JP2006249194A - Cationic thickener - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cationic thickener which has thixotropy and excels in coating properties and a feeling of use as a thickener for cosmetics and toiletries. <P>SOLUTION: The cationic thickener is obtained by the radical polymerization of (A) at least one cation modified polysaccharide, (B) at least one nonionic vinyl monomer represented by formula (1) (wherein R<SB>1</SB>is hydrogen or a methyl group; and R<SB>2</SB>and R<SB>3</SB>are the same or different and each is hydrogen, a 1-4C linear or branched alkyl group, an alkenyl group, an alkoxyalkyl group or a hydroxyalkyl group), and (C) at least one crosslinkable vinyl monomer as the essential constituting components. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a cationic thickener. More specifically, the present invention can be suitably used as a thickener for cosmetics, toiletries, water-soluble paints, building materials, and the like, and particularly excellent thixotropy when formulated in cosmetics, toiletries and the like. , Coating properties and touch feeling (smoothness), and when applied to hair, a cationic increase in which a good feeling of use (smoothness of wet hair, slipperiness of dry hair) is expressed. It relates to the adhesive.

Conventionally, N-vinyl lactam, N-vinylimidazole or N-vinylimidazolium salt and dialkylaminoalkyl- (meth) acrylic acid ester or dialkylaminoalkyl- (meth) acrylic acid amide or Various polymers or copolymers composed of the quaternized products have been used. However, these generally have poor thixotropic properties, and when used as a thickener for cosmetics and toiletries, the applicability and usability may not be so good.

Patent Document 1 discloses an alkali metal salt of a polyacrylic acid crosslinked polymer, which has thixotropy and is not bad in applicability, but is not very pleasant to the touch, particularly when applied to hair or the like. .

Patent Document 2 proposes a compound obtained by copolymerizing a cationic vinyl monomer and a nonionic vinyl monomer in the presence of a crosslinking agent. However, the crosslinking agent described in this publication does not have good copolymerizability with the nonionic vinyl monomer, and it is difficult for the crosslinking points to be uniformly introduced into the polymer molecular chain from the beginning to the end of the polymerization. For this reason, since a crosslinking agent is not used effectively and is not fully crosslinked, when it is added to water, it tends to be a very non-uniform gel.

Patent Documents 3 and 4 propose compounds in which amine-containing (meth) acrylic monomers, other vinyl monomers, and the like are polymerized in the presence of a crosslinking agent and then neutralized. In this case, the amino group in the polymer is neutralized with an acid compound to be cationized, so that the thixotropic property of the gel is likely to change greatly depending on the pH in the system, and the compound is increased for cosmetics and toiletries. When used as a sticking agent, it did not have high usability (ease of stretching during application, etc.).

On the other hand, Patent Document 5 discloses that hydroxyethyl cellulose (HEC) is subjected to partial hydrolysis after graft polymerization of an olefin monomer having a substituent that generates a carboxyl group by hydrolysis of acrylic acid ester, acrylamide, or the like. Has been proposed as a superabsorbent material. Since this compound has a carboxyl group and is anionic, it has been difficult to use it as a thickener for hair cosmetics and toiletry products.
Patent No. 1303701 Japanese Patent Laid-Open No. 4-20584 Patent No. 2608214 Japanese Patent No. 2908555 Japanese Patent No. 1897319

Therefore, the problem to be solved by the present invention is to provide a cationic thickener having sufficient thixotropic properties and excellent in applicability and usability when used as a thickener for cosmetics and toiletries. It is in.

〔式中、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２及びＲ^３は同一又は異なって、水素原子又は炭素数１〜４の直鎖状もしくは分岐状のアルキル基又はアルケニル基又はアルコキシアルキル基又はヒドロキシアルキル基を示す。〕で表されるノニオン性ビニルモノマーの少なくとも１種と、（Ｃ）架橋性ビニルモノマーの少なくとも１種とを必須構成成分する混合物をラジカル重合することにより得られるカチオン性増粘剤が上記要件を満たすことを見出し、本発明を完成させた。 Under such circumstances, the present inventors have conducted extensive studies to solve the above problems, and as a result, (A) at least one cation-modified polysaccharide and (B) the following general formula (1):

[Wherein, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ are the same or different and represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, an alkenyl group, or an alkoxyalkyl group. A group or a hydroxyalkyl group. A cationic thickener obtained by radical polymerization of a mixture comprising at least one nonionic vinyl monomer represented by formula (C) and at least one crosslinkable vinyl monomer as essential components satisfies the above requirements. As a result, the present invention was completed.

