WO2021200136A1 - Viscous composition - Google Patents

Viscous composition Download PDF

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Publication number
WO2021200136A1
WO2021200136A1 PCT/JP2021/010729 JP2021010729W WO2021200136A1 WO 2021200136 A1 WO2021200136 A1 WO 2021200136A1 JP 2021010729 W JP2021010729 W JP 2021010729W WO 2021200136 A1 WO2021200136 A1 WO 2021200136A1
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mass
ascorbic acid
acid
parts
meth
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PCT/JP2021/010729
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French (fr)
Japanese (ja)
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山口　博史
亮輔 村上
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住友精化株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • the present disclosure relates to a viscous composition or the like.
  • Ascorbic acid is an ingredient used in compositions for various uses (for example, cosmetics and foods).
  • the present inventors have found that when ascorbic acid or a derivative thereof is added to a viscous composition, the viscosity is significantly reduced. Therefore, in order to find a method for providing a viscous composition in which the viscosity is unlikely to decrease even if ascorbic acid or a derivative thereof is blended, and a viscous composition containing ascorbic acid or a derivative thereof and having an appropriate viscosity. Study was carried out.
  • the present inventors have a viscous composition prepared by using a specific amount of a specific copolymer among the alkyl-modified carboxyl group-containing water-soluble copolymers disclosed in Patent Document 1 (International Publication No. 2007/055354). We have found that even if ascorbic acid or a derivative thereof is blended in the product, it is unlikely that the viscosity will decrease, and further studies have been conducted.
  • the present disclosure includes, for example, the subjects described in the following sections.
  • Item 1. (A) The following (i), (ii), and (iii): (I) 100 parts by mass of (meth) acrylic acid (ii) Compound having two or more ethylenically unsaturated groups 0.01 to 1 part by mass (iii) (meth) acrylic having an alkyl group having 10 to 30 carbon atoms A composition containing 0.3% by mass or more of a polymer obtained by polymerizing 0.5 to 10 parts by mass of an acid alkyl ester, and (B) ascorbic acid or a derivative thereof.
  • Item 2. The above (ii) is A compound having two or more ethylenically unsaturated groups, 0.01 to 0.2 parts by mass.
  • Item 2. The composition according to Item 1. Item 3. Item 2. The composition according to Item 1 or 2, wherein the compound having two or more ethylenically unsaturated groups is pentaerythritol allyl ether. Item 4. Item 2. The composition according to any one of Items 1 to 3, which has a viscosity of 5000 mPa ⁇ s or more. Item 5. Item 2. The composition according to any one of Items 1 to 4, which contains 2.5% by mass or more of the above (B). Item 6.
  • At least one ascorbic acid derivative selected from the group consisting of ascorbic acid salt, ascorbic acid glycoside, ascorbic acid phosphate, fatty acid ascorbyl, ascorbyl ethyl, ascorbic acid-phosphate-fatty acid, and glyceryl octyl ascorbic acid.
  • Seed, Item 8. The composition according to any one of Items 1 to 5.
  • Item 7. The above (ii) is The compound having two or more ethylenically unsaturated groups is 0.01 to 0.2 parts by mass.
  • the compound having two or more ethylenically unsaturated groups is pentaerythritol allyl ether.
  • the viscosity is 5000 mPa ⁇ s or more, Containing 2.5% by mass or more of the above (B), (B) is at least one selected from the group consisting of ascorbic acid, ascorbic acid salt, ascorbic acid glycoside, and ascorbic acid phosphate.
  • Item 2. The composition according to Item 1.
  • (A) The following (i), (ii), and (iii): (I) 100 parts by mass of (meth) acrylic acid (ii) Compound having two or more ethylenically unsaturated groups 0.01 to 1 part by mass (iii) (meth) acrylic having an alkyl group having 10 to 30 carbon atoms Contains a polymer obtained by polymerizing 0.5 to 10 parts by mass of an acid alkyl ester. A thickener for preparing a viscous composition containing 2.5% by mass or more of ascorbic acid or a derivative thereof.
