JP2015155519A - thickening composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thickening composition which shows an extremely high thickening property even by addition of a small amount of thickening agent, and to provide a cosmetic including the same.

SOLUTION: Provided is a thickening composition including a water-absorbing resin and a modified material of polyalkylene oxide, and a cosmetic including the same.

COPYRIGHT: (C)2015,JPO&INPIT

Description

  The present invention relates to a thickening composition. More specifically, the present invention relates to a thickening composition exhibiting a high thickening effect. The present invention also relates to a thickener that exhibits a high thickening effect.

  As hydrophilic thickeners, natural thickeners typified by xanthan gum and guar gum, semisynthetic thickeners typified by hydroxyethylcellulose, carboxymethylcellulose, etc., and carboxyvinyl polymer, polyethylene oxide, etc. Synthetic thickeners are widely used.

  Among these thickeners, carboxyvinyl polymer is frequently used because it is inexpensive and has a high thickening effect and gels in a small amount. However, the carboxyvinyl polymer has a markedly reduced thickening effect when a salt-type active agent is blended, or when the blending amount is increased to obtain a thickening effect, it tends to feel sticky when applied to the skin. There was a problem such as.

  In order to improve such problems, Patent Document 1 proposes an associative alkyl-modified carboxyvinyl polymer excellent in salt resistance. However, the carboxyvinyl polymer has a problem that it does not thicken in a system to which no salt or electrolyte is added.

  Patent Document 2 proposes an emulsified composition in which tranexamic acid is used in combination with an alkyl-modified carboxyvinyl polymer, but it is necessary to increase the blending amount in order to obtain a desired cream.

  Patent Document 3 proposes an acrylic water-absorbing resin obtained by reverse phase suspension polymerization. Although this has the refreshing feeling and the light touch which were excellent when it apply | coated to skin, there existed a subject in the thickening by a small addition amount.

International Publication No. 07/55354 Pamphlet JP 09-263510 A International Publication No. 12/160919 Pamphlet

  An object of the present invention is to provide a thickening composition exhibiting a very high thickening effect even when a small amount of thickener is added, and a cosmetic comprising the same.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that, by using a specific water-absorbing resin and a specific polyalkylene oxide-modified product in combination, an extremely high thickening effect can be obtained even in a small amount. The present invention was completed through repeated headings and further studies.

That is, the present invention includes, for example, the subject matters described in the following sections.
Item 1.
A thickening composition comprising a water absorbent resin and a polyalkylene oxide modified product.
Item 2.
Water absorbent resin and polyalkylene oxide modified product in mass ratio Water absorbent resin: polyalkylene oxide modified product = 1: 9 to 9: 1
Item 2. The thickening composition according to item 1, which is contained in a proportion of
Item 3.
Item 3. The thickening composition according to Item 1 or 2, wherein the water-absorbent resin is a resin obtained by polymerizing a water-soluble ethylenically unsaturated monomer in the presence of a water-soluble crosslinking agent.
Item 4.
Item 4. The thickening composition according to any one of Items 1 to 3, wherein the water-absorbent resin is a water-absorbent resin having a median particle diameter of 5 to 40 µm when dried and dissolved in hexane.
Item 5.
Item 5. The thickening composition according to any one of Items 1 to 4, wherein the modified polyalkylene oxide is a resin obtained by reacting a polyalkylene oxide compound, a diol compound, and a diisocyanate compound.
Item 6.
The polyalkylene oxide compound is polyethylene oxide, polypropylene oxide, polybutylene oxide, ethylene oxide / propylene oxide copolymer, ethylene oxide / butylene oxide copolymer, propylene oxide / butylene oxide copolymer, and ethylene oxide / propylene oxide / butylene oxide. Item 6. The thickening composition according to Item 5, which is at least one selected from the group consisting of copolymers.
The diol compound is ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, Item 7. The thickening composition according to Item 5 or 6, which is at least one selected from the group consisting of 1,5-pentanediol, 1,6-hexanediol, and 1,9-nonanediol.
Item 8.
The diisocyanate compound is 4,4′-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4′-diisocyanate (HMDI), 3-isocyanatomethyl-3, It is at least one selected from the group consisting of 5,5-trimethylcyclohexyl isocyanate (IPDI), 1,8-dimethylbenzole-2,4-diisocyanate, and 2,4-tolylene diisocyanate (TDI) The thickening composition of any one of claim | item 5 -7.
Item 9.
Item 10. A cosmetic comprising the thickening composition according to any one of Items 1 to 8.
Item 10.
A thickener for a water-absorbing resin-containing composition, comprising a polyalkylene oxide modified product.
Item 11.
A hydrophilic thickener containing a water absorbent resin and a polyalkylene oxide modified product.

