 DD08 DD31 EE06 EE07 4C090 BA29 BD34 BD50 DA05 DA11 DA26 4J035 BA02 CA01U CA07M CA11M FB05 FB10 GA01 GB05 LB14

Claims (4)

[Claims] 1. A carboxyl group-containing polysaccharide derivative having an alicyclic epoxy-modified organopolysiloxane compound represented by the following general formula (1): (However, five R ¹ are the same or different from each other and have 1 to 10 carbon atoms.
A monovalent hydrocarbon group, n is a number of 3 to 200) and reacts in an amount less than the equivalent of a carboxyl group, and the resulting siloxane-grafted polysaccharide derivative has an epoxy group-containing cation represented by the following general formula (Chemical Formula 2). Agent (Wherein R ² is a divalent hydrocarbon group having 1 to 10 carbon atoms) is reacted in an amount less than the equivalent of the remaining carboxyl group, thereby producing a cation-modified siloxane-grafted polysaccharide derivative. 2. An organopolysiloxane portion represented by the following general formula (Formula 3) is contained in an amount of 1 to 60% by weight, and a cationic group portion represented by the following general formula (Formula 4) is contained in an amount of 0.1 to 20% by weight. A method for producing a cation-modified siloxane-grafted polysaccharide derivative. Embedded image Embedded image 3. The method according to claim 1, wherein the carboxyl group-containing polysaccharide derivative is hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose acetate succinate,
2. The method for producing a cation-modified siloxane-grafted polysaccharide derivative according to claim 1, which is one or more of carboxymethylethylcellulose and pullulan acetate phthalate. 4. A hair cosmetic comprising the cationically modified siloxane-grafted polysaccharide derivative according to any one of claims 1 to 3.