  • composition containing ascorbic acid or a derivative thereof and having an appropriate viscosity is provided.
  • the viscosity measurement result of the viscous composition containing various polymers and ascorbic acid derivatives is shown.
  • the UV transmittance measurement result of the viscous composition containing various polymers and ascorbic acid derivatives is shown.
  • the present disclosure preferably includes, but is not limited to, a composition containing a specific polymer and ascorbic acid or a derivative thereof, its use, a method for producing the same, and the like, and the present disclosure is described herein. Includes everything disclosed and recognizable to those skilled in the art.
  • compositions included in the present disclosure include (A) a polymer obtained by polymerizing the following (i), (ii), and (iii) (sometimes referred to as “polymer (A)"), and (B. ) Contains ascorbic acid or a derivative thereof (sometimes referred to as “component (B)").
  • (meth) acrylic means acrylic and / or methacryl.
  • acrylic acid either one of acrylic acid and methacrylic acid may be used alone, or both of them may be used in combination.
  • Alkyl groups have 10 to 30 carbon atoms (10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, Alternatively, the (meth) acrylic acid alkyl ester of 30) is an ester of (meth) acrylic acid and a higher alcohol having an alkyl group having 10 to 30 carbon atoms.
  • the alkyl group preferably has, for example, 12 to 30, 14 to 28, 16 to 26, or 18 to 24 carbon atoms.
  • Such (meth) acrylic acid alkyl ester is not particularly limited, and is, for example, an ester of (meth) acrylic acid and stearyl alcohol, an ester of (meth) acrylic acid and eicosanol, and (meth) acrylic acid and behenyl alcohol.
  • an ester of (meth) acrylic acid and tetracosanol preferably an ester of (meth) acrylic acid alkyl esters.
  • these (meth) acrylic acid alkyl esters preferably stearyl methacrylate, eicosanyl methacrylate, behenyl methacrylate, and tetracosanyl methacrylate can be mentioned.
  • These (meth) acrylic acid alkyl esters may be used alone or in combination of two or more. Further, as such a (meth) acrylic acid alkyl ester, for example, commercially available products such as NOF Corporation's trade name Blemmer VMA70 and Brenmer SMA may be used.
  • the amount of the (meth) acrylic acid alkyl ester used is 0.5 to 10 parts by mass, preferably 0.5 to 7.5 parts by mass, 0.5 parts by mass with respect to 100 parts by mass of (meth) acrylic acid. It is ⁇ 5 parts by mass, or 1 to 5 parts by mass, and more preferably 1 to 3 parts by mass.
  • the compound having two or more ethylenically unsaturated groups is not particularly limited, but for example, ethylene glycol, propylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, polyglycerin, trimethylolpropane, penta.
  • Acrylic acid esters with two or more substitutions of polyols such as erythritol, saccharose, and sorbitol; allyl ethers with two or more substitutions of the polyols; diallyl phthalate, triallyl phosphate, allyl methacrylate, tetraallyloxyethane, triallyl cyanurate.
  • Divinyl adipate Vinyl crotonic acid, 1,5-hexadiene, divinylbenzene, polyallyl saccharose and the like.
  • sucrose allyl ether pentaerythritol allyl ether (particularly pentaerythritol triallyl ether and pentaerythritol tetraallyl ether are preferable), tetraallyl oxyethane, and the like.
  • Examples thereof include triallyl phosphate and polyallyl saccharose, among which sucrose allyl ether and pentaerythritol allyl ether are more preferable, and pentaerythritol allyl ether is particularly preferable.
  • These compounds having two or more ethylenically unsaturated groups may be used alone or in combination of two or more.
  • the amount of the compound having two or more ethylenically unsaturated groups used is 0.01 to 1 part by mass with respect to 100 parts by mass of (meth) acrylic acid.
  • the upper or lower limit of the range is, for example, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0. It may be 8, 0.85, 0.9, or 0.95 parts by mass.