  The modified polyalkylene oxide according to Item 10 may be the modified polyalkylene oxide according to Item 5 to Item 8, and the water-absorbent resin-containing composition according to Item 10 is replaced with Item 3 or Item. 4 is a composition containing the water-absorbent resin, and is particularly preferably a cosmetic containing the water-absorbent resin. In addition, the water absorbent resin according to Item 11 may be the water absorbent resin according to Item 3 or 4, and the polyalkylene oxide modified product according to Item 11 is modified with the polyalkylene oxide according to Item 5 to Item 8. It can be a thing.

  The thickening composition of the present invention increases the viscosity dramatically when a specific polyalkylene oxide-modified product is used in combination with a specific water-absorbent resin, and thus exhibits a high viscosity even in a small amount. For this reason, it can be widely used especially in the field of cosmetics.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  The thickening composition of the present invention contains a water-absorbent resin and a polyalkylene oxide modified product, preferably in a mass ratio of (water absorbent resin: polyalkylene oxide modified product) = 1: 9 to 9: 1. contains. When the ratio of the water absorbent resin is 1: 9 or more, that is, when the ratio of the mass of the water absorbent resin to the total mass of the water absorbent resin and the polyalkylene oxide modified product is 10% or more, the thickening effect is further improved. preferable. When the ratio of the water absorbent resin is 9: 1 or less, that is, when the ratio of the mass of the water absorbent resin to the total mass of the water absorbent resin and the polyalkylene oxide modified product is 90% or less, the amount of the polyalkylene oxide modified product is It is sufficient and the thickening effect can be expressed more preferably. The ratio of the water absorbent resin and the polyalkylene oxide modified product is more preferably (water absorbent resin: polyalkylene oxide modified product) = 1.5: 8.5 to 8.5: 1.5 by mass ratio, The ratio is more preferably 2: 8 to 7: 3, still more preferably 2.5: 7.5 to 7.5: 2.5, and 3: 7 to 7.5: 2.5. It is particularly preferred.

  As the water absorbent resin used in the present invention, for example, a polyacrylate cross-linked product (resin) widely used as a water absorbent resin can be used. In particular, a crosslinked polymer (resin) obtained by polymerizing a water-soluble ethylenically unsaturated monomer in the presence of a water-soluble crosslinking agent can be preferably used.

  Examples of the water-soluble ethylenically unsaturated monomer include (meth) acrylic acid [in the present specification, “(meth) acryl” means “acryl or methacryl”. That is, for example, the description “(meth) acrylic acid” is synonymous with the description “acrylic acid or methacrylic acid”. ], 2- (meth) acrylamide-2-methylpropanesulfonic acid or alkali metal salts thereof; (meth) acrylamide, N, N-dimethylacrylamide, 2-hydroxyethyl (meth) acrylate, N-methylol (meth) acrylamide, etc. Nonionic monomers of: amino group-containing unsaturated monomers such as diethylaminoethyl (meth) acrylate and diethylaminopropyl (meth) acrylate, or quaternized products thereof. Examples of the alkali metal in the alkali metal salt include lithium, sodium, and potassium. Of these, (meth) acrylic acid or an alkali metal salt thereof, acrylamide, methacrylamide, and N, N-dimethylacrylamide are preferable. These may be used alone or in combination of two or more.

  The water-soluble crosslinking agent preferably includes a compound having two or more polymerizable unsaturated groups and / or reactive functional groups. The reactive functional group is a functional group that can react with a functional group such as a carboxyl group of the water-soluble ethylenically unsaturated monomer to form a crosslinked structure. Specific examples thereof include a glycidyl group and an isocyanate group. Examples of the water-soluble crosslinking agent having two or more glycidyl groups include ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether. Examples of water-soluble crosslinking agents having two or more polymerizable unsaturated groups include N, N'-methylenebisacrylamide, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and water-soluble sucrose allyl ether.

  More specifically, examples of the water-soluble crosslinking agent include di- or tri (meth) acrylic polyols such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, polyoxyethylene glycol, polyoxypropylene glycol, and polyglycerin. Acid esters; unsaturated polyesters obtained by reacting the polyols with unsaturated acids such as maleic acid and fumaric acid; bisacrylamides such as N, N′-methylenebisacrylamide; polyepoxides and (meth) acrylic Di- or tri (meth) acrylic acid esters obtained by reacting with acid; di (meth) acrylic acid obtained by reacting polyisocyanate such as tolylene diisocyanate or hexamethylene diisocyanate with hydroxyethyl (meth) acrylate Carbyl esters of uric acid; having two or more polymerizable unsaturated groups such as allylated starch, allylated cellulose, diallyl phthalate, sucrose allyl ether, N, N ′, N ″ -triallyl isocyanate, divinylbenzene Compound: (Poly) ethylene glycol diglycidyl ether [“(poly)” means with or without the prefix “poly”. That is, for example, the description “(poly) ethylene glycol diglycidyl ether” is synonymous with the description “ethylene glycol diglycidyl ether or polyethylene glycol diglycidyl ether”. ], (Poly) propylene glycol diglycidyl ether, diglycidyl ether compounds such as (poly) glycerin diglycidyl ether; haloepoxy compounds such as epichlorohydrin, epibromhydrin, α-methylepichlorohydrin; 2,4-tolylene diisocyanate, hexa Compounds having two or more reactive functional groups such as isocyanate compounds such as methylene diisocyanate; 3-methyl-3-oxetanemethanol, 3-ethyl-3-oxetanemethanol, 3-butyl-3-oxetanemethanol, 3-methyl- Examples thereof include oxetane compounds such as 3-oxetane ethanol, 3-ethyl-3-oxetane ethanol, and 3-butyl-3-oxetane ethanol.

