JP2016204331A - Antiperspirant spray composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antiperspirant spray composition which has a small ethanol content and moderate viscosity, imparts a sufficient sense of refreshment, has a fresh use feeling and good stability and causes no dipping.SOLUTION: There is provided an antiperspirant spray composition which comprises (A): menthol or a derivative thereof; (B) a cationic surfactant; (C) zinc para-phenolsulfonate; (D) ethanol; (E) a polymer of an ethylenically unsaturated carboxylic acid monomer crosslinked by a water-soluble crosslinking agent; and (F) an alkyl-modified carboxyl group-containing water-soluble copolymer, wherein the content of the component (D) is 10 to 17 mass% and the composition comprises the component (E) and the component (F) at a mass ratio of (E):(F)=85:15 to 95:5.SELECTED DRAWING: None

Description

  The present invention relates to an antiperspirant spray composition. More particularly, the present invention relates to an antiperspirant spray composition having a sufficient refreshing feeling and a refreshing feeling even when the ethanol content is small, excellent in stability, and free from sagging.

  A side odor that causes discomfort to humans is caused by sweat mixed with sebum and decomposed by skin resident bacteria. Conventionally, a deodorant containing an antiperspirant has been used to prevent this unpleasant side odor. The deodorant is used in various types such as gels, creams, lotions, aerosol sprays, mists and sticks. Among them, the antiperspirant spray is excellent in usability because it can be used by spraying directly on an application object such as a side, and is widely used. However, these antiperspirant sprays are not viscous, and there are problems such as sagging in the applied one.

  In Patent Document 1, menthol or a derivative thereof, a di-long-chain cationic surfactant, and a composition containing zinc paraphenol sulfonate are blended with ethanol and clay minerals to provide a refreshing feeling and an antiperspirant effect. A liquid antiperspirant composition having excellent stability is disclosed.

Patent Document 2 discloses a deodorant composition that includes ethanol, an antiperspirant, and a hydrophobized hydroxyalkyl cellulose as a thickener, and prevents dripping during application.
However, in the prescriptions of these patent documents, it is difficult to obtain a gel-like viscosity that does not drop when used as an antiperspirant spray, and when the ethanol content is 50% or less, white precipitates are generated. occured.

International Publication No. 2014/50487 JP 2014-70022 A

  An object of the present invention is to provide a composition for an antiperspirant spray which has a low ethanol content, has an appropriate viscosity, a sufficient refreshing feeling and a refreshing feeling of use, and has a good stability and no sagging.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have developed an antiperspirant composition containing menthol or a derivative thereof, a cationic surfactant, zinc paraphenolsulfonate, and a specific amount of ethanol. Low ethanol content by blending ethylenically unsaturated carboxylic acid monomer polymer cross-linked with water-soluble crosslinker and alkyl-modified carboxyl group-containing water-soluble copolymer as a thickening agent at a specific ratio As for antiperspirants, it has been found that a composition for an antiperspirant spray having a refreshing feeling of use and good viscosity with an appropriate viscosity can be obtained, and further investigations have been made to complete the present invention. It came.

That is, the present invention
(A): Menthol or its derivative (B): Cationic surfactant (C): Zinc paraphenol sulfonate (D): Ethanol (E): Ethylenically unsaturated carboxylic acid crosslinked by a water-soluble crosslinking agent Monomer polymer (F): Contains an alkyl-modified carboxyl group-containing water-soluble copolymer, the content of component (D) is 10 to 17% by mass, and component (E) and component (F) are combined. It is related with the composition for antiperspirant sprays containing (E) :( F) = 85: 15-95: 5 by mass ratio.

  ADVANTAGE OF THE INVENTION According to this invention, it can provide the composition for antiperspirant sprays which has moderate viscosity, sufficient refreshing feeling, and the refreshing feeling of use, and was excellent in stability and without sagging.

Hereinafter, preferred embodiments of the present invention will be described in detail.
The composition for antiperspirant spray according to this embodiment includes (A) menthol or a derivative thereof, (B) a cationic surfactant, (C) zinc paraphenolsulfonate, and (D) ethanol, and further a thickening component. (E) a polymer of an ethylenically unsaturated carboxylic acid monomer and (F) an alkyl-modified carboxyl group-containing water-soluble copolymer crosslinked with a water-soluble crosslinking agent.

