JP2023121559A - Viscous composition - Google Patents

Abstract

To provide a viscous composition which contains an ethylenically unsaturated monomer and has high light stability (hardly decreases in viscosity by light irradiation).SOLUTION: The viscous composition contains (A) a polymer of a water-soluble ethylenically unsaturated carboxylic acid monomer crosslinked by a crosslinking agent, (B) a neutralizer, (C) water and/or an alcohol, and (D) an ultraviolet absorber. The sphericity of the polymer (A) is 0.7-1.0. The ultraviolet absorber (D) is at least one selected from the group consisting of ethylhexyl methoxycinnamate, ferulic acid, and its salts.SELECTED DRAWING: None

Description

The present disclosure relates to viscous compositions containing polymers of ethylenically unsaturated monomers.

Hydrophilic thickeners include natural thickeners such as xanthan gum and guar gum, semi-synthetic thickeners such as hydroxyethyl cellulose and carboxymethyl cellulose, and carboxyvinyl polymer and polyethylene oxide. Representative synthetic thickeners are widely used. Carboxyl group-containing hydrophilic polymers such as carboxyvinyl polymer exhibit excellent thickening properties when used in small amounts, and are therefore used as thickeners, dispersants, emulsion stabilizers, etc. in various industrial fields including cosmetics and toiletries. is preferably used as A carboxyvinyl polymer is a polymer of a water-soluble ethylenically unsaturated monomer (for example, acrylic acid) having a carboxyl group and a vinyl group, and may be crosslinked with an oil-soluble crosslinking agent such as pentaerythritol triallyl ether. be.

Conventionally, carboxyl group-containing hydrophilic polymers used as hydrophilic thickeners are often produced by a precipitation polymerization method using an organic solvent. In the precipitation polymerization method, polymer particles that become insoluble in an organic solvent and precipitate as the polymerization progresses are recovered. The recovered polymer particles are used as thickening agents. In addition, the use of reversed-phase suspension polymerization is also being studied in the method for producing a water-absorbing resin (for example, Patent Document 1).

JP-A-3-227301 JP-A-1-210463 JP-A-7-291821 Japanese Patent Publication No. 2008-508189 JP 2019-214518 A JP-A-4-218582 JP-A-11-29605 JP-A-1993-97644 JP-A-1997-175977 JP-A-2001-163756 JP 2011-195478 A JP 2011-219424 A

Viscous compositions containing polymers of ethylenically unsaturated carboxylic acid monomers (e.g., carboxyvinyl polymers) have been proposed in the fields of cosmetics, toiletries, hand sanitizers, miscellaneous goods, and the like. In particular, since carboxyvinyl polymer is easily decomposed by light, there is a problem that the viscosity is lowered by light. For this reason, viscous compositions containing stabilizers such as ultraviolet absorbers and chelating agents have been proposed for the purpose of enhancing photostability (see Patent Documents 2 to 12). However, stickiness occurred, and there was also a problem with the feeling of use.

Therefore, in order to obtain a viscous composition containing a polymer of an ethylenically unsaturated carboxylic acid monomer, the polymer contained therein has high light stability, and a good feel during use. ,Study was carried out. It is also desirable to obtain a viscous composition that exhibits excellent thickening properties even if the viscous composition contains alcohol (especially high-concentration alcohol).

The present inventors have developed a water-soluble ethylenically unsaturated monomer polymer crosslinked with a crosslinking agent, which has a high degree of sphericity and is an ethylenically unsaturated carboxylic acid monomer crosslinked polymer, The inventors have found the possibility of preparing a viscous composition in which the crosslinked polymer contained therein has high photostability by using it in combination with a specific ultraviolet absorber, and conducted further studies.

The disclosure includes, for example, subject matter described in the following sections.
Section 1.
(A) a polymer of water-soluble ethylenically unsaturated carboxylic acid monomers crosslinked by a crosslinking agent;
(B) a neutralizing agent;
(C) water and / or alcohol, and (D) containing an ultraviolet absorber,
The sphericity of the polymer (A) is 0.7 to 1.0,
The ultraviolet absorber (D) is at least one selected from the group consisting of ethylhexyl methoxycinnamate and ferulic acid and salts thereof.
Viscous composition.
Section 2.
Item 1. The viscous composition according to Item 1, which has a viscosity of 500 to 15000 mPa·s.
Item 3.
The polymer (A) is
A polymer having a storage modulus G′ (Pa) at 25° C. of 0.1 to 300 for a 0.5% by mass aqueous solution of pH 5 to 6.5,
3. The viscous composition according to Item 1 or 2.
Section 4.
The polymer (A) is
A polymer having a viscosity of 5,000 to 30,000 mPa s at 25° C. in a 0.5% by mass aqueous solution of pH 5 to 6.5.
Item 4. The viscous composition according to any one of Items 1 to 3.
Item 5.
The neutralizing agent (B) is at least one selected from the group consisting of organic amines and alkali metal salts,
Item 5. The viscous composition according to any one of Items 1 to 4.
Item 6.
Item 6. The viscous composition according to any one of Items 1 to 5, wherein the ethylenically unsaturated monomer is at least one compound selected from the group consisting of acrylic acid and its salts, and methacrylic acid and its salts. thing.
Item 7.
Item 7. The viscous composition according to any one of Items 1 to 6, wherein the water-soluble cross-linking agent is a water-soluble sucrose allyl ether having a degree of etherification of 1.8 to 4.0.
Item 8.
The polymer (A) is
A polymer having a viscosity of 200 to 5000 mPa s at 25 ° C. in a 0.3% by mass solution in a 70% by mass ethanol aqueous solution and having a pH of 6 to 8.
Item 8. The viscous composition according to any one of items 1 to 7.
Item 9.
Item 9. The viscous composition according to any one of Items 1 to 8, containing 10% by mass or more of alcohol.