  • the range may be about 0.02 to 0.8 parts by mass.
  • the amount of the compound having two or more ethylenically unsaturated groups in the polymer (A) used is relatively small, the effect of improving the transparency of the composition of the present disclosure is exhibited. Therefore, it is preferable.
  • the amount of the compound having two or more ethylenically unsaturated groups is preferably about 0.01 to 0.2 parts by mass with respect to 100 parts by mass of (meth) acrylic acid.
  • the method of polymerizing (i), (ii) and (iii) is not particularly limited, and for example, these are polymerized in a polymerization solvent in the presence of a radical polymerization initiator. There is a method of making it.
  • the radical polymerization initiator is not particularly limited, and is, for example, ⁇ , ⁇ '-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobismethyl. Examples thereof include isobutyrate, 2,2'-azobis (2-methylpropionamidine) dihydrochloride, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tertiary butyl hydroperoxide and the like. These radical polymerization initiators may be used alone or in combination of two or more.
  • the amount of the radical polymerization initiator used is not particularly limited, but is preferably 0.01 to 0.45 parts by mass and 0.01 to 0.35 parts by mass with respect to 100 parts by mass of (meth) acrylic acid, for example.
  • the portion is more preferable.
  • precipitation polymerization or reverse phase suspension polymerization can be preferably used.
  • reverse phase suspension polymerization may be carried out in a polymerization solvent containing a nonionic surfactant having a polyoxyethylene chain.
  • nonionic surfactant having the polyoxyethylene chain examples include polyhydric alcohol fatty acid ester ethylene oxide adduct, block copolymer of hydroxy fatty acid and ethylene oxide, and polyoxyethylene castor oil.
  • polyhydric alcohol fatty acid ester ethylene oxide adduct an ester compound of polyoxyethylene hydrogenated castor oil and polyhydric alcohol fatty acid is preferably mentioned.
  • the polyhydric alcohol fatty acid here is a saturated or unsaturated polyvalent (14, 15, 16, 17, 18, 19, 20, 21, 22, 23, or 24) having 14 to 24 carbon atoms (14, 15, 16, 17, 18, 19, 20, 21, 22, 23, or 24).
  • divalent alcohol fatty acids are preferable, and more specifically, isopalmitic acid, isostearic acid, isooleic acid and the like are preferably mentioned.
  • the average number of moles of ethylene oxide added to polyoxyethylene in the ester compound of the polyoxyethylene hydrogenated castor oil and the polyhydric alcohol fatty acid is not particularly limited, and examples thereof include about 20 to 100 or about 30 to 70.
  • Particularly preferable as an ester compound of polyoxyethylene hydrogenated castor oil and polyhydric alcohol fatty acid is polyoxyethylene hydrogenated castor oil isostearate.
  • the polyoxyethylene castor oil preferably has an addition mole number of ethylene oxide of about 2 to 10, and more preferably about 2 to 5.
  • the block copolymer of hydroxy fatty acid and ethylene oxide can be said to be a copolymer composed of polyhydroxy fatty acid and polyoxyethylene.
  • the fatty acid of the polyhydroxy fatty acid is preferably a fatty acid having about 14 to 22 carbon atoms, preferably myristic acid, palmitic acid, stearic acid and the like, and examples of the hydroxy fatty acid are hydroxymyristic acid, hydroxypalmitic acid, hydroxystearic acid and the like. Is preferable, and hydroxystearic acid is particularly preferable.
  • As the hydroxystearic acid 12-hydroxystearic acid is particularly preferable.
  • As the polyhydroxy fatty acid polyhydroxystearic acid is particularly preferable.
  • As the block copolymer of hydroxy fatty acid and ethylene oxide a block copolymer of 12-hydroxystearic acid and ethylene oxide is particularly preferable.
  • the nonionic surfactant having the polyoxyethylene chain can be used alone or in combination of two or more.
  • the amount of the nonionic surfactant having the polyoxyethylene chain used is preferably about 0.5 to 10 parts by mass with respect to 100 parts by mass of (i) (meth) acrylic acid.