  The water-soluble crosslinking agents may be used alone or in combination of two or more. Among these, (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, (poly) glycerin diglycidyl ether, water-soluble sucrose allyl ether, and N, N′-methylenebisacrylamide are preferable.

  The water-absorbing resin used in the present invention is at least one water-soluble ethylenically unsaturated monomer selected from the group consisting of (meth) acrylic acid or an alkali metal salt thereof, acrylamide, methacrylamide, and N, N-dimethylacrylamide. The polymer is composed of (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, (poly) glycerin diglycidyl ether, water-soluble sucrose allyl ether, and N, N′-methylenebisacrylamide. Those polymerized in the presence of at least one selected water-soluble crosslinking agent are particularly preferred.

  A resin obtained by polymerizing a water-soluble ethylenically unsaturated monomer in the presence of a water-soluble crosslinking agent, which is a preferred water-absorbing resin used in the present invention, for example, a water-soluble ethylenically unsaturated monomer, It can be obtained by a method including a step of polymerizing by a suspension polymerization method in the presence of a water-soluble crosslinking agent. Among the suspension polymerization methods, the reverse phase suspension polymerization method in which the polymerization reaction is carried out while dispersing water-phase droplets containing a water-soluble ethylenically unsaturated monomer, a water-soluble crosslinking agent and water in a hydrophobic solvent. Is preferred. The water-absorbent resin obtained by the reverse phase suspension polymerization method can be particularly preferably used in the present invention because almost all the particles are spherical.

  As the hydrophobic solvent used for the reverse phase suspension polymerization, for example, a petroleum hydrocarbon solvent selected from aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons is used. Examples of the aliphatic hydrocarbon include n-pentane, n-hexane, and n-heptane. Examples of the alicyclic hydrocarbon include cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane. Aromatic hydrocarbons include benzene, toluene and xylene. In particular, at least one hydrophobic solvent selected from n-hexane, n-heptane, cyclohexane and toluene is suitably used as an industrial general-purpose solvent. The ratio of the hydrophobic solvent is, for example, 100 to 200 parts by mass with respect to 100 parts by mass of the aqueous phase containing the water-soluble ethylenically unsaturated monomer.

  The aqueous phase containing a water-soluble ethylenically unsaturated monomer or the like, or the hydrophobic solvent may contain other components such as a surfactant and a radical initiator.

  Surfactants are mainly used to stabilize the suspension during polymerization. The surfactant is not particularly limited as long as it is usually used in reverse phase suspension polymerization. Preferably, sorbitan fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, sorbitol fatty acid ester, modified polyethylene wax, modified polypropylene wax, polyvinyl alcohol, polyethylene oxide, cellulose ether (hydroxyethyl cellulose, ethyl cellulose, etc.), sodium alkylbenzene sulfonate, And polyoxyethylene alkylphenyl ether sulfate. These can be used individually by 1 type or in combination of 2 or more types.

  The amount of the surfactant is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 5.0% by mass with respect to the water-soluble ethylenically unsaturated monomer.

  The radical initiator is not particularly limited as long as it is used for normal radical polymerization, but potassium persulfate, ammonium persulfate, sodium persulfate, azo initiators, and the like are preferably used. For example, 2,2'-azobis (2-methylpropionamidine) dihydrochloride can be used as a radical initiator.

  The amount of the radical initiator is preferably 0.01 to 0, with respect to the water-soluble ethylenically unsaturated monomer. It is 5 mass%, More preferably, it is 0.02-0.2 mass%.

  In the reverse phase suspension polymerization, the size of the droplets containing a water-soluble ethylenically unsaturated monomer and the like is closely related to the size of the resulting polymer particles. Depending on conditions such as reaction vessel and production scale, for example, when a 2 L flask is used as a reaction vessel, reverse phase suspension polymerization is performed at a stirring speed of 600 to 1000 revolutions per minute (rpm). Resin particles having a size and shape suitable for use in the present invention can be preferably obtained. Further, the molecular weight and degree of crosslinking of the crosslinked polymer (that is, the resulting thickener) can be adjusted by the amount of the water-soluble crosslinking agent to be added. In this way, by adjusting the stirring speed during the polymerization reaction and the amount of water-soluble crosslinking agent added, and controlling the resin particle size, molecular weight and degree of crosslinking, the resin hydrophilicity and thickening properties are adjusted. can do.