A viscous composition containing an ethylenically unsaturated monomer and having high photostability (viscosity is less likely to decrease due to light irradiation) is provided. The viscous composition is also excellent in feeling of use (especially refreshing feeling when applied to the skin).

Each embodiment included in the present disclosure will be described in further detail below. The present disclosure preferably includes, but is not limited to, a viscous composition containing a crosslinked polymer of ethylenically unsaturated monomers, uses thereof, and the like. Include everything a trader can perceive.

Certain viscous compositions encompassed by this disclosure are composed of (A) a polymer of water-soluble ethylenically unsaturated carboxylic acid monomers crosslinked by a crosslinking agent, (B) a neutralizing agent, (C) water and/or alcohol, and a specific (D) UV absorber. The viscous composition may be referred to as the viscous composition of the present disclosure. Further, these components are sometimes referred to as polymer (A), neutralizer (B), solvent (C), and ultraviolet absorber (D), respectively.

Polymer (A) is a polymer of water-soluble ethylenically unsaturated carboxylic acid monomers and is crosslinked with a crosslinking agent. That is, the (A) polymer has a repeating structural unit derived from a water-soluble ethylenically unsaturated carboxylic acid monomer. In addition, the cross-linking agent cross-links polymer chains formed by repeating structural units derived from water-soluble ethylenically unsaturated carboxylic acid monomers.

Water-soluble ethylenically unsaturated monomers include acrylic acid and its salts, methacrylic acid and its salts, 2-acrylamido-2-methylpropanesulfonic acid and its salts, acrylamide, methacrylamide, and N,N-dimethylacrylamide. etc. are exemplified. Among these, monomers having a carboxyl group, that is, acrylic acid and its salts, and methacrylic acid and its salts are preferable from the viewpoint of easily obtaining sufficient thickening properties. As these salts, alkali metal salts are preferable, and sodium salts or potassium salts are particularly preferable. A water-soluble ethylenically unsaturated monomer can be used individually by 1 type or in combination of 2 or more types.

Moreover, as a cross-linking agent, a water-soluble cross-linking agent is preferable. Moreover, compounds having two or more polymerizable unsaturated groups and/or reactive functional groups are preferred. A reactive functional group is a functional group capable of forming a crosslinked structure by reacting with a functional group such as a carboxyl group possessed by a water-soluble ethylenically unsaturated monomer. A specific example thereof is a glycidyl group. Examples of water-soluble crosslinkers with two or more glycidyl groups include ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether. Examples of water-soluble crosslinkers having two or more polymerizable unsaturated groups include N,N'-methylenebisacrylamide, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate and water-soluble sucrose allyl ether.

Generally, sucrose allyl ether is synthesized by a method of allyl-etherifying sucrose using allyl bromide or the like in the presence of an alkali catalyst. Oil-soluble or water-soluble sucrose allyl ether is obtained depending on the degree of etherification at this time. Oil-soluble (hydrophobic) sucrose allyl ether with a high degree of etherification of 5.0 to 8.0 is, like pentaerythritol triallyl ether, a carboxyvinyl polymer produced by a precipitation polymerization method using an organic solvent. Widely used as a cross-linking agent. However, the cross-linking agent used as a cross-linking agent in the cross-linked polymer of the present disclosure is preferably water-soluble, and therefore water-soluble sucrose allyl ether is preferred among sucrose allyl ethers. The degree of etherification of water-soluble sucrose allyl ether is preferably about 1.8 to 4.0. The degree of etherification is the average molar ratio of allyl ether groups to sucrose. The degree of etherification is calculated from the amount of acetic anhydride consumed when hydroxyl groups remaining in sucrose allyl ether are reacted with acetic anhydride in pyridine. The maximum degree of etherification of sucrose allyl ether is 8.0 from its chemical structure.

When 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, tends to be insufficient, making it difficult for the cross-linking reaction to proceed effectively. When 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 water-soluble ethylenically unsaturated monomer progresses with difficulty in the aqueous phase. Tend. From this point of view, the degree of etherification of the water-soluble sucrose allyl ether is preferably 2.0 to 3.5, more preferably 2.2 to 3.2.

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

Polymer (A) is preferably prepared by reversed-phase suspension polymerization. Specifically, the polymerization reaction is preferably carried out while droplets of an aqueous phase containing a water-soluble ethylenically unsaturated monomer, a water-soluble cross-linking agent and water are dispersed in a hydrophobic solvent. According to the reverse phase suspension polymerization, crosslinked polymer particles having a high degree of sphericity can be preferably obtained, so that the below-described crosslinked polymer having a degree of sphericity can be efficiently prepared, which is also advantageous.

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

The aqueous phase containing water-soluble ethylenically unsaturated monomers, etc., or the hydrophobic solvent may contain other ingredients such as surfactants and radical initiators.

Surfactants are mainly used to stabilize the suspension during polymerization. The surfactant is not particularly limited as long as it is commonly used in reversed-phase suspension polymerization. Preferably, sorbitan fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, sorbitol fatty acid ester, modified polyethylene wax, modified polypropylene wax, polyvinyl alcohol, polyethylene oxide, cellulose ether (hydroxyethyl cellulose, ethyl cellulose, etc.), sodium alkylbenzene sulfonate, and polyoxyethylene alkylphenyl ether sulfate.

The amount of surfactant is preferably 0.1-10.0% by weight, more preferably 0.5-5.0% by weight, based on the water-soluble ethylenically unsaturated monomer. If the amount of surfactant is too small, problems may arise in the stability of the suspension state during polymerization, and if the amount of surfactant is too large, it tends to be economically disadvantageous.

The radical initiator is not particularly limited as long as it is used for ordinary 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 radical initiator is preferably 0.01-0.5% by weight, more preferably 0.02-0.2% by weight, based on the water-soluble ethylenically unsaturated monomer. If the amount of the radical initiator is too small, the polymerization reaction tends to be difficult to proceed, or the reaction tends to take a long time. If the amount of the radical initiator is too large, a rapid polymerization reaction may occur, which tends to make process control difficult.