The cationic thickener of the present invention has sufficient thixotropy, applicability and hand feeling (smoothness), and can be suitably used as a thickener for cosmetics, toiletries, water-soluble paints, building materials, etc. When blended in cosmetics, toiletry products, etc., or when applied to hair, a good feeling of use (smooth hair when wet, slipperiness of dry hair) is exhibited.

Below, the cationic thickener of this invention is explained in full detail.
The cation-modified polysaccharide of the component (A) used in the present invention is not particularly limited, but cation-modified hydroxyethyl cellulose, cation-modified hydroxypropyl cellulose, cation-modified guar gum, cation-modified starch, cation-modified tamarind gum, cation-modified. Examples include fenugreek gum, cation-modified tara gum, and cation-modified locust bean gum.

(式中Ｒ_４、Ｒ_５は各々炭素数１〜３個のアルキル基、Ｒ_６は炭素数１〜２４のアルキル基を示し、Ｘ⁻は陰イオンを示す。ｎは、ｎ＝０又はｎ＝１〜３０を示し、ｎ＝１〜３０の時、（Ｒ_７Ｏ）ｎは炭素数２〜４のアルキレンオキサイドの重合体残基であって、単一のアルキレンオキサイドからなるポリアルキレングリコール鎖及び／又は２種類以上のアルキレンオキサイドからなるポリアルキレングリコール鎖を示す。) As a means of cation modification in the above (A) cation-modified polysaccharide, it can be carried out according to a conventionally known method, but a method of introducing a quaternary nitrogen-containing group represented by the following chemical formula (2) is preferable. Examples include a method in which a glycidyltrialkylammonium salt or a 3-halogeno-2-hydroxypropyltrialkylammonium salt is reacted with a part of the hydroxyl group of an alkylene oxide adduct of a saccharide or polysaccharide.

(Wherein R ₄ and R ₅ each represent an alkyl group having 1 to 3 carbon atoms, R ₆ represents an alkyl group having 1 to 24 carbon atoms, X ⁻ represents an anion, and n is n = 0 or n. = 1-30, and when n = 1-30, (R ₇ O) n is a polymer residue of an alkylene oxide having 2 to 4 carbon atoms, and is a polyalkylene glycol chain consisting of a single alkylene oxide And / or a polyalkylene glycol chain composed of two or more alkylene oxides.)

Among these, the cationic charge amount of the cation-modified polysaccharide is preferably in the range of 0.1 to 3.0 meq / g, more preferably the cationic charge amount is in the range of 0.5 to 2.5 meq / g. Cationic modified hydroxyethyl cellulose is particularly preferred.

Examples of the nonionic vinyl monomer (B) used in the present invention include (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-methoxymethyl ( And (meth) acrylamide. In particular, when (meth) acrylamide or N, N-dimethyl (meth) acrylamide is used, the feeling of use is good and particularly preferable. In the present invention, one or more of these nonionic vinyl monomers can be arbitrarily used.

Examples of the crosslinkable vinyl monomer (C) used in the present invention include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and dipropylene. Glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,2-butylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (Meth) acrylates of polyhydric alcohols such as (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate Rylates; acrylamides such as N-methallylacrylamide, N-vinylacrylamide, N, N′-methylenebis (meth) acrylamide, bisacrylamideacetic acid; divinyl compounds such as divinylbenzene, divinyl ether, divinylethyleneurea, etc. And monomers having crosslinkability. Among these, N, N′-methylenebis (meth) acrylamide, which is easily available industrially, is particularly preferable.