  Other conditions for the polymerization reaction, such as the amount of radical initiator, polymerization reaction temperature, reaction time, etc., can be adjusted as appropriate. The polymerization reaction temperature is, for example, 50 to 80 ° C., and the reaction time is, for example, 30 minutes to 3 hours. For example, when a 2 L flask is used as a reaction vessel, the polymerization reaction can be started by adjusting the bath temperature to 60 ° C. In this case, the start of the polymerization reaction can be confirmed from the fact that the temperature in the reaction vessel rises to about 70 ° C. by the polymerization heat. Thereafter, the polymerization reaction is usually completed by conducting an aging reaction for about 30 minutes to 3 hours. After the aging reaction, the water-absorbing resin can be obtained by raising the bath temperature and distilling off the water and the petroleum hydrocarbon solvent in the reaction vessel.

  The water absorbent resin obtained as described above preferably has a median particle size of 5 to 40 μm, more preferably 10 to 30 μm. The median particle diameter is a value measured by using a laser diffraction particle size distribution analyzer (SALD-2000A, manufactured by Shimadzu Corporation) after dispersing the water-absorbing resin in hexane. That is, the median particle diameter is a value measured by a laser diffraction / scattering method after drying the water absorbent resin and dissolving it in hexane.

  When the median particle diameter is less than 5 μm, it is difficult to handle because it is a fine powder. Moreover, when a median particle diameter exceeds 40 micrometers, there exists a possibility that the touch at the time of application | coating of the cosmetics obtained may become a little worse.

    The polyalkylene oxide modified product used in the present invention is preferably a resin obtained by reacting a polyalkylene oxide compound, a diol compound, and a diisocyanate compound.

  Examples of the polyalkylene oxide compound include polyethylene oxide, polypropylene oxide, polybutylene oxide, ethylene oxide / propylene oxide copolymer, ethylene oxide / butylene oxide copolymer, propylene oxide / butylene oxide copolymer, and ethylene oxide / propylene oxide / butylene. An oxide copolymer etc. can be illustrated. These can be used alone or in combination of two or more. Here, “/” is a symbol used to indicate a copolymer of each oxide. For example, an ethylene oxide / propylene oxide copolymer represents a copolymer of ethylene oxide and propylene oxide.

  Although not particularly limited, a polyalkylene oxide compound having a number average molecular weight of 5,000 to 50,000 is preferable, and a polyalkylene oxide compound having a number average molecular weight of 10,000 to 30,000 is more preferable.

  Moreover, the polyalkylene oxide compound which has 90 mass% or more of ethylene oxide groups is preferable, and the polyalkylene oxide compound which has 95 mass% or more of ethylene oxide groups is more preferable.

  Examples of the diol compound include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 2,3-butanediol, and 1,4-butanediol. 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and the like. Among these diol compounds, from the viewpoint that the cosmetic composition containing the resulting thickened composition containing the polyalkylene oxide-modified product improves the familiarity with skin and hair, ethylene glycol and / or 1,4- Butanediol is preferably used. These diol compounds can be used singly or in combination of two or more.

  Although it does not restrict | limit, The usage-amount of the said diol compound becomes like this. Preferably it is 0.8-2.5 mol with respect to 1 mol of said polyalkylene oxide compounds, More preferably, it is 1.0-2.0 mol. The number of moles of the polyalkylene oxide compound can be determined by dividing its mass by the number average molecular weight.

  The diisocyanate compound is not particularly limited as long as it is a compound having two isocyanate groups (—NCO) in the same molecule. For example, 4,4′-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate ( HDI), dicyclohexylmethane-4,4′-diisocyanate (HMDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (IPDI), 1,8-dimethylbenzool-2,4 -Diisocyanate, 2,4-tolylene diisocyanate (TDI), etc. are mentioned. Among these diisocyanate compounds, dicyclohexylmethane-4,4'-diisocyanate (HMDI) and 1,6-hexamethylene diisocyanate (HDI) are preferably used. These diisocyanate compounds may be used alone or in combination of two or more.

  The use ratio of each of the polyalkylene oxide compound, the diol compound, and the diisocyanate compound is not particularly limited. The ratio [R value = (-NCO group / -OH group)] is preferably about 0.7 to 1.2, more preferably about 0.8 to 1.05. When the R value is 0.7 or more, the durability of the thickening composition (and cosmetics comprising the same) containing the resulting polyalkylene oxide-modified product can be further improved. Further, when the R value is 1.2 or less, the water-absorbing ability of the resulting polyalkylene oxide-modified product is enhanced, and a thickening composition containing the polyalkylene oxide-modified product (and a cosmetic comprising the same) is obtained. In particular, the smooth feeling when applied to the skin can be improved.

