JP2016204332A - 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) a urethane associated polyalkylene oxide modified product, 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)=55:45 to 45:55.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. Antiperspirant with low ethanol content by blending a polymer of ethylenically unsaturated carboxylic acid monomer cross-linked with a water-soluble cross-linking agent and a modified urethane-associated polyalkylene oxide at a specific ratio as a thickening component As a result of further investigations, the present inventors completed the present invention by finding that an anti-sweating spray composition having an appropriate viscosity with a refreshed feeling of use and good stability over time can be obtained. .

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): containing a urethane-associated polyalkylene oxide modified product, the content of component (D) is 10 to 17% by mass, and the component (E) and component (F) are in a mass ratio. And (E) :( F) = 55: 45 to 45:55.

  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 crosslinked with a water-soluble crosslinking agent and (F) a urethane-associated polyalkylene oxide modified product.

Hereinafter, each component will be described in detail.
As the menthol of component (A) or a derivative thereof used in the present invention, a component that can be usually blended in an external preparation can be 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 12 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 the content 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 0.3 to 1.0% by mass of the whole composition, more preferably about 0.4 to 0.8% by mass, and about 0.5 to 0.6% 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 urethane-associated polyalkylene oxide-modified product of component (F) used in the present invention is represented by the following formula (I).

（Ｉ）

(I)

In the formula, R ¹ is a linear alkyl group having 15 to 24 carbon atoms, R ² is a methyldiphenylene group, a hexamethylene group, a methyldicyclohexylene group, 3-methyl-3,5,5-trimethylcyclohexyl. A silylene group, a dimethylphenylene group or a tolylene group, [(OCH ₂ CH ₂ ) _a -ran- (OCH ₂ CH (CH ₃ )) _b ] is a structural unit of (OCH ₂ CH ₂ ) and (OCH ₂ CH (CH ₃ )) are copolymerized randomly, and the degree of polymerization of each constituent unit is a and b, a is an integer of 5 to 10, b is an integer of 5 to 8, and n is 130. The integer of -680 and m shows the integer of 1-4.

  The modified urethane-associated polyalkylene oxide is obtained by reacting a specific polyalkylene oxide compound (X), a specific polyether monoalcohol (Y), and a specific diisocyanate compound (Z). Hereinafter, these components may be simply expressed as (X), (Y), or (Z).

(X) is represented by the formula (II):
HO— (CH ₂ CH ₂ O) _n —H (II)
(Wherein n represents an integer of 130 to 680).
The number average molecular weight of the polyethylene oxide is preferably about 6,000 to 30,000, more preferably about 11,000 to 20,000. When the number average molecular weight of (X) is 6,000 or more, the resulting polyalkylene oxide-modified product is less likely to have poor transparency. Moreover, there is little possibility that the aqueous solution viscosity of the polyalkylene oxide modified product obtained as the number average molecular weight is 30,000 or less.

The number average molecular weight of (X) polyethylene oxide here is JIS K 1557-1: 2007 (Plastics—Polyurethane raw material polyol test method—Part 1: Determination of hydroxyl value) from hydroxyl value O ₁ determined by method A It is obtained by the following formula. That is, the number average molecular weight can be obtained by the following formula, using both ends of polyethylene oxide as hydroxyl groups.
Number average molecular weight = (56,100 × 2) / O ₁

In (Y), one end of a random copolymer of ethylene oxide (EO) and propylene oxide (PO) is an OH group, and the other end is a linear alkyl group having 15 to 24 carbon atoms (hereinafter, the alkyl group is referred to as R ¹ ). A polyether monoalcohol having a structure which may be described. And when the addition mole number of the ethylene oxide is a and the addition mole number of the propylene oxide is b, the ratio (a / b) is in the range of 1-2.

  The polyether monoalcohol is “copolymerized randomly in a ratio (a / b) of ethylene oxide and propylene oxide in an addition mole number ratio of 1 to 2 (preferably 1.1 to 1.5). It can also be said that it is a polyoxyethylene polyoxypropylene monoalkyl ether having 24 linear alkyl groups.

(Y) represents a linear alkyl group having 15 to 24 carbon atoms as R ¹ , and the following formula (III):
_{^{R 1 - [(OCH 2 CH}} 2) a -ran- (OCH 2 CH (CH 3)) b] -OH (III)
Can be expressed as

Here, [(OCH ₂ CH ₂ ) _a -ran- (OCH ₂ CH (CH ₃ )) _b ] is a random copolymer of (OCH ₂ CH ₂ ) and (OCH ₂ CH (CH ₃ )) which are constituent units. And the degree of polymerization of each structural unit is a and b, and as understood from this, “ran” is expressed by the notation [α _i -ran-β _j ]. Represents that the structural units α and β are randomly copolymerized at polymerization degrees i and j, respectively.

