JP2016147813A - Composition containing ultraviolet absorber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide cosmetics having refreshed and light feeling when using, while having excellent emulsification stability and smoothness, and rich viscosity, in cosmetics containing an ultraviolet absorber of a UV-A region and ultraviolet absorber of a UV-B region.SOLUTION: Disclosed is a composition containing (A): an ultraviolet absorber of a UV-A region; (B): an ultraviolet absorber of a UV-B region; (C): polyalkylene oxide denatured material that is a resin obtained by reacting a polyalkylene oxide compound, diol compound, and diisocyanate compound; and (D): a polymer of an ethylenic unsaturated carboxylic acid monomer crosslinked by a water-soluble crosslinker.SELECTED DRAWING: None

Description

  The present invention relates to a composition containing an ultraviolet absorber. In more detail, this invention relates to the composition (especially cosmetics composition) containing the ultraviolet absorber of UV-A area | region and the ultraviolet absorber of UV-B area | region.

  In general, for sunscreen cosmetics, UV scattering agents such as fine particle titanium oxide and cerium oxide having a scattering effect in the UV-A region (320 to 400 nm), benzophenone compounds, paraaminobenzoic acid compounds, and cinnamic acid compounds And the like (see Patent Document 1), 4-tert-butyl-4′-methoxydibenzoylmethane, hexyl diethylaminohydroxybenzoyl benzoate, etc. In which UV absorbers in the UV-A region and UV absorbers in the UV-B region such as benzophenone compounds, paraaminobenzoic acid compounds, and cinnamic acid compounds are blended (see Patent Document 2).

  In products containing UV-A region organic UV absorbers, carboxyvinyl polymers, alkyl-modified carboxy polymers, etc. are used as dispersants (see Patent Document 2). Many of them are solid or pasty at room temperature, and sunscreen cosmetics containing these are sometimes unsatisfactory in terms of use feeling because they may cause a sticky feeling.

JP 2002-326906 A JP 2011-046670 A

  The object of the present invention is a composition containing an organic ultraviolet absorber in the UV-A region and an organic ultraviolet absorber in the UV-B region, as compared with the case where a conventional carboxyvinyl polymer or an alkyl-modified carboxyvinyl polymer is used. Another object of the present invention is to provide a composition that is excellent in emulsification stability, has a rich viscosity, and has a refreshing and light feeling to use.

  In the composition containing the organic ultraviolet absorber in the UV-A region and the organic ultraviolet absorber in the UV-B region, the inventors of the present invention are ethylenic crosslinked by a specific polyalkylene oxide modified product and a water-soluble crosslinking agent. By using polymers of unsaturated carboxylic acid monomers, it has excellent emulsification stability. When applied to the skin, (1) a high-viscosity rich viscosity and (2) a refreshing light feeling of use. The present inventors have found that a composition having the properties to be obtained can be obtained, and have further studied to arrive at the present invention.

That is, the present invention includes, for example, the subject matters described in the following sections.
Item 1.
(A): UV absorber in the UV-A region, (B): UV absorber in the UV-B region, and (C): polyalkylene oxide obtained by reacting a polyalkylene oxide compound, a diol compound, and a diisocyanate compound. A composition containing a modified product and (D): a polymer of an ethylenically unsaturated carboxylic acid monomer crosslinked by a water-soluble crosslinking agent.
Item 2.
Item 2. The composition according to Item 1, comprising (C) and (D) in a mass ratio (C) :( D) = 20: 80 to 60:40.
Item 3.
Polyalkylene oxide compounds are 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 copolymer. Item 3. The composition according to Item 1 or 2, which is at least one selected from the group consisting of polymers.
Item 4.
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 4. The composition according to any one of Items 1 to 3, which is at least one selected from the group consisting of 1,5-pentanediol, 1,6-hexanediol, and 1,9-nonanediol.
Item 5.
The diisocyanate compound is 4,4′-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4′-diisocyanate (HMDI), 3-isocyanatomethyl-3,5 , 5-trimethylcyclohexyl isocyanate (IPDI), 1,8-dimethylbenzole-2,4-diisocyanate, and 2,4-tolylene diisocyanate (TDI). Item 5. The composition according to any one of Items 1 to 4.
Item 6.
Item 6. The composition according to any one of Items 1 to 5, wherein the ethylenically unsaturated carboxylic acid monomer is at least one selected from the group consisting of acrylic acid and methacrylic acid.
Item 7.
Item 7. The composition according to any one of Items 1 to 6, which is a cosmetic composition.