  As a method of reacting the polyalkylene oxide compound, the diol compound, and the diisocyanate compound, a known method can be used. For example, a method of reacting these by dissolving or dispersing them in a reaction solvent such as toluene, xylene, or dimethylformamide; a method of uniformly mixing powdery or solid raw materials and then reacting them by heating to a predetermined temperature Etc. From the viewpoint of industrial implementation, a method in which each raw material is continuously supplied in a molten state and mixed and reacted in a multi-screw extruder is preferable. In this case, the reaction temperature is preferably 70 to 210 ° C.

  Moreover, when producing a modified polyalkylene oxide, a catalyst may be added to the reaction system from the viewpoint of promoting the reaction. For example, an appropriate amount of triethylamine, triethanolamine, dibutyltin dilaurate, dioctyltin dilaurate, tin 2-ethylhexanoate, triethylenediamine, or the like can be added as a catalyst.

  By such a method, a modified polyalkylene oxide can be obtained. According to such a method, the polyalkylene oxide-modified product is usually obtained in the form of, for example, a pellet, a sheet, or a film. These may be finely pulverized by a pulverizer or the like, and can be easily dissolved in water by pulverization.

  Although it does not specifically limit as a grinder, For example, an atomizer, a pin mill, a jet mill, a pulverizer etc. are mentioned as a grinder suitably used for a fine grinding.

  The thickening composition of the present invention can be prepared, for example, by dissolving the water absorbent resin and the polyalkylene oxide modified product in water. More specifically, for example, by mixing 0.01 to 10 parts by mass of the water absorbent resin and 0.1 to 10 parts by mass of the polyalkylene oxide modified product with respect to 100 parts by mass of water, the mixture is dissolved. can get. The water-absorbent resin and the polyalkylene oxide modified product may be prepared separately by dissolving them in water and mixed, or may be mixed and dissolved at the same time. When the blending amount with respect to 100 parts by mass of water is 0.01 parts by mass or more and 0.1 parts by mass or more, respectively, the synergistic effect of thickening can be particularly preferably achieved. Moreover, although the upper limit of each compounding quantity can be set suitably, from a viewpoint of obtaining a preferable viscosity when using as cosmetics, all are about 10 mass parts or less, for example.

  In the thickening composition of the present invention, the viscosity is greatly increased by using the water-absorbent resin in combination with the polyalkylene oxide modified product. For this reason, in order to obtain the target viscosity, the blending amount may be small as compared with the case where the water absorbent resin is blended alone. Even if the upper limit of the combined amount is, for example, 1 part by mass, or even 0.5 part by mass, a sufficient thickening effect can be exhibited.

  The thickening composition of the present invention preferably contains, for example, an aqueous medium (particularly water) in addition to the water-absorbent resin and the polyalkylene oxide-modified product, and may further contain other components. In particular, the thickening composition of the present invention can be preferably used as a cosmetic. For example, cosmetics can be prepared by mixing the thickening composition of the present invention and known ingredients used in cosmetics. Although it will not restrict | limit especially as a component used together with the thickening composition of this invention if it is a well-known component used for cosmetics, For example, glycerol, glycol, sorbitol, dipropylene glycol, polyethyleneglycol etc. can be mentioned. These are particularly suitable when the cosmetic of the present invention is used as a humectant. In addition, aluminum hydroxychloride, tannic acid, zinc sulfate, zinc oxide, etc., coloring agents, surfactants (anionic, nonionic, amphoteric or cationic), other perfumes, antioxidants, UV absorbers, plant extracts, etc. Can be illustrated. These are particularly suitable when the cosmetic of the present invention is used as an antiperspirant.

  Specific examples of the cosmetic of the present invention include skin care cosmetics, makeup cosmetics, hair care cosmetics, body care cosmetics, and fragrance cosmetics. Although not particularly limited, examples of more specific forms of cosmetics include powder foundations, liquid foundations, emulsions, lotions, liquid cosmetics, packs, facial cleansing foams, shampoos, rinses, hair set agents, emollient creams, etc. Can do. These cosmetics can be produced according to conventional methods.

  Moreover, this invention includes the thickener for water-absorbing-resin containing compositions containing a polyalkylene oxide modified substance. The said thickener may consist only of polyalkylene oxide modified material, and may contain other components (for example, well-known thickener).

  The polyalkylene oxide modified product in the thickener of the present invention is preferably the above polyalkylene oxide modified product. In addition, the water-absorbing resin composition that is a target for using the thickener is preferably a composition containing the water-absorbing resin, and a composition containing the water-absorbing resin and an aqueous medium (particularly water). It is more preferable that the cosmetic composition contains the water-absorbent resin. Further, when the thickener is used in a water absorbent resin-containing composition, the mass ratio of the water absorbent resin to the polyalkylene oxide modified product (water absorbent resin: polyalkylene oxide modified product) is preferably 1: 9. To 9: 1, more preferably 1.5: 8.5 to 8.5: 1.5, more preferably 2: 8 to 7: 3, and even more preferably 2.5: 7.5 to 7.5. : 2.5, particularly preferably 3: 7 to 7.5: 2.5.