The cationic thickener of the present invention has a viscosity at 0.6 rpm when the viscosity at 25 ° C. when added to ion exchange water so as to be 0.5% by weight is measured with a B-type viscometer. η ₁ is in the range of 3,000 to 500,000 mPa · s, more preferably 50,000 to 400,000 mPa · s, particularly preferably 150,000 to 300,000 mPa · s, and viscosity η ₂ at 12 rpm Is in the range of 300 to 50,000 mPa · s, more preferably 5,000 to 40,000 mPa · s, particularly preferably 10,000 to 35,000 mPa · s, and thixotropic properties such that η ₁ > η ₂ It is preferable from the viewpoint of good coatability and expression of use feeling.

Moreover, when the compounding quantity of (C) is 0.001 to 3 weight% with respect to the total amount of (A) and (B), when adding the obtained cationic thickener to water It is preferable from the viewpoint of viscosity, good coatability, and usability.

In addition to the essential components, the cationic thickener of the present invention can also contain other monomers copolymerizable therewith. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, neopentyl (meth) acrylate, cyclopentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate Isostearyl (meth) acrylate, behenyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, xylyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (Meth) acrylate, 2-phenoxy (meth) acrylate, 2-methoxypropyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 2-ethoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, etc. (Meth) acrylic acid derivatives; anionic monomers such as 2-acrylamido-2-methylpropanesulfonic acid, sodium styrenesulfonate, acrylic acid, methacrylic acid, 2-sulfoethyl methacrylate; -(3-sulfopropyl) -N-acryloyloxyethyl-N, N-dimethylammonium betaine, N- (3-sulfopropyl) -N-methacryloylamidopropyl-N, N-dimethylammonium betaine, N- (3- Carboxymethyl) -N-methacryloylamidopropyl-N, N-dimethylammonium betaine, N- (3-sulfopropyl) -N-methacryloyloxyethyl-N, N-dimethylammonium betaine, N-carboxymethyl-N-methacryloyloxy Examples thereof include betaine monomers such as ethyl-N, N-dimethylammonium betaine.

The method for producing the cationic thickener of the present invention is not particularly limited, but usually a method such as a solution polymerization method or a reverse phase suspension polymerization method is preferable. Also, the polymerization apparatus is not particularly limited, and a reaction vessel such as a kneader can be used as necessary when the viscosity becomes high. As the solution polymerization method, water or a hydrophilic organic solvent that can be uniformly mixed with water, or a cation-modified polysaccharide and a monomer component are uniformly dissolved or dispersed in a solvent such as a mixed solvent thereof. A method may be mentioned in which dissolved oxygen in the system is removed by substitution with an inert gas or the like, and then a polymerization initiator is added and reacted. The polymerization initiation temperature is usually about 20 to 90 ° C., and the reaction time is about 1 to 10 hours. The initial concentration of the cation-modified polysaccharide and the monomer mixture aqueous solution used here is preferably 5 to 50% by weight.

If the monomer is difficult to dissolve in water, use a lower alcohol such as methyl alcohol, ethyl alcohol or propyl alcohol, a cyclic ether such as tetrahydrofuran or dioxane, and a hydrophilic organic solvent such as acetone, acetonitrile, dimethylformamide, dimethylacetamide or dimethyl sulfoxide. You can also. Of these, isopropyl alcohol is particularly preferred.

Moreover, as a polymerization initiator, it dissolves uniformly in a solvent. Peroxides such as lauroyl peroxide, t-butyl hydroperoxide, cyclohexyl hydroperoxide, tetralin hydroperoxide, t-butyl peracetate, t-butyl perbenzoate, bis (2-ethylhexyl peroxydicarbonate), 2,2'-azobisisobutyronitrile, phenylazotriphenylmethane, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (5-methyl-2- Imidazoline-2 Yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] a redox initiator by an azobis compound such as dihydrochloride alone or in combination with a reducing agent, Organic or inorganic peracids or salts thereof such as sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, combinations of persulfate with tertiary amines such as triethylamine, triethanolamine, dimethylaniline, cerium ammonium nitrate And ceric salt-based redox catalysts such as Among these, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazoline) -2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, sodium persulfate, potassium persulfate or ammonium persulfate alone, persulfate A redox catalyst comprising a combination of sodium and sodium bisulfite, cerium ammonium nitrate is preferred. More preferred are 2,2′-azobis (2-amidinopropane) dihydrochloride and cerium ammonium nitrate.