  According to the present invention, the emulsification stability is improved, and when applied to the skin, a lighter and lighter feeling of use and a higher-class feeling than when a conventional carboxyvinyl polymer or an alkyl-modified carboxyvinyl polymer is used. Compositions that provide a certain viscosity can be provided. Therefore, the said composition is useful as cosmetics (especially sunscreen cosmetics), a pharmaceutical (or those raw materials), for example.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

The composition according to the present embodiment reacts (A) an ultraviolet absorber in the UV-A region, (B) an ultraviolet absorber in the UV-B region, and (C) a polyalkylene oxide compound, a diol compound, and a diisocyanate compound. And (D) a polymer of an ethylenically unsaturated carboxylic acid monomer crosslinked with a water-soluble crosslinking agent.
Examples of the ultraviolet absorber in the UV-A region used in the present invention include 4-tert-butyl-4′-methoxydibenzoylmethane, diethylaminohydroxybenzoyl hexyl benzoate, dimethoxybenzylidene dioxoimidazolidine propionate 2-ethylhexyl , Methylenebisbenzotriazolyltetramethylbutylphenol, bisethylhexyloxyphenol methoxyphenyltriazine, and the like. Among them, 4-tert-butyl-4′-methoxydibenzoylmethane is preferable. These ultraviolet absorbers in the UV-A region can be used alone or in combination of two or more.

  Examples of the ultraviolet absorber in the (B) UV-B region include octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, and methyl. -2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate, 2-ethoxyethyl-p-methoxycinnamate Mate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate Cinnamic acid-based purple Linear absorber; 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'- Benzophenone ultraviolet absorbers such as phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone; paraaminobenzoic acid (hereinafter abbreviated as PABA) monoglycerin ester , Paraaminobenzoic acid series such as N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N, N-dimethyl PABA ethyl ester, N, N-dimethyl PABA butyl ester, N, N-dimethyl PABA methyl ester UV absorbers; salicylic acid UV absorbers such as amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate; 3- (4-methylbenzylidene) camphor, 3-benzylidene- Examples thereof include ultraviolet absorbers such as d1-camphor, urocanic acid, urocanic acid ethyl ester, octyl triazone, and 4-methoxy-4′-t-butyldibenzoylmethane. Of these, octyl-p-methoxycinnamate (also referred to as 2-ethylhexyl-p-methoxycinnamate, 2-ethylhexyl 4-methoxycinnamate) is preferable. The ultraviolet absorber of a UV-B area | region can be used individually by 1 type or in combination of 2 or more types.

  The (C) 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, ethylene glycol and / or 1,4-butanediol are 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.

  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.

  The polymer of the ethylenically unsaturated carboxylic acid monomer cross-linked by the water-soluble cross-linking agent (D) used in the present invention is preferably water-absorbing and may be a water-absorbing resin. That is, (D) is a water-absorbing resin containing a polymer of an ethylenically unsaturated carboxylic acid monomer, preferably crosslinked by a water-soluble crosslinking agent, more preferably a water-absorbing resin comprising the polymer. is there.

  As the ethylenically unsaturated carboxylic acid monomer in (D), a water-soluble ethylenically unsaturated carboxylic acid monomer is preferable, and specific examples thereof include acrylic acid and methacrylic acid. An ethylenically unsaturated carboxylic acid monomer can be used individually by 1 type or in combination of 2 or more types. In the present invention, the neutralization degree of the resulting polymer can be easily adjusted by neutralizing the carboxyl group of the ethylenically unsaturated carboxylic acid with an alkali. In the present invention, the degree of neutralization refers to the ratio of the number of moles of neutralized groups to the total number of moles of carboxyl groups in the ethylenically unsaturated carboxylic acid. Examples of the alkali used for neutralization include sodium hydroxide, potassium hydroxide, triethanolamine, diisopropylamine, ammonia and the like. The neutralization method is not particularly limited, and examples thereof include a method of previously neutralizing an ethylenically unsaturated carboxylic acid monomer and a method of neutralizing a polymer obtained by polymerization.