  Furthermore, the present invention also includes a hydrophilic thickener containing a water absorbent resin and a polyalkylene oxide modified product. The said thickener may consist only of a water absorbing resin and a polyalkylene oxide modified material, and may contain other components (for example, well-known hydrophilic thickener).

  The water absorbent resin in the thickener of the present invention is preferably the above water absorbent resin, and the polyalkylene oxide modified product in the thickener is preferably the above polyalkylene oxide modified product. . The said thickener can be used suitably especially for cosmetics. In addition, the thickener has a mass ratio of the water absorbent resin to the polyalkylene oxide modified product (water absorbent resin: polyalkylene oxide modified product) of preferably 1: 9 to 9: 1, more preferably 1.5: 8.5 to 8.5: 1.5, more preferably 2: 8 to 7: 3, still more preferably 2.5: 7.5 to 7.5: 2.5, particularly preferably 3: 7 to 7.5: 2.5.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
Production Example 1-1: Manufacture of water-absorbent resin 90 g of 80% by mass of acrylic acid aqueous solution was added to a 500 mL Erlenmeyer flask, and 94 g of 30% by mass of sodium hydroxide aqueous solution was added dropwise while cooling the flask from outside. Neutralized. Furthermore, 56 g of ion exchange water, water-soluble sucrose allyl ether having a low degree of substitution as a cross-linking agent 36 g (0.4% by mass with respect to the acrylic acid aqueous solution), 2,64 'as an initiator, 0.064 g of 2,2′-azobis (2-methylpropionamidine) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries, Ltd.) In addition, an aqueous solution of neutralized acrylic acid (water-soluble ethylenically unsaturated monomer aqueous solution) was prepared. Separately, 330 g of n-heptane was added to a 2 L four-necked separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a nitrogen gas introduction tube, and sucrose stearate (as a surfactant) 2.7 g of Mitsubishi Chemical Foods Co., Ltd. S-370) was dispersed and dissolved. Then, the previously prepared aqueous solution of neutralized acrylic acid (water-soluble ethylenically unsaturated monomer aqueous solution) was added and the system was purged with nitrogen while stirring at a stirring speed of 1200 rpm and the bath temperature was kept at 60 ° C. The polymerization was carried out for 1 hour by the reverse phase suspension polymerization method. After completion of the polymerization, water and n-heptane were distilled off to obtain 103 g of water absorbent resin powder. The obtained water-absorbent resin was spherical, and its median particle diameter was 11 μm.

Production Example 1-2: Production of water-absorbing resin 550 mL of n-heptane was added to a 1 L four-necked cylindrical round bottom flask equipped with a stirrer, a reflux condenser, and a nitrogen gas introduction tube. To this, 1.38 g of hexaglyceryl monobeherate (surfactant; nonionic GV-106 manufactured by NOF Corporation) with an HLB of 13.1 was added and dispersed, and the temperature was raised to 50 ° C. to obtain the surfactant. After dissolution, it was cooled to 30 ° C.

  On the other hand, a 500 mL Erlenmeyer flask was separately prepared, and 92 g of an 80% by mass acrylic acid aqueous solution was added thereto. To this, 152.6 g of a 20.1 mass% aqueous sodium hydroxide solution was added dropwise while cooling from the outside to neutralize 75 mol%, and then 0.11 g of potassium persulfate and ethylene glycol disulfide as a crosslinking agent. Further, 0.019 g of glycidyl ether was added and dissolved. Thereby, an aqueous solution of partially neutralized acrylic acid (water-soluble ethylenically unsaturated monomer aqueous solution) was prepared.

  Next, the entire amount of the resulting aqueous solution of partially neutralized acrylic acid is added to and dispersed in the four-necked cylindrical round bottom flask under the condition of 1500 rpm, the system is replaced with nitrogen, and the temperature is raised. The temperature was kept at 70 ° C., and the polymerization reaction was carried out by reverse phase suspension polymerization for 3 hours.

  After completion of the polymerization reaction, the obtained slurry was dried at 120 ° C. for 2 hours to obtain 191.2 g of a crosslinked polyacrylate (water absorbent resin). The obtained water-absorbent resin was spherical, and its median particle size was 20 μm.

Production Example 2-1: Production of Modified Polyalkylene Oxide In a storage tank a equipped with a stirrer kept at 80 ° C., 100 parts by mass of fully dehydrated polyethylene oxide having a number average molecular weight of 20000, 1,4-butanediol 0 9.9 parts by mass and dioctyltin dilaurate 0.1 parts by mass were stirred in a nitrogen gas atmosphere to obtain a uniform mixture. Separately, dicyclohexylmethane-4,4′-diisocyanate was charged into a storage tank b kept at 30 ° C. and stored in a nitrogen gas atmosphere.