The polymerization initiator is used in an amount of 0.01 to 5% by weight, preferably 0.01 to 5%, based on the total amount of (A) cation-modified polysaccharide, (B) nonionic monomer, and (C) crosslinkable monomer. It is 3% by weight, particularly preferably in the range of 0.01 to 1% by weight. When the amount of the polymerization initiator used is less than 0.01% by weight, the reaction rate does not increase and the amount of residual monomer increases, which is not preferable. On the other hand, when the amount is more than 5% by weight, the degree of polymerization does not increase and it is easy to dissolve in water, so that the expected effect cannot be exhibited.

In the reverse phase suspension polymerization method, the cation-modified polysaccharide and the monomer component are uniformly dissolved in water, and suspended or emulsified in an organic solvent that is not uniformly mixed with water using a dispersant or the like. Do. As a polymerization initiator, not only a water-soluble thing but a thing soluble in an organic solvent is necessarily used. As the organic solvent used here, in addition to the above, for example, hydrocarbon organic solvents such as hexane, cyclohexane, heptane, octane, benzene, toluene, xylene, ethylbenzene, and halogenated carbonization such as carbon tetrachloride and dichloroethane. Hydrogen-based organic solvents, mineral oil such as Isobar, etc. are also used. Examples of the dispersant include polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, sorbitan monostearate, sorbitan monopalmitate, and polyvinyl alcohol.

As the operation method, removal of dissolved oxygen in the system, treatment of the reaction product and the like are the same as those in the aqueous solution polymerization method, and the reaction conditions are not necessarily limited but are as follows. Solvent usage: equimolar to 20 times the monomer aqueous solution, preferably equivalent to 10 times, polymerization initiator usage: 0.01 to 5 mol%, preferably 0.01 based on the monomer component ˜3 mol%, polymerization initiation temperature: about 10 to 90 ° C., reaction time: about 1 to 10 hours.

The reaction product obtained by a method such as an aqueous solution polymerization method or a reverse phase suspension polymerization method is in the form of a gel or a slurry containing the solvent used in the reaction, and is usually a product in water or a solvent or a mixed solution thereof. Then, the solvent is removed by a method such as washing, heating, and decompression, followed by drying and pulverization to obtain a powder.

The dosage form of the cationic thickener according to the present invention is not limited and can take any dosage form, and can be suitably used as a thickener for cosmetics, toiletries, water-soluble paints, building materials, Especially when formulated in cosmetics, toiletries, etc., it has excellent thixotropy, applicability, and hand feeling (smoothness), and when applied to hair, it feels good when used (smooth hair slipperiness) Slidability of dry hair).

EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to an Example. The specific manufacturing method of the cationic thickener was shown in Examples 1-8 and Comparative Examples 1-4. The cationic thickeners obtained in Examples 1 to 8 and Comparative Examples 1 to 4 were subjected to viscosity measurement by adjusting the gel as follows, and the obtained gel was evaluated for applicability and feel (smoothness). Sensory comparison of evaluation and usability when applied to hair (slipperiness of wet hair, slipperiness of dry hair) and comprehensive evaluation based on the results obtained Were evaluated according to the following criteria, and the results are shown in Tables 2 to 4.

[Gel adjustment method]
A gel was obtained by adding to the ion-exchanged water so that the concentration of the cationic thickener was 0.5% by weight and leaving it at 50 ° C. for 10 to 15 hours.

[Method of measuring viscosity]
About the obtained gel, a B-type viscometer (device name: Bismetron VS-A1 [manufactured by Shibaura System Co., Ltd.], rotor: No. 4, rotation speed: 0.6 rpm, 12 rpm, measurement temperature: 25 ° C.) Measurement was performed in accordance with “Method of measuring viscosity with a single cylindrical rotational viscometer described in JIS Z8803”, and the results are shown in Tables 2 to 4.