In reversed-phase suspension polymerization, the size of the droplets containing the water-soluble ethylenically unsaturated monomer and the like is closely related to the size of the resulting polymer particles. Depending on conditions such as the reaction vessel and production scale, for example, when a 2 L flask is used as the reaction vessel, reverse phase suspension polymerization is performed at a stirring speed of 600 to 1500 rpm to achieve the object of the present invention. It is likely that polymer particles of suitable size can be obtained. Moreover, the molecular weight and the degree of crosslinking of the crosslinked polymer can be adjusted by the amount of the water-soluble crosslinking agent to be added.

Other conditions of the polymerization reaction, such as the amount of radical initiator, polymerization reaction temperature, reaction time, etc., are also appropriately adjusted. 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 the reaction vessel, the bath temperature can be adjusted to 60° C. to initiate the polymerization reaction. In this case, the initiation of the polymerization reaction can be confirmed from the fact that the temperature in the reaction vessel rises to 70-odd degrees Celsius due to the heat of polymerization. After that, the polymerization reaction is usually completed by performing an aging reaction for about 30 minutes to 3 hours. After the aging reaction, the bath temperature is raised to distill off the water and petroleum-based hydrocarbon solvent in the reaction vessel to obtain the product.

Further, the polymer (A) is particles having a sphericity of 0.7 to 1.0. The particles preferably have a sphericity of 0.75 to 1.0 or 0.8 to 1.0, more preferably 0.85 to 1.0, and more preferably 0.9 to 1.0. are more preferably particles of The sphericity is measured as follows. That is, the particles of each crosslinked polymer are observed with a scanning microscope, 10 particles are randomly selected from the observed image, the major axis and minor axis of each particle are measured, and the minor axis / major axis ratio Let the average value be the sphericity.

Moreover, the polymer (A) preferably has a median particle size of about 1 to 40 μm. The upper or lower end of the range may be, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, or 35 μm. For example, the range may be about 2 to 35 μm. The median particle size is the volume median size determined from the particle size distribution. More specifically, the median particle size is obtained by dispersing 0.01 g of the crosslinked polymer in 5 ml of heptane, and then using a particle size distribution measuring device (for example, SALD-7100 manufactured by Shimadzu Corporation, using a batch cell). is used to measure the particle size distribution, and is the median particle size on a volume basis, which is obtained from the obtained particle size distribution.

The polymer (A) is a crosslinked polymer having a storage elastic modulus G' (Pa) at 25°C of 0.1 to 300 when made into a 0.5 mass% aqueous solution of pH 5 to 6.5. is preferred. The upper or lower limit of the range is, for example, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, or 290. For example, the range may be 1-250, or 2-200, and so on.

When preparing the 0.5% by mass aqueous solution, if the pH needs to be adjusted, a pH adjuster can be used. As the pH adjuster, for example, sodium hydroxide is preferable. If the pH is within the above range (5 to 6.5), even if the pH changes, the storage modulus G' (Pa) of the 0.5% by mass aqueous solution at 25°C does not change significantly. In addition, pH is measured using a pH meter at 25 degreeC.

The storage modulus G' (Pa) is a value measured under conditions of 25° C., strain of 1% or less, and angular velocity of 0.1 rad/s. The measurement is performed using a rheometer (eg, AR-2000ex, manufactured by TA, Instruments). In addition, the gap is preferably 1000 μm at the time of measurement. Also, it is preferable to use a 60 mm parallel plate.

A crosslinked polymer that achieves the above range of storage elastic modulus G' is obtained by adjusting the concentration of the monomer (that is, the water-soluble ethylenically unsaturated monomer) when preparing the polymer, and the amount of the crosslinking agent used relative to the monomer. Furthermore, it can be obtained by adjusting the molecular weight of the uncrosslinked product, if necessary. The uncrosslinked product is a polymer obtained by polymerization reaction in the same manner as in preparation of a crosslinked polymer, except that no crosslinking agent is added.

In this specification, unless otherwise specified, the molecular weight of the polymer refers to the weight average molecular weight.

For example, although it is just a guideline, in the reverse phase suspension polymerization, the water-soluble ethylenically unsaturated monomer, the cross-linking agent, and the aqueous phase containing water, the water-soluble ethylenically unsaturated monomer amount is 35 to 50 When it is about mass %, the amount of the cross-linking agent is preferably about 0.01 to 0.15 mass % with respect to the water-soluble ethylenically unsaturated monomer. Note that the molecular weight of the polymer (uncrosslinked polymer) obtained by polymerization reaction in the same manner except that the crosslinking agent is not added can also be used as a guideline for preparing the crosslinked polymer of the present disclosure. When the amount of ethylenically unsaturated monomer and the amount of crosslinking agent are used, it is more preferable that the uncrosslinked molecular weight is about 1,600,000 to 1,900,000.

In addition, when the amount of the water-soluble ethylenically unsaturated monomer in the aqueous phase is about 20 to 35% by mass, the amount of the cross-linking agent is 0.16 to 0.1% relative to the water-soluble ethylenically unsaturated monomer. It is preferably about 4% by mass. Note that the molecular weight of the polymer (uncrosslinked polymer) obtained by polymerization reaction in the same manner except that the crosslinking agent is not added can also be used as a guideline for preparing the crosslinked polymer of the present disclosure. When the amount of ethylenically unsaturated monomer and the amount of crosslinking agent are used, it is more preferable that the uncrosslinked molecular weight is about 1,400,000 to 1,700,000.

Further, when the amount of the water-soluble ethylenically unsaturated monomer in the aqueous phase is about 15 to 20% by mass, the amount of the cross-linking agent is 0.4 to 0.4% relative to the water-soluble ethylenically unsaturated monomer. It is preferably about 6% by mass. Note that the molecular weight of the polymer (uncrosslinked polymer) obtained by polymerization reaction in the same manner except that the crosslinking agent is not added can also be used as a guideline for preparing the crosslinked polymer of the present disclosure. When the amount of ethylenically unsaturated monomer and the amount of crosslinking agent are used, it is more preferable that the uncrosslinked molecular weight is about 1,100,000 to 1,400,000.