Hereinafter, each component will be described in detail.
As (A) menthol or its derivative used for this invention, the component which can be normally mix | blended with an external preparation can be mix | blended.

  Examples thereof include menthol such as l-menthol and dl-menthol; and menthol derivatives such as menthyl lactate, l-menthyl glyceryl ether, l-menthyl glucoside, l-menthyl hydroxybutyrate, menthoxypropanediol, and menthoxyfuran.

  0.001 mass% or more of the whole composition is preferable, and, as for content of a component (A), 0.01 mass% or more is more preferable. When content is less than 0.001 mass%, it may be hard to feel a refreshing feeling. Moreover, 3 mass% or less is preferable and, as for content of a component (A), 1.5 mass% or less is more preferable. The content may be large, but the irritation to people with sensitive skin may be too strong.

  As the cationic surfactant of component (B), for example, benzalkonium chloride solution is used. 0.001 mass% or more of the whole composition is preferable, and, as for content of a component (B), 0.005 mass% or more is more preferable. When the content is less than 0.001% by mass, the refreshing feeling may not be satisfied. Moreover, 1 mass% or less is preferable and, as for content of a component (B), 0.5 mass% or less is more preferable. The content may be large, but the effect may not be increased.

  The content of the component (C), zinc paraphenol sulfonate, is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, based on the entire composition. When the content is less than 0.01% by mass, the antiperspirant effect may not be satisfied. Moreover, 3 mass% or less is preferable and, as for content of a component (C), 1 mass% or less is more preferable. The content may be large, but the effect may not be increased.

  The content of the component (D) ethanol is 10 to 17% by mass, preferably 11 to 16% by mass, based on the entire composition. When the content is less than 10% by mass, white precipitates are generated, and a stable antiperspirant may not be prepared. If it exceeds 17% by mass, there is a risk of separation without viscosity.

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

  The ethylenically unsaturated carboxylic acid monomer is preferably a water-soluble ethylenically unsaturated carboxylic acid monomer, 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, the compound which has 2 or more of a polymerizable unsaturated group and / or a reactive functional group 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.

  The polymer of the ethylenically unsaturated carboxylic acid monomer cross-linked by the water-soluble cross-linking agent of component (E), for example, suspends the ethylenically unsaturated carboxylic acid monomer in the presence of the water-soluble cross-linking agent. It can be obtained by a method including a step of polymerizing by a turbid polymerization 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.

  The content of the component (E) is preferably about 0.7 to 1.5% by mass of the whole composition, more preferably about 0.8 to 1.2% by mass, and about 0.8 to 1.1% by mass. Further preferred. By containing the component (E), a white precipitate can be suppressed, an appropriate viscosity for preventing sagging can be given, and a composition having excellent stability can be obtained even with a small ethanol content.

The water-soluble copolymer containing an alkyl-modified carboxyl group as component (F) is composed of meth) acrylic acid, (meth) acrylic acid alkyl ester having 12 to 24 carbon atoms in the alkyl group, and, if necessary, ethylenic. It is obtained by polymerizing a compound having two or more unsaturated groups. The polymer is preferably water-soluble. In addition, carbon number of the (meth) acrylic acid alkyl ester is preferably 16 to 24, and more preferably 18 to 24.
The (meth) acrylic acid alkyl ester having 12 to 24 carbon atoms in the alkyl group refers to an ester of (meth) acrylic acid and a higher alcohol having 12 to 24 carbon atoms in the alkyl group. Examples include esters of (meth) acrylic acid and stearyl alcohol, esters of (meth) acrylic acid and eicosanol, esters of (meth) acrylic acid and behenyl alcohol, and esters of (meth) acrylic acid and tetracosanol. it can. Among these, stearyl methacrylate, eicosanyl methacrylate, behenyl methacrylate and tetracosanyl methacrylate are preferably used. In addition, as a (meth) acrylic-acid alkylester whose carbon number of an alkyl group is 12-24, you may use commercial items, such as brand name Blemmer VMA70 by Nippon Oil & Fats Co., Ltd., for example.

  In the present specification, “(meth) acrylic acid” means “methacrylic acid or acrylic acid”. Thus, for example, “(meth) acrylic acid alkyl ester” indicates “methacrylic acid alkyl ester or acrylic acid ester”.

  Combinations of (meth) acrylic acid and (meth) acrylic acid alkyl ester having 12 to 24 carbon atoms in the alkyl group may be combined with each other, or either one or both types. You may combine the above thing together. That is, the (meth) acrylic acid alkyl ester can be used alone or in combination of two or more.