  • the lower limit of the mass range may be, for example, about 0.75, 1.0, 1.25, or 1.5, and the upper limit of the mass range may be, for example, 9.5, 9, 8. It may be about 5.5, 8, 7.5, 7, 6.5, 6, or 5.5. For example, about 1 to 7.5 parts by mass is more preferable.
  • the polymerization solvent is not particularly limited, but is a polymer (A) obtained by dissolving (meth) acrylic acid, the (meth) acrylic acid alkyl ester, and a compound having two or more ethylenically unsaturated groups. ) Is preferably a solvent that does not dissolve.
  • polymerization solvent examples include normal pentane, normal hexane, normal heptane, normal octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, chlorobenzene, ethylene dichloride, ethyl acetate. , Isopropyl acetate, ethyl methyl ketone, isobutyl methyl ketone and the like.
  • polymerization solvents ethylene dichloride, normal hexane, normal heptane, and ethyl acetate are preferable from the viewpoint of stable quality and easy availability.
  • These polymerization solvents may be used alone or in combination of two or more.
  • the amount of the polymerization solvent used is not particularly limited, but for example, it is preferably 200 to 10000 parts by mass and more preferably 300 to 2000 parts by mass with respect to 100 parts by mass of (meth) acrylic acid.
  • the polymerization solvent within the above range, even if the polymerization reaction proceeds, the alkyl-modified carboxyl group-containing water-soluble copolymer is preferably suppressed from agglomeration and uniformly stirred, and the polymerization reaction is made more efficient. It becomes possible to proceed in a targeted manner.
  • the atmosphere when the polymerization reaction is carried out is not particularly limited as long as the polymerization reaction is possible, and examples thereof include an inert gas atmosphere such as nitrogen gas and argon gas.
  • the reaction temperature at the time of carrying out the above polymerization reaction is not particularly limited as long as the polymerization reaction is possible, but for example, it is preferably 50 to 90 ° C, more preferably 55 to 75 ° C. By carrying out the polymerization reaction at such a reaction temperature, it is possible to preferably suppress an increase in the viscosity of the reaction solution, facilitate reaction control, and preferably control the bulk density of the obtained polymer (A). can.
  • the reaction time for carrying out the above polymerization reaction varies depending on the reaction temperature and cannot be unconditionally determined, but is usually 2 to 10 hours.
  • reaction solution can be heated to 80 to 130 ° C. to remove the polymerization solvent, whereby the white fine powder polymer (A) can be isolated.
  • ascorbic acid includes, for example, ascorbate, ascorbic acid glycoside, ascorbic acid phosphate, fatty acid ascorbyl (ester of fatty acid and ascorbic acid), ascorbyl ethyl, ascorbic acid-phosphate-fatty acid, glyceryl octyl ascorbin. Acids and the like can be mentioned.
  • ascorbic acid salt include sodium ascorbate and calcium ascorbate.
  • Ascorbic acid glycosides are preferably ascorbic acid glucosides, and more specifically, ascorbic acid 2-glucosides, ascorbic acid 6-glucosides and the like can be mentioned.
  • Examples of the ascorbate phosphate include sodium ascorbate phosphate and magnesium ascorbate phosphate.
  • Examples of the fatty acid ascorbyl include ascorbyl palmitate, ascorbyl stearate, and ascorbyl isopalmitate.
  • Examples of the ascorbic acid-phosphoric acid-fatty acid include ascorbic acid-2 phosphoric acid-6 palmitic acid and the like. Ascorbic acid or a derivative thereof can be used alone or in combination of two or more. Although not particularly limited, ascorbic acid or a glycoside thereof is preferable as ascorbic acid or a derivative thereof.
  • the degree of neutralization of the polymer (A) can be easily adjusted by neutralizing the carboxyl group of acrylic acid and / or methacrylic acid with an alkali.
  • the degree of neutralization here refers to the ratio of the number of moles of neutralized groups to the total number of moles of carboxyl groups of acrylic acid and / or methacrylic acid.