As described above, these are merely guidelines for preparation, and even if these conditions are not satisfied, the polymer (A) is preferable as long as it is a crosslinked polymer that achieves the above range of storage elastic modulus G′. can be used as

As used herein, the molecular weight (weight average molecular weight) of a polymer is calculated from the absolute molecular weight measured using gel permeation chromatography (GPC). More specifically, using a gel permeation chromatography (GPC) light scattering apparatus, the absolute molecular weight is measured under the following conditions, and the weight average molecular weight is calculated.

GPC light scattering device: MODEL302 (manufactured by VISCOTEK. Co.)
Column: SB807 + SB806 + SB804 (manufactured by Showa Denko K.K.)
Carrier: 0.2 M sodium nitrate Column temperature: 40 degrees Flow rate: 0.5 mL/min
Injection volume: 500 μL
Concentration: 0.09 mg/mL

A polymer (A) that achieves the range of storage elastic modulus G' described above can exhibit particularly excellent thickening properties. Specifically, when used in combination with the ultraviolet absorber (D), particularly excellent thickening properties can be exhibited not only for water but also for high-concentration alcohol. A polymer of a water-soluble ethylenically unsaturated monomer usually cannot be thickened even when mixed with an aqueous alcohol solution (especially 30% by mass or more), or precipitates (separates). In some cases, the feeling of use was remarkably deteriorated. The composition of the present disclosure contains the above (A) to (D) (especially the polymer (A) and the ultraviolet absorber (D)), so that even if it contains a high concentration of alcohol, it is sufficiently A good viscosity can be imparted to the composition, and the photostability thereof can also be improved. These effects can be exhibited.

The polymer (A) is also more preferably a 0.3% by mass solution in a 70% by mass aqueous ethanol solution having a pH of 6 to 8 and a viscosity at 25° C. of 200 to 5000 mPa s. It is a crosslinked polymer. The upper or lower limit of the range is, for example, 4000 800, Or it may be 4900 mPa·s. For example, the range may be 1100-4900 mPa·s.

In addition, when preparing the said 0.3 mass % solution, when it is necessary to adjust pH, a pH adjuster can be used. As the pH adjuster, for example, an organic amine is preferable. Preferred organic amines include, for example, diisopropanolamine, 2-amino-2-methyl-1-propanol, and triethanolamine. An organic amine can be used individually by 1 type or in combination of 2 or more types. In addition, pH is measured using a pH meter at 25 degreeC.

Polymer (A) is more preferably a crosslinked polymer having a viscosity of 5000 to 30000 mPa·s at 25° C. in a 0.5 mass % aqueous solution of pH 5 to 6.5. The upper or lower limit of the range is, for example, 5500, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, 21000, 22000, 23000, 2400 0, 25000, It may be 26000, 27000, 28000 or 29000 mPa·s. For example, the range may be 5500-14000 mPa·s.

As described above, when the 0.5% by mass aqueous solution is prepared, if the pH needs to be adjusted, a pH adjuster can be used. As the pH adjuster, for example, sodium hydroxide is preferable. In addition, pH is measured using a pH meter at 25 degreeC.

In this specification, the viscosities of various compositions are values measured at 25° C. using a Brookfield viscometer (LV type) at a rotational speed of 20 revolutions per minute.

As the neutralizing agent (B), for example, organic amines and alkali metal salts can be preferably used. Preferred organic amines include, for example, diisopropanolamine, 2-amino-2-methyl-1-propanol, and triethanolamine. Moreover, as an alkali metal salt, sodium hydroxide, potassium hydroxide, etc. are preferable, for example. A neutralizing agent can be used individually by 1 type or in combination of 2 or more types.

The polymer (A) has a repeating structural unit derived from an ethylenically unsaturated carboxylic acid monomer, but by using the neutralizing agent (B), the carboxyl group in this repeating structural unit is neutralized to form a salt ( metal salts or ammonium salts). (Depending on the neutralizing agent used, the carboxyl groups may remain as they are.) At that time, not all the carboxyl groups need to be neutralized, and some of them may be neutralized.

In the viscous composition of the present disclosure, when the polymer (A) is contained as a partially neutralized product, it is not particularly limited, but among the repeating structural units derived from all ethylenically unsaturated carboxylic acid monomers It is preferably 5 to 90 mol % neutralized, more preferably 40 to 70 mol % neutralized.

The partially neutralized product can be obtained, for example, by treatment with an alkali metal salt such as sodium hydroxide.

Solvent (C) is water and/or alcohol, but this does not preclude the viscous composition of the present disclosure from containing solvents other than these. That is, the viscous composition of the present disclosure includes those containing solvents other than water and alcohol.

The alcohol is preferably a linear or branched alkyl alcohol having 1, 2, 3 or 4 carbon atoms, more preferably ethanol. Alcohol can be used individually by 1 type or in combination of 2 or more types.

The ultraviolet absorber (D) used in the viscous composition of the present disclosure is at least one selected from the group consisting of ethylhexyl methoxycinnamate (also referred to as octyl paramethoxycinnamate) and ferulic acid and salts thereof. be. Preferred salts are alkali metal salts or ammonium salts. More preferred alkali metal salts are, for example, sodium salts and potassium salts.

Where the viscous composition of the present disclosure contains (C) water and/or alcohol as described above, the alcohol content in the composition may be 0% by mass (that is, it does not contain), and for example 0 to 99% by mass can be exemplified. The upper or lower limit of the range may be, for example, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 95% by weight. For example, the range may be 1-90% by weight.