  Moreover, as a water-soluble crosslinking agent in (D), the compound which has 2 or more of polymerizable unsaturated groups and / or reactive functional groups is mentioned preferably. The reactive functional group is a functional group that can react with the carboxyl group of the ethylenically unsaturated carboxylic acid 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. A water-soluble crosslinking agent can be used individually by 1 type or in combination of 2 or more types. Of these, water-soluble sucrose allyl ether is preferably used.

  The degree of etherification of the water-soluble sucrose allyl ether used as the water-soluble crosslinking agent is preferably 2.0 to 3.5, more preferably 2.2 to 3.2. If the degree of etherification of the water-soluble sucrose allyl ether is low, the allyl group, which is a functional group involved in the cross-linking reaction, is insufficient, and the cross-linking reaction tends not to proceed effectively. If the degree of etherification of the water-soluble sucrose allyl ether is high, the solubility in water decreases, so that the cross-linking reaction between the sucrose allyl ether and the ethylenically unsaturated carboxylic acid monomer is difficult to proceed in the aqueous phase. Tend. This degree of etherification is the average value of the molar ratio of allyl ether groups to sucrose. The degree of etherification can be calculated from the amount of acetic anhydride consumed by reacting the hydroxyl group remaining in sucrose allyl ether with acetic anhydride in pyridine.

  The water-soluble sucrose allyl ether can be obtained, for example, by adding sodium hydroxide as a catalyst to an aqueous sucrose solution to convert sucrose to alkaline sucrose and then adding allyl bromide dropwise to perform etherification. it can. At this time, water-soluble sucrose allyl ether is efficiently obtained by adjusting the amount of allyl bromide to a range of preferably 2 to 6 times mol, more preferably 2 to 5 times mol of sucrose. be able to. The etherification reaction temperature is, for example, about 80 ° C. Usually, the reaction is completed in about 3 hours after the addition of allyl bromide. Water-soluble sucrose allyl ether can be recovered by adding alcohol to the aqueous phase separated from the reaction solution, filtering out precipitated salts, and distilling off excess alcohol and water.

(D) A polymer of an ethylenically unsaturated carboxylic acid monomer cross-linked by a water-soluble cross-linking agent is, for example, a suspension of an ethylenically unsaturated carboxylic acid monomer in the presence of a water-soluble cross-linking agent. It can be obtained by a method including a step of polymerizing by a legal method. Among the suspension polymerization methods, the reverse phase suspension polymerization method in which a polymerization reaction is carried out while dispersing droplets of an aqueous phase containing an ethylenically unsaturated carboxylic acid monomer, a water-soluble crosslinking agent and water in a hydrophobic solvent. Is preferred.
As the hydrophobic solvent used for the reverse phase suspension polymerization, for example, at least one 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 ethylenically unsaturated carboxylic acid monomer and the like.

  In the reverse phase suspension polymerization, the aqueous phase containing an ethylenically unsaturated carboxylic acid 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 one or more surfactants selected from polyoxyethylene alkylphenyl ether sulfates.

  The amount of the surfactant is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass with respect to the ethylenically unsaturated carboxylic acid monomer. If the amount of the surfactant is small, there may be a problem in the stability of the suspension state during polymerization, and if the amount of the surfactant is large, it tends to be economically disadvantageous.

  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 0.5% by mass, more preferably 0.02 to 0.2% by mass with respect to the ethylenically unsaturated carboxylic acid monomer. If the amount of the radical initiator is small, the polymerization reaction tends not to proceed or a long time is required for the reaction. When the amount of the radical initiator is increased, the chain length of the polymer to be produced is shortened, and the viscosity of the aqueous liquid of the water absorbent resin tends to decrease.