  Using a metering pump, set the mixture in storage tank a at a rate of 500 g / min, and dicyclohexylmethane-4,4′-diisocyanate in storage tank b at a rate of 19.4 g / min. Was continuously supplied to the twin-screw extruder (R value (-NCO group / -OH group) = 1), mixed and reacted in the extruder, a strand was taken out from the outlet of the extruder, and pelletized by a pelletizer. Further, the product was made into a fine powder product by a jet mill to obtain a modified polyalkylene oxide.

Production Example 2-2: Production of modified polyalkylene oxide Ethylene oxide / propylene oxide (mass ratio: 90/10) copolymer having a number average molecular weight of 15000 was heated to 40 ° C. at a rate of 250 g / min. Glycol was supplied at a rate of 2.1 g / min to a 40 mmφ single screw extruder (L / D = 40, set temperature: 90 ° C.), and both were melt mixed.

  A mixture obtained from the discharge port (discharged in a uniform molten state and analyzed by HPLC to confirm that it was mixed at a charging ratio) was mixed with a 30 mmφ twin screw extruder (L / D = 41. 5) was continuously supplied to the hopper port (set temperature: 80 ° C.). At the same time, dioctyltin dilaurate was supplied to the hopper port of the twin-screw extruder at a rate of 0.5 g / min.

  Separately, dicyclohexylmethane-4,4′-diisocyanate adjusted to 30 ° C. is supplied at a rate of 12.4 g / min to the screw barrel portion located downstream of the hopper port of the twin-screw extruder. (R value = 0.95), the reaction was continued under a nitrogen atmosphere (set temperature: 180 ° C.). The strand obtained from the twin-screw extruder outlet was cooled, pelletized with a pelletizer, and further pulverized to obtain a polyalkylene oxide-modified product.

Example 1
1 L beakers A and B containing 792 g of ion-exchanged water were set in a jar tester and stirred at 400 rpm. To beaker A, 8 g of the water-absorbent resin obtained in Production Example 1-1 was slowly added, and to beaker B, 8 g of polyalkylene oxide obtained in Production Example 2-1 were slowly added, and dissolved by stirring for 3 hours. The solution of beaker A was used as solution A, and the solution of beaker B was used as solution B. 75 g of the solution A and 225 g of the solution B were weighed into a 500 mL plastic container and mixed for 5 minutes with a hand mixer. And after defoaming with a centrifuge, it was immersed in a 25 degreeC constant temperature water tank, and the viscosity was measured 1 hour afterward.

Example 2
150 g of solution A and 150 g of solution B prepared in Example 1 were weighed in a 500 mL plastic container and mixed for 5 minutes with a hand mixer. And after defoaming with a centrifuge, it was immersed in a 25 degreeC constant temperature water tank, and the viscosity was measured 1 hour afterward.

Example 3
225 g of the solution A prepared in Example 1 and 75 g of the solution B were weighed into a 500 mL plastic container and mixed for 5 minutes with a hand mixer. And after defoaming with a centrifuge, it was immersed in a 25 degreeC constant temperature water tank, and the viscosity was measured 1 hour afterward.

Comparative Example 1
300 g of the solution A prepared in Example 1 was weighed into a 500 mL plastic container and mixed for 5 minutes with a hand mixer. And after defoaming with a centrifuge, it was immersed in a 25 degreeC constant temperature water tank, and the viscosity was measured 1 hour afterward.

Comparative Example 2
300 g of the solution B prepared in Example 1 was weighed into a 500 mL plastic container and mixed for 5 minutes with a hand mixer. And after defoaming with a centrifuge, it was immersed in a 25 degreeC constant temperature water tank, and the viscosity was measured 1 hour afterward.

Example 4
Add 198.5 g of ion-exchanged water to a 200 mL beaker, set in a jar tester, and stir at 400 rpm. 1.0 g of the water-absorbent resin obtained in Production Example 1-1 and polyalkylene oxide 0 obtained in Production Example 2-1. .5 g was slowly added and dissolved by stirring for 3 hours. And it was immersed in a 25 degreeC constant temperature water tank, and the viscosity was measured 1 hour afterward.

Example 5
Add 198.0 g of ion-exchanged water to a 200 mL beaker, set in a jar tester, and stir at 400 rpm. 1.0 g of the water absorbent resin obtained in Production Example 1-1 and polyalkylene oxide 1 obtained in Production Example 2-1. 0.0 g was slowly added and stirred for 3 hours to dissolve. And it was immersed in a 25 degreeC constant temperature water tank, and the viscosity was measured 1 hour afterward.

Example 6
197.5 g of ion-exchanged water was added to a 200 mL beaker, set in a jar tester and stirred at 400 rpm, 1.0 g of the water-absorbent resin obtained in Production Example 1-1 and polyalkylene oxide 1 obtained in Production Example 2-1. .5 g was slowly added and dissolved by stirring for 3 hours. And it was immersed in a 25 degreeC constant temperature water tank, and the viscosity was measured 1 hour afterward.