The content of the polymer (A) in the viscous composition of the present disclosure is preferably, for example, about 0.01 to 2% by mass. The upper or lower limit of the range is, for example, 0.02, 0.03, 0.04, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.000. 7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9% by weight There may be. For example, the range may be 0.05-1.5% by weight.

In addition, the content of the ultraviolet absorber (D) in the viscous composition of the present disclosure is not particularly limited as long as the effect is obtained, but is preferably about 1 to 1000 ppm, for example. The upper or lower limit of the range is, for example, 650, 700, 750, 800, 850, 900, or 950 ppm. For example, the range may be 5-900 ppm.

The viscous composition of the present disclosure may also contain components other than the above (A) to (D) as long as the effects are not impaired. As such other ingredients, for example, ingredients known as ingredients for external use compositions are preferably used. Examples include, but are not limited to, bases, absorption enhancers, humectants, thickeners, emulsifiers, colorants, fragrances, antioxidants, stabilizers, bactericides, preservatives, and the like. The composition for external use can be preferably used for application to the skin (face, arms, fingers, feet, hair and scalp, etc.). Preferred examples of external compositions include pharmaceutical compositions and cosmetic compositions. More specifically, for example, they are preferably used as hand sanitizers, astringent lotions, antiperspirants, cleansing agents, repellents for pests or pests, and the like. be able to.

Further, the viscous composition of the present disclosure preferably has a viscosity of 500 to 15000 mPa·s at 25°C. The upper or lower limit of the range may be, for example, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, or 14000 mPa s. good. For example, the range may be 1000-5000 mPa·s.

As described above, the viscous composition of the present disclosure has high photostability (viscosity is less likely to decrease due to light irradiation). Although it is not particularly limited, the viscosity after 400 hours of light irradiation at a temperature of 25 ° C. and an illumination intensity of 3000 Lx is measured, and the viscosity ratio (%) when the viscosity before the light irradiation is 100% is taken as the viscosity retention rate. At this time, the viscosity retention rate is preferably 40% or more, more preferably 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95% or more. Although the upper limit of the viscosity retention rate is not particularly limited, it may be 100%.

In this specification, the term "comprising" includes "consisting essentially of" and "consisting of." Also, the present disclosure encompasses any and all combinations of the constituent elements described herein.

Also, the various characteristics (property, structure, function, etc.) described for each of the embodiments of the disclosure described above may be combined in any way to identify subject matter encompassed by the disclosure. That is, the present disclosure encompasses all subject matter consisting of any and all possible combinations of the features described herein.

Hereinafter, the embodiments of the present disclosure will be described more specifically with examples, but the embodiments of the present disclosure are not limited to the following examples.

Preparation and Evaluation of Crosslinked Polymer Production Example 0 (Synthesis of water-soluble sucrose allyl ether)
55.4 g of ion-exchanged water and 16.1 g of sodium hydroxide were added to a 1 L four-necked separable flask equipped with a stirrer, a reflux condenser and a dropping funnel to dissolve sodium hydroxide in the ion-exchanged water. Further, 55.0 g of sucrose was added and reacted at 80° C. for 60 minutes with stirring to obtain an alkaline sucrose aqueous solution. To this alkaline sucrose aqueous solution, 48.6 g of allyl bromide was added dropwise over 2 hours while controlling rapid heat generation accompanying the etherification reaction. Thereafter, the reaction solution was aged at 80° C. for 3 hours to complete the etherification reaction. After cooling, acetic acid was added to adjust the pH to 7, and dehydration was carried out so that the water-soluble sucrose allyl ether content was 40% by mass to obtain 169 g of an aqueous solution. The degree of etherification of this water-soluble sucrose allyl ether was 2.3.

Production example 1
135 g of an 80% by mass acrylic acid aqueous solution was added to a 500 mL Erlenmeyer flask, 97 g of ion-exchanged water, and 0.102 g of a 40% by mass water-soluble sucrose allyl ether aqueous solution with a low degree of substitution obtained in Production Example 1 as a cross-linking agent (water sucrose allyl ether is 0.03% by mass with respect to the acrylic acid aqueous solution), 2,2'-azobis (2-methylpropionamidine) dihydrochloride as an initiator (manufactured by Wako Pure Chemical Industries, Ltd. V-50 ) was added to prepare a water-soluble ethylenically unsaturated monomer aqueous solution. Separately, 377 g of n-heptane was added to a 2 L four-necked separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a nitrogen gas introduction tube, and PEG30 Dipolyhydroxystearate (supplied to Croda Japan Co., Ltd.) as a surfactant was added. Company product name CITHROL DPHS-S-(MV)) 2.04 g were dispersed and dissolved. The previously prepared water-soluble ethylenically unsaturated monomer aqueous solution was added thereto, and while stirring at a stirring speed of 1200 rpm, the inside of the system was replaced with nitrogen and the bath temperature was maintained at 60°C for 1 hour. Polymerization was carried out by the reverse phase suspension polymerization method. After the polymerization was completed, water and n-heptane were distilled off to obtain 102 g of a crosslinked polymer powder.

Production example 2
123 g of an 80% by mass acrylic acid aqueous solution was added to a 500 mL Erlenmeyer flask, 109 g of ion-exchanged water, and 0.092 g of a 40% by mass water-soluble sucrose allyl ether aqueous solution with a low degree of substitution obtained in Production Example 1 as a crosslinking agent (water sucrose allyl ether is 0.03% by mass with respect to the acrylic acid aqueous solution), 2,2'-azobis (2-methylpropionamidine) dihydrochloride as an initiator (manufactured by Wako Pure Chemical Industries, Ltd. V-50 ) was added to prepare a water-soluble ethylenically unsaturated monomer aqueous solution. Separately, 377 g of n-heptane was added to a 2 L four-necked separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a nitrogen gas introduction tube, and PEG30 Dipolyhydroxystearate (supplied to Croda Japan Co., Ltd.) as a surfactant was added. Company product name CITHROL DPHS-S-(MV)) 1.84 g was dispersed and dissolved. The previously prepared water-soluble ethylenically unsaturated monomer aqueous solution was added thereto, and while stirring at a stirring speed of 1200 rpm, the inside of the system was replaced with nitrogen and the bath temperature was maintained at 60°C for 1 hour. Polymerization was carried out by the reverse phase suspension polymerization method. After completion of the polymerization, water and n-heptane were distilled off to obtain 81 g of crosslinked polymer powder.