  • the alkali used for neutralization include sodium hydroxide, potassium hydroxide, triethanolamine, diisopropylamine and the like.
  • the neutralization method is not particularly limited, and examples thereof include a method of neutralizing acrylic acid and / or methacrylic acid in advance, a method of neutralizing a polymer obtained by polymerization, and the like.
  • the degree of neutralization of the polymer (A) is, for example, preferably 0 to 80%, more preferably 10 to 60%, and even more preferably 20 to 50%.
  • composition of the present disclosure further contains water.
  • the water contained is not particularly limited, and for example, tap water, distilled water, ion-exchanged water, or the like can be used.
  • the composition of the present disclosure may further contain a pH adjuster, if necessary.
  • a pH regulator can preferably be used to adjust the pH of the composition to near neutral.
  • the composition of the present disclosure preferably has a pH of, for example, about 6 to 8.
  • the upper or lower limit of the pH range is 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, It may be 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, or 7.9.
  • the pH range may be about 6.5 to 7.
  • a known pH adjuster can be used, and a pH adjuster known in the cosmetics field or the food field is preferable.
  • a pH adjuster known in the cosmetics field or the food field is preferable.
  • sodium hydroxide, potassium hydroxide and the like can be mentioned.
  • the viscosity of the composition of the present disclosure is preferably 5000 mPa ⁇ s or more, and more preferably about 5000 to 50,000 mPa ⁇ s, for example.
  • the upper or lower limit of the range is, for example, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, 21000, 22000, 23000, 24000, 25000, 26000, 27000, 28000, 29000, 30000, 31000, 32000, 33000, 34000, 35000, 36000, 37000, 38000, 39000, 40000, 41000, 42000, 43000, 44000, 45000, It may be 46000, 47000, 48000, or 49000 mPa ⁇ s.
  • the range may be about 5500 to 40,000 mPa ⁇ s or about 6000 to 30000 mPa ⁇ s.
  • Viscosity is measured using a BH type rotational viscometer. Specifically, it is measured by reading the viscosity value 1 minute after the start of rotation of the rotor at 25 ° C., assuming that the rotation speed of the spindle rotor is 20 rotations per minute.
  • the rotor used for measurement is less than 2000 mPa ⁇ s, the rotor No. In the case of 3, 2000 mPa ⁇ s or more and less than 5000 mPa ⁇ s, the rotor No.
  • each viscous composition can be used after defoaming by centrifuging (for example, 2000 rpm ⁇ 10 to 20 minutes).
  • the polymer (A) is preferably contained in an amount of 0.3% by mass or more, more preferably 0.4 or 0.5% by mass or more. Further, as described above, the composition of the present disclosure has a characteristic that the viscosity is less likely to decrease as compared with the case where the component (B) is not contained, although the composition contains the component (B). ) When the viscosity is not relatively high when the component (B) is not contained, the amount of decrease in viscosity is small even if the component (B) is blended, so that it can be considered that the effect of the composition of the present disclosure is not sufficiently exhibited. ..
  • the polymer (A) content in the composition is 0.2% by mass or less.
  • the viscosity when the component (B) is not contained is not relatively high in the first place, so that it can be said that the effect of the composition of the present disclosure is not sufficiently exhibited. ..
  • the upper limit of the polymer (A) content is not particularly limited as long as the effect of the composition of the present disclosure is not impaired. For example, 5% by mass or less is exemplified.
  • the upper or lower limit of the polymer (A) content range (0.3 to 5% by mass) is, for example, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 , 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3 2, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.3.1, 3.2, 3.3, 3.4, 3.5, 3.6 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, or 4. It may be 9% by mass. For example, the range may be about 0.4 to 4.5 or 0.5 to 4% by mass.
  • the component (B) is preferably contained in an amount of 2.5% by mass or more, and more preferably 3% by mass or more.
  • the upper limit of the content of the component (B) is not particularly limited as long as the effect of the present invention is not impaired. For example, 15% by mass is exemplified.