Example 7
Add 197.0 g of ion-exchanged water to a 200 mL beaker, set in a jar tester, and stir at 400 rpm. 1.0 g of the water absorbent resin obtained in Production Example 1-1 and polyalkylene oxide 2 obtained in Production Example 2-1. 0.0 g was slowly added and stirred for 3 hours to dissolve. And it was immersed in a 25 degreeC constant temperature water tank, and the viscosity was measured 1 hour afterward.

Comparative Example 3
Add 199.0 g of ion-exchanged water to a 200 mL beaker, set in a jar tester and stir at 400 rpm, slowly add 1.0 g of the water-absorbent resin obtained in Production Example 1-1, and stir for 3 hours to dissolve. . And it was immersed in a 25 degreeC constant temperature water tank, and the viscosity was measured 1 hour afterward.

Comparative Example 4
197.0 g of ion-exchanged water was added to a 200 mL beaker, set in a jar tester and stirred at 400 rpm, 3.0 g of the water-absorbent resin obtained in Production Example 1-1 was slowly added, and the mixture was stirred for 3 hours to dissolve. . And it was immersed in a 25 degreeC constant temperature water tank, and the viscosity was measured 1 hour afterward.

Comparative Example 5
197.0 g of ion-exchanged water was added to a 200 mL beaker, set in a jar tester and stirred at 400 rpm, 3.0 g of the polyalkylene oxide obtained in Production Example 2-1 was slowly added, and the mixture was stirred for 3 hours to dissolve. . And it was immersed in a 25 degreeC constant temperature water tank, and the viscosity was measured 1 hour afterward.

[Evaluation method]
The median particle diameter measurement of each water-absorbing resin in the above example and the viscosity measurement of each sample were both performed under the following conditions.
<Medium particle size measurement>
The water-absorbing resin 0.1 g was dispersed in 5 ml of hexane, and the median particle size was measured using a particle size distribution measuring apparatus (using Shimadzu Corporation SALD2000 flow cell).
<Viscosity measurement conditions>
Equipment used: B-type viscometer (VDH2 manufactured by Shibaura Semtec Co., Ltd.)
Measurement temperature: 25 ° C., rotation speed: 20 rpm, rotor: No. 7

  From Table 1, it was found that the combined use of the water-absorbent resin and the polyalkylene oxide-modified product increased the viscosity of the water-absorbent resin alone or the polyalkylene oxide-modified product alone. In the case of the modified polyalkylene oxide alone, no thickening effect was observed, so it was considered that the modified polyalkylene oxide had an effect of increasing the thickening effect of the water absorbent resin.

  From Table 2, it was found that by adding the polyalkylene oxide-modified product to the aqueous solution of the water absorbent resin, the thickening effect was dramatically improved as compared with the case of the water absorbent resin alone.

Claims (11)

A thickening composition comprising a water absorbent resin and a polyalkylene oxide modified product. Water absorbent resin and polyalkylene oxide modified product in mass ratio Water absorbent resin: polyalkylene oxide modified product = 1: 9 to 9: 1
The thickening composition of Claim 1 contained in the ratio of.   The thickening composition according to claim 1 or 2, wherein the water-absorbing resin is a resin obtained by polymerizing a water-soluble ethylenically unsaturated monomer in the presence of a water-soluble crosslinking agent.   The thickening composition according to any one of claims 1 to 3, wherein the water absorbent resin is a water absorbent resin having a median particle diameter of 5 to 40 µm when dried and dissolved in hexane.   The thickening composition according to any one of claims 1 to 4, wherein the modified polyalkylene oxide is a resin obtained by reacting a polyalkylene oxide compound, a diol compound, and a diisocyanate compound.   The polyalkylene oxide compound is polyethylene oxide, polypropylene oxide, polybutylene oxide, ethylene oxide / propylene oxide copolymer, ethylene oxide / butylene oxide copolymer, propylene oxide / butylene oxide copolymer, and ethylene oxide / propylene oxide / butylene oxide. The thickening composition according to claim 5, which is at least one selected from the group consisting of copolymers.   The diol compound is ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, The thickening composition according to claim 5 or 6, which is at least one selected from the group consisting of 1,5-pentanediol, 1,6-hexanediol, and 1,9-nonanediol.   The diisocyanate compound is 4,4′-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4′-diisocyanate (HMDI), 3-isocyanatomethyl-3, It is at least one selected from the group consisting of 5,5-trimethylcyclohexyl isocyanate (IPDI), 1,8-dimethylbenzole-2,4-diisocyanate, and 2,4-tolylene diisocyanate (TDI) The thickening composition of any one of Claims 5-7.   Cosmetics containing the thickening composition in any one of Claims 1-8. A thickener for a water-absorbing resin-containing composition, comprising a polyalkylene oxide modified product. A hydrophilic thickener containing a water absorbent resin and a polyalkylene oxide modified product.