Production example 3
109 g of an 80% by mass acrylic acid aqueous solution was added to a 500 mL Erlenmeyer flask, 124 g of ion-exchanged water, and 0.22 g of a 40% by mass water-soluble sucrose allyl ether aqueous solution with a low degree of substitution obtained in Production Example 1 as a crosslinking agent (water sucrose allyl ether is 0.08% by mass with respect to the acrylic acid aqueous solution), 2,2'-azobis (2-methylpropionamidine) dihydrochloride as an initiator (manufactured by Wako Pure Chemical Industries, Ltd. V-50 ) was added to prepare a water-soluble ethylenically unsaturated monomer aqueous solution. Separately, 377 g of n-heptane was added to a 2 L four-necked separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a nitrogen gas introduction tube, and PEG30 Dipolyhydroxystearate (supplied to Croda Japan Co., Ltd.) as a surfactant was added. Company product name CITHROL DPHS-S-(MV)) 1.64 g was dispersed and dissolved. The previously prepared water-soluble ethylenically unsaturated monomer aqueous solution was added thereto, and while stirring at a stirring speed of 1200 rpm, the inside of the system was replaced with nitrogen and the bath temperature was maintained at 60°C for 1 hour. Polymerization was carried out by the reverse phase suspension polymerization method. After completion of the polymerization, water and n-heptane were distilled off to obtain 80 g of crosslinked polymer powder.

Production example 4
Except for changing the amount of the water-soluble sucrose allyl ether obtained in Production Example 1 to 0.3 g (the water-soluble sucrose allyl ether is 0.11% by mass relative to the acrylic acid aqueous solution), Production Example 3 80 g of a crosslinked polymer powder was obtained by the same operation as in .

Production example 5
73 g of an 80% by mass acrylic acid aqueous solution was added to a 500 mL Erlenmeyer flask, 156 g of ion-exchanged water, and 0.458 g of a 40% by mass water-soluble sucrose allyl ether aqueous solution with a low degree of substitution obtained in Production Example 1 as a cross-linking agent (water sucrose allyl ether is 0.25% by mass with respect to the acrylic acid aqueous solution), 2,2'-azobis (2-methylpropionamidine) dihydrochloride as an initiator (manufactured by Wako Pure Chemical Industries, Ltd. V-50 ) was added to prepare a water-soluble ethylenically unsaturated monomer aqueous solution. Separately, 377 g of n-heptane was added to a 2 L four-necked separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a nitrogen gas introduction tube, and PEG30 Dipolyhydroxystearate (supplied to Croda Japan Co., Ltd.) as a surfactant was added. Company product name CITHROL DPHS-S-(MV)) 1.10 g was dispersed and dissolved. The previously prepared water-soluble ethylenically unsaturated monomer aqueous solution was added thereto, and while stirring at a stirring speed of 1200 rpm, the inside of the system was replaced with nitrogen and the bath temperature was maintained at 60°C for 1 hour. Polymerization was carried out by the reverse phase suspension polymerization method. After completion of the polymerization, water and n-heptane were distilled off to obtain 54 g of a crosslinked polymer powder.

Production example 6
55 g of an 80% by mass acrylic acid aqueous solution was added to a 500 mL Erlenmeyer flask, 173 g of ion-exchanged water, and 0.556 g of a 40% by mass water-soluble sucrose allyl ether aqueous solution with a low degree of substitution obtained in Production Example 1 as a cross-linking agent (water sucrose allyl ether is 0.4% by mass with respect to the acrylic acid aqueous solution), 2,2'-azobis (2-methylpropionamidine) dihydrochloride as an initiator (manufactured by Wako Pure Chemical Industries, Ltd. V-50 ) was added to prepare a water-soluble ethylenically unsaturated monomer aqueous solution. Separately, 377 g of n-heptane was added to a 2 L four-necked separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a nitrogen gas introduction tube, and PEG30 Dipolyhydroxystearate (supplied to Croda Japan Co., Ltd.) as a surfactant was added. Company product name CITHROL DPHS-S-(MV)) 0.83 g was dispersed and dissolved. The previously prepared water-soluble ethylenically unsaturated monomer aqueous solution was added thereto, and while stirring at a stirring speed of 1200 rpm, the inside of the system was replaced with nitrogen and the bath temperature was maintained at 60°C for 1 hour. Polymerization was carried out by the reverse phase suspension polymerization method. After completion of the polymerization, water and n-heptane were distilled off to obtain 41 g of crosslinked polymer powder.

Production example 7
80 g of crosslinked polymer powder was obtained by the same operation as in Production Example 3, except that the rotation speed during polymerization was changed to 1000 rpm.

Production example 8
82 g of crosslinked polymer powder was obtained by the same operation as in Production Example 3, except that the rotation speed during polymerization was changed to 700 rpm.

Production example 9
81 g of crosslinked polymer powder was obtained in the same manner as in Production Example 3, except that the rotation speed during polymerization was changed to 600 rpm.

Production example 10
80 g of a crosslinked polymer powder was obtained by the same operation as in Production Example 3, except that the rotation speed during polymerization was changed to 500 rpm.