  • the upper or lower limit of the component (B) content range (2.5 to 15% by mass) is, for example, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7. , 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, or 14.5% by mass There may be.
  • the range may be about 3 to 10% by mass.
  • compositions of the present disclosure can be prepared by a known method or a method that can be very easily conceived from a known method.
  • it can be prepared by appropriately mixing the polymer (A), the component (B), and water, and if necessary, a pH adjuster and other components.
  • composition of the present disclosure is useful, for example, as a cosmetic composition.
  • composition of the present disclosure may contain a component other than the above components as long as the effect is not impaired, and may contain, for example, a component known in the cosmetics field.
  • a thickener may be contained as long as the effect is not impaired.
  • the thickener include polysaccharide-based water-soluble polymers such as hydroxyethyl cellulose and xanthan gum, carboxyvinyl polymers, and alkyl-modified carboxyvinyl polymers.
  • powder components liquid fats and oils, solid fats and oils, waxes, hydrocarbon oils, higher fatty acids, higher alcohols, ester oils, silicone oils, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants.
  • Activators, moisturizers, water-soluble polymers, film agents, UV absorbers, metal ion blockers, lower alcohols, polyhydric alcohols, sugars, amino acids, organic amines, polymer emulsions, pH adjusters, skin nutrients, vitamins , Antioxidants, antioxidant aids, fragrances and the like may be contained.
  • composition of the present disclosure is used in the field of cosmetics
  • its form is not particularly limited, but for example, medicated cream, lotion, milky lotion, beauty essence, cream, cream pack, massage cream, cleansing cream, cleansing gel, gel cream, etc.
  • Examples include facial cleansing foams, moisturizing gels, hair setting gels, sunscreens, styling gels, eyeliners, mascara, lipsticks and foundations.
  • the present disclosure also preferably includes a thickener for preparing a viscous composition containing ascorbic acid or a derivative thereof.
  • the thickener comprises the polymer (A).
  • the thickener is preferably for preparing a viscous composition containing 2.5% by mass or more of ascorbic acid or a derivative thereof.
  • all the above-mentioned contents regarding the compositions of the present disclosure may also apply to the thickener.
  • Polymer preparation 45 g (0.625 mol) of acrylic acid, Blemmer VMA70 (manufactured by Nippon Oil & Fats Co., Ltd .: 10 to 20 mass of stearyl methacrylate) in a 500 mL four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube and cooling tube. 1.35 g, pentaerythritol tetraallyl ether 0.02 g, normal 150 g of hexane and 0.081 g (0.00035 mol) of 2,2'-azobismethylisobutyrate were charged.
  • the copolymer After stirring and uniformly mixing the solution, nitrogen gas was blown into the solution to remove oxygen present in the upper space of the reaction vessel (four-necked flask), raw materials and solvent. Then, it was kept at 60 to 65 ° C. under a nitrogen atmosphere and reacted for 4 hours. After completion of the reaction, the produced slurry was heated to 90 ° C. to distill off normal hexane, and further dried under reduced pressure at 110 ° C. and 10 mmHg for 8 hours to obtain a white fine powder of alkyl-modified carboxyl group-containing water-soluble material. 43 g of the copolymer was obtained.
  • the copolymer may be referred to as polymer 1.
  • a block copolymer of 12-hydroxystearic acid and polyoxyethylene (Hypermer B246 manufactured by Croda) was charged into the reaction vessel as a nonionic surfactant. .. Then, after the temperature of the solution reached 60 ° C., it was kept at 60 to 65 ° C. for 3 hours. Then, the generated slurry is heated to 100 ° C., normal hexane is distilled off, the set temperature of the heating device is set to 115 ° C., the set pressure of the decompression device is set to 10 mmHg, and the mixture is dried for 8 hours. , 41 g of white fine particles of an alkyl-modified carboxyl group-containing copolymer was obtained.
  • the copolymer may be referred to as polymer 2.