[Evaluation of coating properties]
The ease of application (ease of extension) when the obtained gel (5 ml) was placed on the right arm forearm of 10 panelists and slowly extended with the palm of the left hand was evaluated according to the following evaluation criteria.
◎: When there are 9 or more people who answered that it was easy to apply ○: When there were 6-8 or more people who answered that it was easy to apply △: When 3-5 or more people answered that it was easy to apply × : When two or less people answered that it was easy to apply [Evaluation of feel (smoothness)]
5 ml of the gel thus obtained was placed on the back of the left hand of 10 panelists, slowly stretched with the palm of the right hand, rinsed with tap water and wiped with a towel, and the feel (smoothness) was evaluated according to the following evaluation criteria.
◎: When the number of people who answered that there was a smooth hand feeling was 9 or more ○: When there were 6 to 8 people who answered that there was a smooth hand feeling Δ: Three people who answered that there was a smooth hand feeling ~ For 5 people: When there are 2 or less people who answered that there is a smooth hand feeling (evaluation of the slipperiness of the hair in a wet state, the slipperiness of the hair after drying)
5 ml of the gel thus obtained was applied to the hair of 10 panelists, and the slipperiness of the hair when wet and the slipperiness of the hair after drying were evaluated according to the following evaluation criteria.
◎: If there are more than 9 people who answered good ○: If there are 6-8 people who answered good △: If there are 3-5 people who answered good ×: People who answered good When there are two or less people [overall evaluation]
Point system (◎: 3 points, ○: 2 points) for evaluation of applicability, evaluation of touch (smoothness), evaluation of slipperiness of hair when wet, and evaluation of slipperiness of hair after drying , Δ: 1 point, ×: 0 point), and the total was evaluated according to the following criteria.
◎: 10 points or more ○: 7-9 points △: 4-6 points ×: 3 points or less

[Production of cation-modified polysaccharide]
Synthesis Example After adding 9.4 g of 20% by weight aqueous sodium hydroxide solution to 364 mL of 80% by volume isopropanol aqueous solution, 80.0 g of hydroxyethylcellulose was gradually added and dispersed. Next, 23.7 g of an aqueous 75 wt% glycidyltrimethylammonium chloride (hereinafter also referred to as GTA) solution was added, heated and reacted at 50 ° C. for 3 hours. After completion of the reaction, 2.4 g of 35% hydrochloric acid was added and stirred for 1 hour. Neutralized. The reaction product was removed from the resulting polymer slurry solution by filtration under reduced pressure, washed twice with 600 mL of 80% by volume acetone aqueous solution and acetone, and then the obtained solid was dried under reduced pressure. The cation charge amount of the cation-modified hydroxyethyl cellulose (referred to as A-1) thus obtained was 0.8 meq / g. The cation charge amount of A-1 was measured by colloid titration using 0.0025N polyvinyl potassium sulfate solution.

Similarly, cation-modified polysaccharides having different kinds of polysaccharides and different amounts of cationic charges were produced. The results are shown in Table 1 (Table 1, A-2 to A-7).

[Synthesis of cationic thickener]
Example 1
In a 1 liter four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 39.2 g of cation-modified hydroxyethyl cellulose prepared in Synthesis Example A-1 and 68.8 g (80.2 mol) of acrylamide were prepared. %, Polysaccharide-constituting monosaccharide unit), 0.186 g of N, N-methylenebisacrylamide, and 494 mL of 80 volume% isopropyl alcohol aqueous solution were charged, and oxygen in the reaction system was removed through nitrogen gas. Next, the system was brought to 50 ° C., and 0.68 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added as a polymerization initiator with stirring. After the addition of the initiator, the mixture was kept at 50 ° C. for 10 hours, and then cooled. Then, the polymerization was stopped. The reaction product was removed from the resulting polymer slurry solution by filtration under reduced pressure, washed twice with 600 mL of 80% by volume acetone aqueous solution and acetone, and then the obtained solid was dried under reduced pressure and then pulverized to obtain a white powder. A cationic thickener was obtained.