  The amount of alkyl (meth) acrylic acid alkyl ester having 12 to 24 carbon atoms in the alkyl group is 0.5 to 5 parts by mass, preferably 1 to 3 parts by mass with respect to 100 parts by mass of (meth) acrylic acid. Part. When the amount ratio of the (meth) acrylic acid alkyl ester is less than 0.5 parts by mass, the resulting composition containing the alkyl-modified carboxyl group-containing copolymer may be insufficiently thickened. On the other hand, when the amount exceeds 5 parts by mass, the resulting composition containing the alkyl-modified carboxyl group-containing copolymer has a sticky feeling, which may impair the feeling of use particularly when applied to the skin.

  The compound having two or more ethylenically unsaturated groups used as necessary in the present invention is not particularly limited, and examples thereof include pentaerythritol diallyl ether, pentaerythritol triallyl ether, and pentaerythritol tetraallyl ether. Pentaerythritol allyl ether such as diethylene glycol diallyl ether, polyethylene glycol diallyl ether and polyallyl saccharose are preferred. These compounds having two or more ethylenically unsaturated groups may be used alone or in combination of two or more.

  When using the compound which has 2 or more of ethylenically unsaturated groups, the usage-amount is more than 0 mass parts and 0.1 mass parts or less with respect to 100 mass parts of (meth) acrylic acid, 0.001-0 1 part by mass is preferable, and 0.01 to 0.05 part by mass is more preferable.

  Alkyl modification by polymerizing (meth) acrylic acid, (meth) acrylic acid alkyl ester having 12 to 24 carbon atoms in the alkyl group, and, if necessary, a compound having two or more ethylenically unsaturated groups. The method for obtaining the carboxyl group-containing copolymer is not particularly limited, and it is possible to use a usual method such as a method in which these raw materials are stirred in a solvent under an inert gas atmosphere and polymerized using a polymerization initiator. it can. The polymerization method is not particularly limited, and usual emulsion polymerization, suspension polymerization, dispersion polymerization, solution polymerization, precipitation polymerization and the like can be used, and emulsion polymerization, suspension polymerization, dispersion polymerization method, precipitation polymerization are preferable. . Examples of the inert gas for obtaining the inert gas atmosphere include nitrogen gas and argon gas.

  The solvent dissolves (meth) acrylic acid, (meth) acrylic acid alkyl ester having 12 to 24 carbon atoms in the alkyl group, and a compound having two or more ethylenically unsaturated groups. There is no particular limitation as long as it does not dissolve the carboxyl group-containing copolymer and does not inhibit the reaction. Specific examples of the solvent include normal pentane, normal hexane, normal heptane, cyclopentane, cycloxane, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, etc. Among these, normal hexane, normal heptane and ethyl acetate are preferable. Can be used.

  It is preferable that the usage-amount of a solvent is 300-5000 mass parts with respect to 100 mass parts of (meth) acrylic acid from a viewpoint of improving stirring operativity and economical efficiency, for example.

  For example, the polymerization initiator is preferably a radical polymerization initiator, and specific examples include α, α′-azoisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, and 2,2 ′. -Azobismethyl isobutyrate etc. can be mentioned. Among these, 2,2'-azobismethylisobutyrate is preferably used from the viewpoint of obtaining a high molecular weight alkyl-modified carboxyl group-containing polymer.

  The amount of the polymerization initiator used is desirably 0.00003 to 0.002 mol with respect to 1 mol of (meth) acrylic acid, for example. When the amount of the polymerization initiator used is less than 0.00003 mol, the reaction rate becomes slow, which may not be economical. Moreover, when the usage-amount of a polymerization initiator exceeds 0.002 mol, there exists a possibility that a polymerization reaction may advance rapidly and control of reaction may become difficult.

  The reaction temperature is preferably 50 to 90 ° C, more preferably 55 to 75 ° C. When the reaction temperature is less than 50 ° C., the polymerization reaction cannot be started, or the viscosity of the reaction solution increases and it may be difficult to stir uniformly. Moreover, when reaction temperature exceeds 90 degreeC, reaction may advance rapidly and there exists a possibility that control of reaction may become difficult. Since the reaction time varies depending on the reaction temperature, it cannot be generally specified, but is usually 0.5 to 5 hours.