  (A / b) in (Y) is 1 to 2 as described above, preferably 1.1 to 1.5. When the ratio is less than 1, the solubility of the resulting polyalkylene oxide-modified product in water decreases, and the aqueous solution viscosity decreases. Moreover, it is preferable that a is an integer of 5-10. Moreover, it is preferable that b is an integer of 5-8. When a is 5 or more, the aqueous solution viscosity of the resulting polyalkylene oxide-modified product can be further increased. When a is 10 or less, the transparency of the aqueous solution of the resulting polyalkylene oxide-modified product can be further increased. When b is 5 or more, the transparency of the aqueous solution of the resulting polyalkylene oxide-modified product can be further increased. When b is 8 or less, the aqueous solution viscosity of the resulting polyalkylene oxide-modified product can be further increased.

R ¹ is a linear alkyl group having 15 to 24 carbon atoms as described above, preferably a linear alkyl group having 16 to 22 carbon atoms, more preferably a linear alkyl group having 16 to 20 carbon atoms. It is a group. When the carbon number is 15 or more, the aqueous solution viscosity of the resulting polyalkylene oxide-modified product can be further improved. When the carbon number is 24 or less, the transparency of the aqueous solution of the resulting polyalkylene oxide-modified product can be further improved.

(Y) has a structure in which a random copolymer (polyalkylene oxide) of ethylene oxide and propylene oxide is added to a linear monovalent saturated alcohol.
If the random copolymer of ethylene oxide and propylene oxide here is, for example, a block copolymer of ethylene oxide and propylene oxide, the solubility of the resulting polyalkylene oxide-modified product in an aqueous medium is reduced, resulting in an aqueous solution. This is not preferable because the transparency of the film deteriorates.

The number average molecular weight of (Y) is preferably 800 to 3,000, and more preferably 1,000 to 2,500. When the number average molecular weight is 800 or more, the aqueous solution viscosity of the resulting polyalkylene oxide-modified product can be further improved. When the number average molecular weight is 3,000 or less, the resulting polyalkylene oxide-modified aqueous solution is less likely to be reduced in viscosity even in the presence of a surfactant.

Here, the number average molecular weight of (Y) is JIS K1557-1: 2007 (Plastics—Polyurethane raw material polyol test method—Part 1: Determination of hydroxyl value) From the hydroxyl value O ₁ determined by the method A It is calculated by the formula. That is, the number average molecular weight is obtained by the following formula, where one end of the polyether monoalcohol is a hydroxyl group.
Number average molecular weight = (56,100) / O ₁

  As for the usage-amount of (Y), the ratio of 1-2 mol is preferable with respect to 1 mol of (X), 1.1-2 mol is more preferable, and 1.5-2 mol is further more preferable. When the amount of (Y) used is 1 mol or more with respect to 1 mol of (X), the aqueous solution viscosity of the resulting polyalkylene oxide-modified product is less likely to decrease. When the amount of (Y) used is 2 mol or less with respect to 1 mol of (X), the transparency of the aqueous solution of the resulting polyalkylene oxide-modified product can be further improved.

(Z) is the formula (IV):
^{O = C = N-R 2} -N = C = O (IV)
It is a diisocyanate compound represented by these. R ² represents a methyldiphenylene group, a hexamethylene group, a methyldicyclohexylene group, a 3-methyl-3,5,5-trimethylcyclohexylene group, a dimethylphenylene group or a tolylene group.

  Specific examples of (Z) include 4,4′-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4′-diisocyanate (HMDI), and 3-isocyanate methyl. -3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,8-dimethylbenzole-2,4-diisocyanate, 2,4-tolylene diisocyanate (TDI) and the like. Among these diisocyanate compounds, dicyclohexylmethane-4,4'-diisocyanate (HMDI) and 1,6-hexamethylene diisocyanate (HDI) are preferable from the viewpoint of excellent transparency of the resulting polyalkylene oxide-modified product. These diisocyanate compounds may be used alone or in combination of two or more.

  The use ratio of the diisocyanate compound is such that the total number of moles of terminal hydroxyl groups (X) and (Y) (number of moles of [—OH]) is 1, the number of moles of isocyanate groups of the diisocyanate compound ([—NCO). ] Is preferably 0.8 to 1.2, more preferably 0.9 to 1.1. That is, it is preferable that the isocyanate group of a diisocyanate compound is 0.8-1.2 mol with respect to 1 mol of total terminal hydroxyl groups of (X) and (Y), and it is 0.9-1.1 mol. Is more preferable. If the usage ratio is 0.8 mol or more, the residual amount of unreacted polyether monoalcohol is unlikely to increase, and the aqueous solution viscosity of the resulting polyalkylene oxide-modified product is less likely to decrease. If the usage ratio is 1.2 mol or less, the solubility of the resulting polyalkylene oxide-modified product in an aqueous medium can be further improved.