Production Example 11
100 g of an 80% by mass acrylic acid aqueous solution was added to a 500 mL Erlenmeyer flask, 117 g of ion-exchanged water, and 0.375 g of a 40% by mass water-soluble sucrose allyl ether aqueous solution with a low degree of substitution obtained in Production Example 1 as a cross-linking agent (water sucrose allyl ether is 0.15% by mass with respect to the acrylic acid aqueous solution), 2,2'-azobis (2-methylpropionamidine) dihydrochloride as an initiator (Wako Pure Chemical Industries, Ltd. V-50 ) was added to prepare a water-soluble ethylenically unsaturated monomer aqueous solution. Separately, 323 g of n-heptane was added to a 2 L four-necked separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a nitrogen gas inlet tube. 1.0 g of S-370 manufactured by Kagaku Foods Co., Ltd. was dispersed and dissolved. The previously prepared water-soluble ethylenically unsaturated monomer aqueous solution was added thereto, and while stirring at a stirring speed of 700 rpm, the inside of the system was replaced with nitrogen and the bath temperature was maintained at 60°C for 1 hour. Polymerization was carried out by the reverse phase suspension polymerization method. After completion of the polymerization, water and n-heptane were distilled off to obtain 79 g of crosslinked polymer powder.

Comparative production example 1
63 g of acrylic acid, 0.176 g of pentaerythritol tetraallyl ether, 0.016 g of azobisisobutyronitrile, and 375 g of ethylene dichloride were placed in a 500 mL four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube and condenser. I prepared. Subsequently, after uniformly stirring and mixing, nitrogen gas was blown into the solution in order to remove oxygen present in the upper space of the reaction vessel, raw materials and solvent. Then, while stirring at a stirring speed of 400 rpm, polymerization was carried out by a precipitation polymerization method for 3 hours at 70 to 75° C. in a nitrogen atmosphere. After completion of the polymerization, ethylene dichloride was distilled off to obtain 62 g of a crosslinked polymer.

Production Examples 1 to 11 are preparations of crosslinked polymers by reverse phase suspension polymerization, and Comparative Production Example 1 is preparation of crosslinked polymers by precipitation polymerization.

Various measurement methods
[Molecular weight]
In each of the above production examples (except for production example 0) and comparative production example 1, the same operation was performed except that the cross-linking agent (water-soluble sucrose allyl ether) was not added. body) were prepared. Then, the molecular weight (weight average molecular weight) of each uncrosslinked product was measured under the following conditions.

That is, using a gel permeation chromatography (GPC) light scattering apparatus equipped with a triple detector, the absolute molecular weight (viscosity method) was measured under the following conditions, and the weight average molecular weight was calculated.

GPC light scattering device: MODEL302 (manufactured by VISCOTEK. Co.)
Column: SB807 + SB806 + SB804 (manufactured by Showa Denko K.K.)
Carrier: 0.2 M sodium nitrate Column temperature: 40 degrees Flow rate: 0.5 mL/min
Injection volume: 500 μL
Concentration: 0.09 mg/mL

[Median particle size]
After dispersing 0.01 g of each crosslinked polymer in 5 ml of heptane, the particle size distribution was measured using a particle size distribution analyzer (manufactured by Shimadzu Corporation, SALD-7100, using a batch cell). From the obtained particle size distribution, the median particle size on a volume basis was determined.

[Storage modulus G']
1.5 g of the crosslinked polymer was placed in a 500 ml beaker with 296.7 g of ion-exchanged water, which was stirred at 400 rpm with a stirrer equipped with a 4-bladed paddle (blade diameter: 50 mm). . Dissolution of the crosslinked polymer was visually confirmed, and the resulting 0.5% by weight solution was neutralized to pH 5-6.5 with sodium hydroxide. −2000ex) was used to measure the storage modulus (G′) under the conditions of a measurement temperature of 25° C., a 60 mm parallel plate, a gap of 1000 μm, a strain of 1% or less, and an angular velocity of 0.1 rad/s.

[Sphericality]
Observe the particles of each crosslinked polymer with a scanning microscope, randomly select 10 particles from the observed image, measure the major axis and minor axis of each particle, and average the minor axis / major axis ratio was defined as sphericity.

[Aqueous solution viscosity]
296.7 g of ion-exchanged water was placed in a beaker with a capacity of 500 ml and stirred at 400 rpm with a stirrer equipped with a 4-blade paddle (blade diameter of 50 mm). . Dissolution of the crosslinked polymer was visually confirmed, and the resulting 0.5% by weight solution was neutralized to pH 5 to 6.5 with sodium hydroxide, and the resulting aqueous solution was measured with a Brookfield viscometer under the following conditions. did.

<Viscosity measurement conditions>
B-type viscometer: LV type manufactured by BROOKFIELD Temperature: 25°C
Rotor: LV-4
Rotation speed: 20r/min

[Viscosity of solution using 70% by mass ethanol aqueous solution as solvent]
99.7 g of 70% by mass ethanol aqueous solution was placed in a beaker with a volume of 200 ml, and this was stirred at 400 rpm using a stirrer equipped with a four-blade paddle (blade diameter: 50 mm). was put in. Dissolution of the crosslinked polymer was visually confirmed, and the resulting 0.3% by weight solution was neutralized to pH 6 to 8 with an organic amine (triethanolamine). measured by a meter.

<Viscosity measurement conditions>
B-type viscometer: LV type manufactured by BROOKFIELD Temperature: 25°C
Rotor: LV-3
Rotation speed: 20r/min

The above results are summarized in Table 1. In addition, the monomer concentration in the water-soluble ethylenically unsaturated monomer aqueous solution (that is, the water phase containing the water-soluble ethylenically unsaturated monomer, the water-soluble cross-linking agent and water) used for the reversed-phase suspension polymerization is (Acrylic acid) concentration (% by mass) is shown. Therefore, for Comparative Production Example 1, the value of the monomer concentration is not described. Further, the concentration of the cross-linking agent indicates the usage ratio (% by mass) when the mass of the monomer used is taken as 100%.