  After completion of the reaction, the alkyl-modified carboxyl group-containing copolymer can be obtained by heating the reaction solution to, for example, 80 to 130 ° C. to volatilize and remove the solvent.

  Content of a component (F) is the ratio of (E) :( F) 85: 15-95: 5 by mass ratio with a component (E), and the ratio of 88: 12-93: 7 is preferable. By containing the component (F), a composition having good sprayability can be obtained.

  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.

  In producing the composition for antiperspirant spray, known components generally used for antiperspirants can be further used.

  For example, a solvent other than ethanol may be included as a solvent. Examples of the solvent include polyhydric alcohols such as glycerin, propylene glycol, 1,3-butylene glycol, dipropylene glycol, polyethylene glycol, and diglycerin.

  The antiperspirant composition according to the present invention includes, for example, a surfactant, a moisturizing agent, a bactericidal agent, an oil component, a sequestering agent, a preservative, a refreshing agent, an anti-inflammatory agent, a plant extract, and a fragrance. May be included.

  Examples of the surfactant include an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, and a cationic surfactant. Examples of the humectant include sorbitol. Glycerin can also be used as a humectant. Examples of the oil component include esters, hydrocarbons, and silicone.

  The viscosity of the antiperspirant composition according to the present invention is preferably 1000 m Pa · s or more, more preferably 1500 m Pa when measured using a BH viscometer at a rotation speed of 20 rpm and a measurement temperature of 25 ° C. S or more, preferably 10,000 mPa · s or less, more preferably 6000 mPa · s or less. When the viscosity is 1000 mPa · s or more, sagging during coating is suppressed, and coating properties are improved. When the viscosity exceeds 10,000 mPa · s, the refreshed feeling of use is lowered, and there is a possibility that the spray becomes rod-like and does not become uniform mist.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples.
<Synthesis of water-soluble sucrose allyl ether>
(Production Example 1)
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 2)
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 obtained in Production Example 1 as a crosslinking agent (0.35% by mass with respect to an aqueous acrylic acid solution), and 2,2′- as an initiator 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 alkyl-modified carboxyl group-containing copolymer>
(Production Example 3)
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 an alkyl (meth) acrylate having 12 to 24 carbon atoms in the alkyl group Blemmer VMA70 as an ester (manufactured by NOF Corporation: 10-20 parts by mass of stearyl methacrylate, 10-20 parts by mass of eicosanyl methacrylate, 59-80 parts by mass of behenyl methacrylate, and tetracosanyl methacrylate content of 1 1.35 g of a mixture of parts by mass or less), 0.02 g of pentaerythritol allyl ether, 150 g of normal hexane, and 0.081 g (0.00035 mol) of 2,2′-azobismethylisobutyrate were charged. 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 water-soluble alkyl-modified carboxyl group-containing white fine powder. 43 g of copolymer was obtained.

<Preparation of antiperspirant composition>
Example 1
An antiperspirant spray composition containing the following components in various proportions was prepared. That is, components 2) and 3) are dissolved in a part of purified water, a predetermined amount of an aqueous solution of a water-absorbing resin previously dissolved is added, and the alkyl-modified carboxyl group-containing polymer previously dissolved in water is further added with caustic soda to pH = A predetermined amount of an aqueous solution neutralized in 6 was added, and component 1) dissolved in ethanol was added and mixed uniformly to obtain a composition for antiperspirant spray having a viscosity of 3800 mPa · s.
1. L-Menthol 0.5%
2. Benzalkonium chloride solution (50%) 0.05%
3. Zinc paraphenol sulfonate 0.35%
4). Ethanol 12%
5. Water absorbent resin (prepared in Production Example 2) 0.9%
6). Alkyl-modified carboxyl group-containing polymer (prepared in Production Example 3) 0.1%
7). Purified water residue (Example 2)
A composition for antiperspirant spray having a viscosity of 3250 mPa · s was obtained in the same manner as in Example 1 except that the amount of ethanol added was changed to 15% by mass in Example 1.

(Comparative Example 1)
The same procedure as in Example 1 was performed except that the amount of ethanol added was changed to 18% by mass in Example 1, but there was no viscosity and the components were separated.
(Comparative Example 2)
In Example 2, the addition amount of the water-absorbing resin was changed to 0.7% by mass, and the addition amount of the alkyl-modified carboxyl group-containing copolymer was changed to 0.3% by mass, as in Example 2. Thus, a composition for antiperspirant spray having a viscosity of 14800 mPa · s was obtained.
(Comparative Example 3)
In Example 1, the addition amount of ethanol was changed to 20% by mass, the addition amount of the water absorbent resin was changed to 1.2% by mass, and the alkyl-modified carboxyl group-containing copolymer was not added. In the same manner as in Example 1, an antiperspirant spray composition having a viscosity of 8200 mPa · s was obtained.