Example 2
31.3 g of cation-modified hydroxyethyl cellulose prepared in Synthesis Example A-2, 79.3 g of N, N-dimethylacrylamide (86.0 mol% with respect to the polysaccharide-constituting monosaccharide unit), 0.154 g of N, N-methylenebisacrylamide A cationic thickener was prepared in the same manner as in Example 1 except that 492 mL of an 80% by volume isopropyl alcohol aqueous solution and 0.68 g of 2,2′-azobis (2-amidinopropane) dihydrochloride as a polymerization initiator were added. Obtained.

Example 3
27.0 g of cation-modified hydroxyethyl cellulose prepared in Synthesis Example A-3, 84.6 g of N, N-dimethylacrylamide (89.5 mol% with respect to the polysaccharide-constituting monosaccharide unit), 0.154 g of N, N-methylenebisacrylamide A cationic thickener was prepared in the same manner as in Example 1 except that 488 mL of 80 volume% isopropyl alcohol aqueous solution and 0.57 g of 2,2′-azobis (2-amidinopropane) dihydrochloride as a polymerization initiator were added. Obtained.

Example 4
101.8 g of cation-modified locust bean gum produced according to Synthesis Example A-4, 76.2 g of N, N-diethylacrylamide (75.9 mol% with respect to a polysaccharide-constituting monosaccharide unit), N, N-methylenebisacrylamide A cationic thickener was obtained in the same manner as in Example 1, except that 117 g, 422 mL of an 80% by volume isopropyl alcohol aqueous solution, and 0.51 g of diammonium cerium (IV) nitrate as a polymerization initiator were added.

Example 5
172.3 g of cation-modified fenugreek gum produced according to Synthesis Example A-5, 59.4 g of N, N-dimethylacrylamide (81.1 mol% with respect to a polysaccharide-constituting monosaccharide unit), 0.117 g of N, N-methylenebisacrylamide A cationic thickener was obtained in the same manner as in Example 1, except that 368 mL of an 80% by volume isopropyl alcohol aqueous solution and 0.51 g of diammonium cerium (IV) nitrate as a polymerization initiator were added.

Example 6
75.0 g of cation-modified guar gum produced according to Synthesis Example A-6, 59.4 g of N, N-dimethylacrylamide (78.9 mol% with respect to polysaccharide-constituting monosaccharide unit), 0.1156 g of N, N-methylenebisacrylamide, A cationic thickener was obtained in the same manner as in Example 1 except that 465 mL of an 80% by volume isopropyl alcohol aqueous solution and 0.51 g of 2,2′-azobis (2-amidinopropane) dihydrochloride as a polymerization initiator were added. It was.

Example 7
In a 1 liter kneader, 27.0 g of the cation-modified hydroxyethyl cellulose prepared in Synthesis Example A-7, 84.6 g of N, N-dimethylacrylamide (89.5 mol% vs. polysaccharide-constituting monosaccharide unit), N, N— 0.1542 g of methylene bisacrylamide and 488 g of ion exchange water were charged, and oxygen in the reaction system was removed through nitrogen gas. Next, the inside of the system was set to 50 ° C., and 0.68 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added as a polymerization initiator with stirring. After the addition of the initiator, the mixture was held at 50 ° C. for 10 hours. The polymerization was stopped by cooling. From the obtained polymer slurry solution, 20 volume times of acetone is used to precipitate the reaction product by reprecipitation method, and the solution is taken out by filtration under reduced pressure, washed twice with acetone, solid content is dried under reduced pressure, and then pulverized. A white powdery cationic thickener was obtained.

Example 8
A cationic thickener was obtained by the same operation as in Example 7, except that the amount of raw material charged was the same as in Example 2.

Comparative Example 1
31.3 g of cation-modified hydroxyethyl cellulose produced in Synthesis Example A-2, 79.3 g of N, N-dimethylacrylamide (86.0 mol% vs. polysaccharide-constituting monosaccharide unit), 492 mL of 80 volume% isopropyl alcohol aqueous solution, polymerization initiation A cationic thickener was obtained in the same manner as in Example 1 except that 0.68 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added as an agent.