Preparation and evaluation of viscous composition Comparative preparation example 3a
63 g of acrylic acid, 0.35 g of pentaerythritol tetraallyl ether, 0.016 g of azobisisobutyronitrile, and 375 g of ethylene dichloride were placed in a 500 mL four-neck flask equipped with a stirrer, thermometer, nitrogen blowing tube and condenser. I prepared. Subsequently, they were uniformly stirred and mixed to obtain a solution. Nitrogen gas was bubbled through the solution to remove oxygen present in the headspace of the reaction vessel, feedstock and solvent. Then, while stirring at a stirring speed of 400 rpm, polymerization was carried out by a precipitation polymerization method for 3 hours at 70 to 75° C. in a nitrogen atmosphere. After completion of the polymerization, ethylene dichloride was distilled off to obtain 63 g of a crosslinked polymer.

Comparative production example 3b
62 g of a crosslinked polymer powder was obtained in the same manner as in Comparative Production Example 3a, except that the amount of pentaerythritol allyl ether added was changed to 0.176 g.

The sphericity of the crosslinked polymers produced in Comparative Production Examples 3a and 3b was also measured by the above method.

Example 1
A 200 ml beaker was charged with 29.7 g of purified water, 69.9 g of ethyl alcohol, and 20 mg of 2-ethylhexyl 4-methoxycinnamate, and the mixture was stirred with a stirrer with four paddle blades having a diameter of 50 mmφ. 0.3 g of the prepared crosslinked polymer was dispersed. Next, 0.093 g of triethanolamine (TEA) was added as a neutralizing agent to the dispersion liquid of the crosslinked polymer to increase the viscosity, and the mixture was stirred until undissolved matter disappeared to obtain a viscous composition.

Example 2
A viscous composition was obtained in the same manner as in Example 1, except that the amount of 2-ethylhexyl 4-methoxycinnamate added was changed to that shown in Table 2.

Examples 3-4
A viscous composition was obtained in the same manner as in Example 1, except that the ultraviolet absorber was changed to feralic acid and the amount added was changed to that shown in Table 2.

Comparative Examples 1-6
A viscous composition was obtained in the same manner as in Example 1, except that the ultraviolet absorber was changed to the compound and/or addition amount shown in Table 2.

Comparative example 7
A viscous composition was obtained in the same manner as in Comparative Example 1 except that the crosslinked polymer produced in Comparative Production Example 3a was used instead of the crosslinked polymer.

Comparative example 8
A viscous composition was obtained in the same manner as in Comparative Example 1, except that the crosslinked polymer produced in Comparative Production Example 3b was used instead of the crosslinked polymer.

[Photo stability test]
The viscous composition was irradiated with light for 400 hours using a photostability tester (LST-2010, manufactured by Tokyo Rikakikai Co., Ltd.) at a temperature of 25° C. and an illumination of 3000 Lx. The viscosity before light irradiation and after light irradiation for 400 hours was measured with a Brookfield viscometer at 25° C., and the viscosity retention rate was calculated from the following formula.

Viscosity retention rate = (viscosity after light irradiation for 400 hours)/(viscosity before light irradiation) x 100

<Viscosity measurement conditions>
B-type viscometer: LV type manufactured by BROOKFIELD Temperature: 25°C
Rotor: LV-3 or LV-4
Rotation speed: 20r/min

[Tactile sensation (refreshing feeling)]
A certain amount of the viscous composition was taken on the hand and applied to the fingers, and the refreshing feeling was evaluated. According to the following evaluation criteria, evaluation was carried out by 5 expert panelists, and evaluation was performed on a 5-point scale from 1 to 5 (the more refreshed, the higher the numerical value), and the average value was obtained.

<Evaluation Criteria>
Refreshing feeling ○: Refreshing Average value of 4.0 or more △: Slightly refreshing Average value of 3.0 or more to less than 4.0 ×: Not refreshing Average value of less than 3.0 Evaluation results Table 2 shows.

Formulation examples for which it is assumed that the crosslinked polymer is used are shown below. It is expected that the manufacture of the formulation examples will produce products that exhibit the effects of the present invention. In addition, the composition ratio % in the prescription examples represents mass % when the total amount is 100 mass %.

Claims (9)

(A) a polymer of water-soluble ethylenically unsaturated carboxylic acid monomers crosslinked by a crosslinking agent;
(B) a neutralizing agent;
(C) water and / or alcohol, and (D) containing an ultraviolet absorber,
The sphericity of the polymer (A) is 0.7 to 1.0,
The ultraviolet absorber (D) is at least one selected from the group consisting of ethylhexyl methoxycinnamate and ferulic acid and salts thereof.
Viscous composition. The viscous composition according to claim 1, having a viscosity of 500 to 15000 mPa·s. The polymer (A) is
A polymer having a storage modulus G′ (Pa) at 25° C. of 0.1 to 300 for a 0.5% by mass aqueous solution of pH 5 to 6.5,
The viscous composition according to claim 1 or 2. The polymer (A) is
A polymer having a viscosity of 5,000 to 30,000 mPa s at 25° C. in a 0.5% by mass aqueous solution of pH 5 to 6.5.
The viscous composition according to any one of claims 1-3. The neutralizing agent (B) is at least one selected from the group consisting of organic amines and alkali metal salts,
The viscous composition according to any one of claims 1-4. The viscosity according to any one of claims 1 to 5, wherein the ethylenically unsaturated monomer is at least one compound selected from the group consisting of acrylic acid and its salts, and methacrylic acid and its salts. Composition. The viscous composition according to any one of claims 1 to 6, wherein the water-soluble cross-linking agent is a water-soluble sucrose allyl ether having a degree of etherification of 1.8 to 4.0. The polymer (A) is
A polymer having a viscosity of 200 to 5000 mPa s at 25 ° C. in a 0.3% by mass solution in a 70% by mass ethanol aqueous solution and having a pH of 6 to 8.
The viscous composition according to any one of claims 1-7. The viscous composition according to any one of claims 1 to 8, containing 10% by mass or more of alcohol.