  During the reverse phase suspension polymerization, the size of the droplets containing the ethylenically unsaturated carboxylic acid 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, a polymer of an appropriate size can be obtained by carrying out reverse phase suspension polymerization at a stirring speed of 800 to 1000 rpm. It is likely that particles can be obtained. Thus, the size of the polymer particles can be controlled by adjusting the stirring speed during the polymerization reaction. In this way, water absorbent resin particles having a median particle diameter of preferably about 5 to 30 μm can be obtained. The shape of the polymer particles obtained in this way is spherical and is retained even in an aqueous liquid such as cosmetics, so in cosmetics using this, it has a positive effect on various properties, touch and feel. Conceivable.

  Other conditions for the polymerization reaction, such as the amount of radical initiator, polymerization reaction temperature, reaction time, etc., are also 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 temperature 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. If the aging time is shorter than that, the reaction may not be completed sufficiently, and the remaining ethylenically unsaturated carboxylic acid monomer may increase. After the aging reaction, for example, the product can be obtained by elevating the bath temperature and distilling off the water and the petroleum hydrocarbon solvent in the reaction vessel.

  About content of the said component (A)-(D) contained in the composition of this invention, it can set suitably in the range which does not impair the effect of this invention.

  In particular, from the viewpoint that the effects of the present invention can be preferably exhibited, (C) and (D) are preferably included in a mass ratio of (C) :( D) = 20: 80 to 60:40, and 20: More preferably, it is contained in a ratio of 80 to 50:50.

  Moreover, about (A) and (B), what is necessary is just to mix | blend with a composition in the range with which an ultraviolet-ray absorption effect is show | played, respectively. For example, it is preferable that (A) and (B) are included in a mass ratio of (A) :( B) = 30: 70 to 70:30, and (A) :( B) = 40: 60-60 : More preferably, it is contained in a ratio of 40. Moreover, it is preferable that (A) is contained 1 mass% or more with respect to the whole composition, About 1-15 mass% is more preferable, About 2-10 mass% is further more preferable. (B) is preferably contained in an amount of 1% by mass or more, more preferably about 1 to 15% by mass, and still more preferably about 2 to 10% by mass with respect to the entire composition.

  In addition, in this specification, the numerical value of content and the content rate about each component which the composition of this invention contains represents the value when not absorbing water (dry mass conversion value) regarding a water absorbing component.

  The composition of the present invention is preferably used as a cosmetic composition. When used as a cosmetic composition, it is particularly preferably used as a sunscreen cosmetic composition. Although the form of cosmetics is not specifically limited, For example, a lotion, a milky lotion, a cosmetic liquid, a cream, a cream pack, a gel cream etc. can be illustrated. When the cosmetic composition according to the present embodiment is used as an emulsified cosmetic composition such as cream, emulsion, gel cream, etc., it provides a refreshing feeling and lightness in addition to a rich viscosity without causing kinks, and is particularly advantageous.

  In producing the cosmetic composition, known components that are usually used in cosmetics can be further used. Examples of such components include oily components, humectants, surfactants, thickeners, and the like.

  In general, an oil-in-water emulsified cosmetic is produced in a process in which an aqueous phase and an oil phase are heated and dissolved at around 60 ° C., emulsified with a homomixer, and then cooled with stirring. Components (C) and (D) function as a rheology control agent for oil-in-water emulsion cosmetics and an emulsion stabilizer for ultraviolet absorbers. The total amount of (C) and (D) is, for example, about 0.1 to 0.3% by mass with respect to all components in a general emulsion, and about 0.2 to 2% by mass in a general cream, for example. In general, when 1% by mass or more is blended, there is an increased risk of stickiness and twisting. However, for products such as ultraviolet absorbers, ultraviolet scattering agents, whitening agents, etc., 0.5 to 2 mass% of components (C) and (D) may be added from the viewpoint of obtaining a desired viscosity. preferable.

  The oil component used in the cosmetic is not particularly limited, but may be natural oil, silicone oil, ester oil, or the like in consideration of the texture to the skin, familiarity, appearance, slipperiness, and the like.

  Examples of natural oils include paraffinic hydrocarbons such as liquid paraffin, olive oil, macadamia nut oil, castor oil, jojoba oil, orange luffy oil, beeswax, lanolin, mineral oil, and squalane.