  As a method of reacting the polyalkylene oxide compound (X), the polyether monoalcohol (Y) and the diisocyanate compound (Z), 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 powder or solid raw materials, and then reacting 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, a small amount of triethylamine, triethanolamine, dibutyltin dilaurate, dioctyltin dilaurate, tin 2-ethylhexanoate, triethylenediamine or the like can be added as a catalyst.

  The amount of the catalyst used is preferably 200 to 2,000 ppm by mass, more preferably 500 to 1,000 ppm by mass, based on the polyalkylene oxide compound.

  By such a method, a modified urethane-associated polyalkylene oxide can be obtained.

  Content of a component (F) is a ratio of (E) :( F) of 45: 55-55: 45 by mass ratio with a component (E), and the ratio of 48: 52-52: 48 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 mPa · s or more, more preferably 1200 mPa when measured at a rotation speed of 20 rpm and a measurement temperature of 25 ° C using a BH viscometer. S or more, preferably 7000 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 7000 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 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 modified urethane-associated polyalkylene oxide>
(Production Example 3)
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, polyoxyethylene polyoxypropylene stearyl ether (EO / PO = 50/50, Mw = 1000) ) 10 parts by mass and dioctyltin dilaurate 0.2 parts by mass and stirred in a nitrogen gas atmosphere to obtain a uniform mixture. Separately, dicyclohexylmethane-4,4′-diisocyanate was charged into 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 11.9 g / min. Continuously fed to the twin-screw extruder (R value = 1.00), mixed and reacted in the extruder, a strand was taken out from the outlet of the extruder, pelletized by a pelletizer, and modified polyalkylene oxide Got.

<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 and a urethane-associated polyalkylene oxide-modified product dissolved in advance is added, and component 1) dissolved in ethanol is added. And mixed uniformly to obtain a composition for antiperspirant spray having a viscosity of 1300 mPa · s.
1. L-Menthol 0.5%
2. Benzalkonium chloride solution (50%) 0.05%
3. Zinc paraphenol sulfonate 0.35%
4). Ethanol 15%
5. Water absorbent resin (prepared in Production Example 2) 0.5%
6). Urethane-associated polyalkylene oxide modified product (prepared in Production Example 3) 0.5%
7). Purified water residue (Example 2)
In Example 1, except that the addition amount of the water-absorbent resin was changed to 0.6% by mass, and the addition amount of the urethane-associated polyalkylene oxide-modified product was changed to 0.6% by mass, A composition for antiperspirant spray having a viscosity of 5800 mPa · s was obtained.

(Comparative Example 1)
In Example 2, an antiperspirant spray composition having a viscosity of 750 mPa · s was obtained in the same manner as in Example 2 except that the amount of the polyalkylene oxide-modified product was changed to 0.4% by mass.
(Comparative Example 2)
In Example 2, an antiperspirant spray composition having a viscosity of 200 mPa · s was obtained in the same manner as in Example 2, except that the amount of ethanol added was changed to 20% by mass.
(Comparative Example 3)
In Example 1, except that 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 urethane-associated polyalkylene oxide modified product was not added. In the same manner as in Example 1, a composition for antiperspirant spray 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: ○
The components were slightly 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.
X: Spraying is possible, but sagging occurs.
(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-absorbent resin and a urethane-associated polyalkylene oxide modified product 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-absorbent resin and the modified urethane-associated polyalkylene oxide 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): containing a urethane-associated polyalkylene oxide modified product, the content of component (D) is 10 to 17% by mass, and the component (E) and component (F) are in a mass ratio. (E): (F) = An antiperspirant spray composition containing 55:45 to 45:55.   The composition for antiperspirant spray according to claim 1, wherein the content of the component (E) is 0.4 to 0.7 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 antiperspirant spray composition 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. A modified urethane-associated polyalkylene oxide is represented by the formula (I)

(I)
(In the formula, R ¹ is a linear alkyl group having 15 to 24 carbon atoms, R ² is a methyldiphenylene group, a hexamethylene group, a methyldicyclohexylene group, 3-methyl-3,5,5-trimethyl. cyclohexylene group, a dimethyl phenylene group or tolylene _{group, [(OCH 2 CH 2)} a -ran- (OCH 2 CH (CH 3)) b] is a structural unit _(OCH 2 CH ₂₎ and (OCH ₂ CH (CH ₃ )) is randomly copolymerized, and the degree of polymerization of each constituent unit is a and b, a is an integer of 5 to 10, b is an integer of 5 to 8, and n is (An integer of 130 to 680 and m represents an integer of 1 to 4)
The composition for antiperspirant sprays in any one of Claims 1-4 which are modified | denatured represented by these. The composition for antiperspirant spray according to any one of claims 1 to 5, which has a viscosity of less than 1000 to 7000 mPa · s when measured at a rotation speed of 20 rpm and a measurement temperature of 25 ° C using a BH viscometer.