Comparative Example 2
31.3 g of cation-modified hydroxyethyl cellulose produced in Synthesis Example A-3, 0.1542 g of N, N-methylenebisacrylamide, 492 mL of 80% by volume isopropyl alcohol aqueous solution, 2,2′-azobis (2-amidinopropane as a polymerization initiator) ) A cationic thickener was obtained in the same manner as in Example 1 except that 0.68 g of dihydrochloride was added.

Comparative Example 3
31.3 g of cation-modified hydroxyethyl cellulose prepared in Synthesis Example A-1, 79.3 g of N, N-dimethylacrylamide (85.1 mol% vs. monosaccharide unit comprising polysaccharide), 492 mL of 80 vol% aqueous isopropyl alcohol, polymerization initiation A cationic thickener was obtained in the same manner as in Example 1 except that 0.51 g of diammonium cerium (IV) nitrate was added as an agent.

Comparative Example 4
A cationic thickener was obtained by the same operation as in Example 7 except that the amount of raw material charged was the same as in Comparative Example 1.

Gel viscosity measurement results prepared from the cationic thickeners obtained from Examples 1 to 8, evaluation of gel applicability, evaluation of hand feeling (smoothness), slipperiness of hair in a wet state From the results of sensory evaluation and evaluation of the slipperiness of the hair after evaluation and drying, the cationic thickener of the present invention showed an excellent effect.

According to the present invention, it can be suitably used as a thickener for cosmetics, toiletry products, water-soluble paints, building materials, etc., and particularly when blended in cosmetics, toiletry products, etc., excellent thixotropy, applicability and hand feeling (smoothness) When applied to hair, it is clear that a cationic thickener that exhibits a very good feeling of use (smooth hair when wet, slipperiness of dry hair) is provided. is there.

Claims (8)

(A) at least one cation-modified polysaccharide and (B) the following general formula (1)

[Wherein, R ₁ represents a hydrogen atom or a methyl group, and R ₂ and R ₃ are the same or different and represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, an alkenyl group, or an alkoxyalkyl group. A group or a hydroxyalkyl group. ] A cationic thickener obtained by radical polymerization of a mixture comprising at least one nonionic vinyl monomer represented by formula (C) and at least one crosslinkable vinyl monomer as essential constituents. (A) The cation according to claim 1, wherein the cation-modified polysaccharide is obtained by substituting a part of the hydroxyl group of the polysaccharide with a quaternary nitrogen-containing group represented by the following chemical formula (2). Sexual thickener.

(Wherein R ₄ and R ₅ each represent an alkyl group having 1 to 3 carbon atoms, R ₆ represents an alkyl group having 1 to 24 carbon atoms, X ⁻ represents an anion, and n is n = 0 or n. = 1-30, and when n = 1-30, (R ₇ O) n is a polymer residue of an alkylene oxide having 2 to 4 carbon atoms, and is a polyalkylene glycol chain consisting of a single alkylene oxide And / or a polyalkylene glycol chain composed of two or more alkylene oxides.) When the viscosity at 25 ° C. when added to ion exchange water so as to be 0.5% by weight is measured with a B-type viscometer, the viscosity (η ₁ ) at 0.6 rpm is 3,000 to 500. The cationic thickening according to claim 1, wherein the viscosity (η ₂ ) at 300 rpm and 12 rpm is 300 to 50,000 mPa · s, and η ₁ > η _2. Agent. The cationic property according to any one of claims 1 to 3, wherein the blending amount of (C) is 0.001 to 3% by weight with respect to the total amount of (A) and (B). Thickener. The cationic thickener according to any one of claims 1 to 4, wherein (A) the cationic charge amount of the cation-modified polysaccharide is 0.1 to 3.0 meq / g. (A) The cationic thickener according to any one of 1 to 5, wherein the cation-modified polysaccharide is cation-modified hydroxyethyl cellulose. (B) The cationic thickener according to any one of claims 1 to 6, wherein the nonionic vinyl monomer is (meth) acrylamide or N, N-dimethyl (meth) acrylamide. The cationic thickener according to any one of claims 1 to 7, wherein (C) the crosslinkable vinyl monomer is N, N'-methylenebis (meth) acrylamide.