  Examples of the silicone oil include modified silicone oils such as methylpolysiloxane, methylphenylpolysiloxane, cyclic methylsiloxane, and silicone polyether copolymer.

  Examples of the ester oil include various fatty acid esters. For example, octyldodecyl ester of each fatty acid such as oleic acid, erucic acid, myristic acid, ricinoleic acid is preferable.

  These oily components may be used alone or in combination of two or more.

  The humectant is suitably selected from glycerin, propylene glycol, sorbit, polyethylene glycol, dipropylene glycol, 1,3-butylene glycol, diglycerin, mannitol, polyoxyethylene methyl glycoside, and the like.

As the surfactant, nonionic glyceryl monostearate, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, and the like are often used. However, anionic, cationic or amphoteric surfactants can also be used.
The cosmetic of the present invention may further contain a polysaccharide water-soluble polymer such as hydroxyethyl cellulose and xanthan gum, a carboxyvinyl polymer, and an alkyl-modified carboxyvinyl polymer as a thickener.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

<Production of polyalkylene oxide modified product>
(Production Example 1)
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, 0.9 part by mass of 1,4-butanediol and 0.1 part by mass of dioctyltin dilaurate The mixture was 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) = 1.00), mixed and reacted in the extruder, a strand was taken out from the outlet of the extruder, and the pelletizer was used. Pelletization was performed to obtain a modified polyalkylene oxide.

<Synthesis of water-soluble sucrose allyl ether>
(Production Example 2)
A stirrer, a reflux condenser and a dropping funnel were attached to a 1000 mL separable flask. In this separable flask, 48 g (1.2 mol) of sodium hydroxide was dissolved in 144 g of water. 136.8 g (0.4 mol) of sucrose was added thereto, and the mixture was stirred at 70 to 85 ° C. for 120 minutes to prepare an alkaline sucrose aqueous solution. To this alkaline sucrose aqueous solution, 145.2 g (1.2 mol) of allyl bromide was added dropwise at 70 to 85 ° C. over 1.5 hours, and then aged at 80 ° C. for 3 hours to obtain sucrose. Was allyl etherified. After cooling, 440 g of water was added, and excess oil was separated with a separatory funnel to obtain a crude sucrose allyl ether aqueous solution. After adjusting the pH to 6-8 by adding hydrochloric acid to this crude sucrose allyl ether aqueous solution, water was removed using a rotary evaporator until the mass of the aqueous solution reached 480 g. Then, 200 g of ethanol was added to precipitate a by-product salt such as sodium bromide, and the precipitate was removed from the aqueous solution by filtration. Further, excess water was removed from the aqueous solution by using an evaporator to obtain 166 g of purified water-soluble sucrose allyl ether having a degree of etherification of 2.4.

<Synthesis of Polymer (Water Absorbing Resin) of Ethylenically Unsaturated Carboxylic Acid Monomer Crosslinked by Water-soluble Crosslinking Agent>
(Production Example 3)
A stirrer, a reflux condenser, and a dropping funnel were attached to a 500 mL separable flask. In this separable flask, 72 g of acrylic acid and water were put to prepare 90 g of an 80% by mass acrylic acid aqueous solution. While cooling the acrylic acid aqueous solution, 54 g of a 30% by mass aqueous sodium hydroxide solution was added dropwise to neutralize the aqueous solution. Furthermore, 56 g of ion-exchanged water, 0.32 g of water-soluble sucrose allyl ether of Production Example 2 as a crosslinking agent (0.35% by mass with respect to an aqueous acrylic acid solution), and 2,2′-azobis (2 -Methylpropionamidine) dihydrochloride (V-50 manufactured by Wako Pure Chemical Industries, Ltd.) (0.04 g) was added to prepare an ethylenically unsaturated carboxylic acid monomer aqueous solution.