<Evaluation of composition for antiperspirant spray>
The following evaluation was performed about the composition obtained in Example 1, 2 and Comparative Examples 1-3. The results are shown in Table 1.
(viscosity)
Toki Sangyo BH viscometer, rotation speed 20rpm
Measurement temperature: 25 ° C
(Stability after centrifugation)
The stability after treatment at 2000 rpm for 20 minutes was evaluated with a centrifuge.
Stability without separation of components: ○
Ingredients separated: ×
(50 ° C storage stability)
The stability after storage for 7 days in a constant temperature layer at 50 ° C. was evaluated.
Stability without separation of components: ○
Ingredients separated: ×
(Sprayability)
Sauce and sprayability were evaluated in a spray container.
○: Can be sprayed uniformly in a circular shape without sagging.
Δ: Donut-shaped spray, but no sagging.
×: Cannot be rod-shaped or sprayed.
(Sensation of coolness)
A total of 10 testers of 5 males and 5 females gave a 5-step evaluation of 1 to 5 points based on the following criteria for the refreshing feeling at the time of application, and the evaluation was an average of 10 persons.
Very good 5 points Good 4 points Normal 3 points Somewhat bad 2 Points Bad 1 point (Refreshing feeling)
A total of 10 testers of 5 males and 5 females gave a 5-step evaluation of 1 to 5 points on the following criteria for the refreshed feeling after application, and the evaluation was an average of 10 people.
Very good 5 points Good 4 points Normal 3 points Somewhat bad 2 points Bad 1 point (Comprehensive evaluation)
The evaluation criteria are shown below.
○: Stability, refreshing feeling, refreshing feeling and sprayability are all good.
(Triangle | delta): Although stability, a refreshing feeling, and a refreshing feeling are favorable, it becomes a donut-shaped spray.
X: Stability is poor or sprayability is poor.

  As shown in Table 1, Examples 1 and 2 using a water-absorbing resin and an alkyl-modified carboxyl group-containing copolymer are stable even with a small amount of ethanol, have an appropriate viscosity, have a good feeling of use and are sagging. No antiperspirant spray composition was obtained. It can be seen that the effect of adding the water-absorbing resin and the alkyl-modified carboxyl group-containing copolymer is clearly reflected in the sprayability.

Claims (6)

(A): Menthol or its derivative (B): Cationic surfactant (C): Zinc paraphenol sulfonate (D): Ethanol (E): Ethylenically unsaturated carboxylic acid crosslinked by a water-soluble crosslinking agent Monomer polymer (F): Contains an alkyl-modified carboxyl group-containing water-soluble copolymer, the content of component (D) is 10 to 17% by mass, and component (E) and component (F) are combined. A composition for antiperspirant spray, which is contained at a mass ratio of (E) :( F) = 85: 15 to 95: 5.   The composition for antiperspirant spray according to claim 1, wherein the content of component (E) is 0.8 to 1.5 mass%.   The water-soluble crosslinking agent was selected from the group consisting of ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, N, N′-methylenebisacrylamide, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and water-soluble sucrose allyl ether. The composition for antiperspirant spray according to claim 1 or 2, which is at least one kind.   The composition for antiperspirant spray according to any one of claims 1 to 3, wherein the ethylenically unsaturated carboxylic acid monomer is at least one selected from the group consisting of acrylic acid and methacrylic acid.   Alkyl-modified carboxyl group-containing water-soluble copolymer is 100 parts by weight of (meth) acrylic acid, 0.5 to 5 parts by weight of (meth) acrylic acid alkyl ester having 12 to 24 carbon atoms, and ethylenic. The antiperspirant spray composition according to any one of claims 1 to 4, which is a polymer obtained by copolymerizing 0 to 0.1 parts by mass of a compound having two or more unsaturated groups.   The composition for antiperspirant spray according to any one of claims 1 to 5, having a viscosity of less than 1000 to 10000 mPa · s when measured at a rotation speed of 20 rpm and a measurement temperature of 25 ° C using a BH viscometer.