  Separately, 330 g of n-heptane was put into a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube, and sorbitan monostearate (NOF CORPORATION) as a surfactant. (Nonion SP-60R, 2.7 g) was added, and this was dispersed and dissolved in n-heptane. The ethylenically unsaturated carboxylic acid monomer aqueous solution prepared previously was added there. In order to remove oxygen present in the atmosphere, raw materials and solvent in the reaction vessel, nitrogen gas was blown into the solution to replace the system with nitrogen, while the bath temperature was maintained at 60 ° C. and the stirring rate was 1000. Polymerization was carried out by the reverse phase suspension polymerization method over 1 hour with stirring at rotation / min. After completion of the polymerization, water and n-heptane were distilled off to obtain 90 g of water-absorbent resin powder which was a polymer of acrylic acid and its sodium salt and was crosslinked with water-soluble sucrose allyl ether. It was.

<Synthesis of carboxyvinyl polymer>
(Production Example 4)
In a 500 mL four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube and cooling tube, 45 g (0.625 mol) of acrylic acid, 0.27 g of pentaerythritol allyl ether, 150 g of normal hexane and 2,2 ′ -A reaction liquid was prepared by charging 0.081 g (0.00035 mol) of azobismethylisobutyrate. After stirring the reaction solution and mixing the raw materials uniformly, nitrogen gas was blown into the solution in order to remove oxygen present in the upper space of the reaction vessel, the raw material and the solvent. Next, the reaction solution was kept at 60 to 65 ° C. for 4 hours under a nitrogen atmosphere. After completion of the reaction, the resulting slurry was heated to 90 ° C. to distill off normal-hexane, and further dried under reduced pressure at 110 ° C. and 10 mmHg for 8 hours to obtain 42 g of white fine powdery carboxyvinyl polymer. It was.

<Synthesis of acrylic acid / methacrylic acid alkyl ester copolymer>
(Production Example 5)
In a 500 mL four-necked flask equipped with a stirrer, a thermometer, a nitrogen blowing tube and a cooling tube, 45 g (0.625 mol) of acrylic acid and alkyl methacrylate having 18 to 24 carbon atoms as an alkyl methacrylate ester BLEMMER VMA70 (manufactured by NOF Corporation: 10-20 parts by weight of stearyl methacrylate, 10-20 parts by weight of eicosanyl methacrylate, 59-80 parts by weight of behenyl methacrylate, and tetracosanyl methacrylate content of 1 part by weight or less A mixture of 1.125 g of pentaerythritol allyl ether, 150 g of normal hexane and 0.081 g (0.00035 mol) of 2,2′-azobismethylisobutyrate. Subsequently, after stirring and mixing uniformly, nitrogen gas was blown into the solution in order to remove oxygen present in the upper space of the reaction vessel, the raw material and the solvent. Subsequently, it was made to react for 4 hours, hold | maintaining at 60-65 degreeC under nitrogen atmosphere. After completion of the reaction, the resulting slurry was heated to 90 ° C. to distill off normal hexane, and further dried under reduced pressure at 110 ° C. and 10 mmHg for 8 hours to obtain a white fine powdery acrylic acid / methacrylic acid alkyl ester. 44 g of copolymer was obtained.

<Cosmetics: Preparation of sunscreen cream>
Example 1
After adding components 4 to 6 to the 60 ° C. mixed solution of the following components 1 to 3, the 60 ° C. uniform mixed solution of the following components 7 to 13 prepared in advance was added while being dispersed with the homomixer. (13000 rpm, 5 minutes) was emulsified to prepare a sunscreen cream. In addition,% which shows the following each component amount shows the mass% when the sunscreen cream prepared is set to 100%.
Oil phase Liquid paraffin 10%
2. Isopropyl myristate 10%
3. 5% ethylhexyl salicylate
4.4-tert-butyl-4′-methoxydibenzoylmethane 5%
5. Modified polyalkylene oxide (15% ethanol solution) 0.2%
6). Water absorbent resin (prepared in Production Example 3) 0.2%
Aqueous phase 7. Polysorbate 60 3%
8). Glycerin 5%
9. Butylene glycol 5%
10. Ethanol 5%
11 Methylparaben 0.5%
12.6% sodium hydroxide (pH = 6) Purified water residue

(Example 2)
A sunscreen cream was prepared in the same manner as in Example 1, except that the polyalkylene oxide modified product was changed to 0.12% and the water absorbent resin was changed to 0.28%.

(Comparative Example 1)
In Example 1, the polyalkylene oxide modified product was changed to 0.15% of the acrylic acid / methacrylic acid alkyl ester water-soluble copolymer obtained in Production Example 5 and the water-absorbing resin was changed to 0.15%. A sunscreen cream was prepared in the same manner as in Example 1 except for the above.

(Comparative Example 2)
A sunscreen cream was prepared in the same manner as in Example 1 except that the polyalkylene oxide modified product was changed to 0% in Example 1.

(Comparative Example 3)
A sunscreen cream was prepared in the same manner as in Example 1 except that the polyalkylene oxide modified product was changed to 0%, the water absorbent resin was changed to 0%, and the carboxyvinyl polymer was changed to 0.2%. Prepared.

<Characteristic evaluation of cosmetics>
The sunscreen creams obtained in Examples 1 and 2 and Comparative Examples 1 to 3 were evaluated for rich viscosity, touch and viscosity by the following methods. The results are shown in Table 1. In the evaluation, the total of the average points of the following evaluations was 18 points or more, ◯, 15 points to less than 18 points, and less than 15 points ×.
<Bright viscosity>
An appropriate amount of cosmetic was applied to the back of the hand and evaluated relative to the viscosity of the thick by a total of 10 testers of 5 males and 5 females. The evaluation was performed with a 5-point evaluation of 1 to 5 points, with Comparative Example 3 as the reference 3 points. The evaluation was an average of 10 people.
<Tactile sense>
A total of 10 testers of 5 men and women each apply a suitable amount of cosmetics to the back of the hand for a touch (feel refreshment, lightness, elongation), and feel refreshed, lightness, and elongation when stretched with fingers. As evaluated. The evaluation was performed with a 5-point evaluation of 1 to 5 points, with 3 points as a reference. The evaluation was an average of 10 people.
<Viscosity>
The steady flow viscosity was measured with a rheometer under the following measurement conditions, and the viscosity at a shear rate of 4 [1 / s] was measured. (B-type viscometer shear rate equivalent to 20 rpm.)
Measurement conditions Rheometer: AR-2000ex manufactured by TA Instruments
Geometry: 60mm Parallel plate Gap: 300μm
Shear rate: 0.001 to 1000 [1 / s]
Measurement temperature: 25 ° C
The results are shown in Table 1. In addition, the numerical value in the bracket | parenthesis of the "Thickener" column of Table 1 represents the mass ratio of each component used as a thickener.

  As shown in Table 1, according to Examples 1 and 2 in which a polyalkylene oxide modified product and a water-absorbent resin are used in combination, a cosmetic containing a UV-A region UV absorber and a UV-B region UV absorber. Also in the preparation, a sunscreen cosmetic with a refreshing and light touch feeling having a rich viscosity was obtained. It can be seen that the combined effect of the polyalkylene oxide modified product and the water absorbent resin is clearly reflected in the cosmetic.

Claims (7)

(A): UV absorber in the UV-A region, (B): UV absorber in the UV-B region, and (C): polyalkylene oxide obtained by reacting a polyalkylene oxide compound, a diol compound, and a diisocyanate compound. A composition containing a modified product and (D): a polymer of an ethylenically unsaturated carboxylic acid monomer crosslinked by a water-soluble crosslinking agent. The composition of Claim 1 which contains (C) and (D) in the ratio of mass ratio (C) :( D) = 20: 80-60: 40.   Polyalkylene oxide compounds are 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 copolymer. The composition according to claim 1 or 2, which is at least one selected from the group consisting of polymers.   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 composition according to any one of claims 1 to 3, 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-3,5 , 5-trimethylcyclohexyl isocyanate (IPDI), 1,8-dimethylbenzole-2,4-diisocyanate, and 2,4-tolylene diisocyanate (TDI). The composition of any one of Claims 1-4.   The composition according to any one of claims 1 to 5, wherein the ethylenically unsaturated carboxylic acid monomer is at least one selected from the group consisting of acrylic acid and methacrylic acid.   The composition according to any one of claims 1 to 6, which is a cosmetic composition.