  • the copolymer was obtained.
  • the copolymer may be referred to as polymer 3.
  • the copolymer may be referred to as polymer 4.
  • the produced slurry was heated to 90 ° C. to distill off n-hexane, and further dried under reduced pressure at 110 ° C. and 10 mmHg for 8 hours to obtain 42 g of a carboxyvinyl polymer.
  • the carboxyvinyl polymer may be referred to as polymer 6.
  • PETA represents pentaerythritol tetraallyl ether.
  • the viscosity of each of the obtained viscous compositions was measured.
  • the viscosity was measured using a BH type rotational viscometer. Assuming that the rotation speed of the spindle rotor was 20 rotations per minute, the viscosity value 1 minute after the start of rotation of the rotor was read at 25 ° C. Rotor No. 3, No. 4, No. 5, No. 6 or No. 7 was used. Before the viscosity measurement, each viscous composition was defoamed by centrifugation (2000 rpm ⁇ 10 to 20 minutes) before use.
  • ⁇ Transmittance measurement method> The transmittance of the evaluation sample was measured using a spectrophotometer (model number: UV-1850) manufactured by Shimadzu Corporation. First, the sample was placed in a cell for UV measurement (optical path length 1 cm), and defoamed by a centrifuge at 2,000 rpm for 5 minutes. When the defoaming was not completed, the same operation was performed with a centrifuge, and it was confirmed that the bubbles were completely removed from the upper part of the sample. Then, the sample was set in a spectrophotometer, and the transmittance was measured with the measurement wavelength set to 425 nm. Distilled water was calibrated so as to have a transmittance of 100%.
  • the viscosity measurement result is shown in FIG. 1, and the UV (425 nm) transmittance measurement result is shown in FIG. 2, respectively.
  • a viscous composition having a polymer concentration of 0.6% by mass or 0.8% by mass and an ascorbic acid glycoside concentration of 3% by mass was prepared in the same manner as described above, and the viscosity and UV ( When the transmittance (425 nm) was measured, the viscosity was 7650 mPa ⁇ s and the UV transmittance was 97.2 (% T) at a polymer concentration of 0.6% by mass, and the viscosity was 16000 mPa ⁇ s at a polymer concentration of 0.8% by mass. The UV transmittance was 97.3 (% T).
  • a viscous composition having a polymer concentration of 1% by mass and an ascorbic acid glycoside concentration of 7% by mass was prepared in the same manner as described above, and the viscosity was measured.
  • the product had a viscosity of 5,800 mPa ⁇ s
  • the polymer 2-containing viscous composition had a viscosity of 13,600 mPa ⁇ s.
  • a viscous composition (Example a) was prepared in the same manner as in Example 1 except that magnesium L-ascorbic acid phosphate (L-ascorbic magnesium phosphate) was used instead of the ascorbic acid glycoside.
  • magnesium L-ascorbic acid phosphate L-ascorbic magnesium phosphate
  • UV (425 nm) transmittance were measured, the viscosity was 12,600 mPa ⁇ s and the UV transmittance was 94.7 (% T).
  • the viscous composition (the former is the same as in Example 2) except that magnesium L-ascorbic acid phosphate (L-ascorbic magnesium phosphate) or sodium L-ascorbic acid was used instead of the ascorbic acid glycoside.
  • the viscosity was 16,600 mPa ⁇ s and the UV transmission rate was 96.4 (% T), and the composition using sodium L-ascorbic acid had a viscosity of 5,160 mPa ⁇ s and a UV transmission rate of 90.6 (% T). rice field.

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Abstract

Provided is a viscous composition comprising ascorbic acid or a derivative thereof, and having appropriate viscosity. More specifically, provided is the following composition. A composition comprising: (A) at least 0.3 mass% of a polymer obtained by polymerizing (i), (ii), and (iii), where (i) is 100 parts by mass of (meth)acrylic acid, (ii) is 0.01-1 parts by mass of a compound containing at least two ethylenically unsaturated groups, and (iii) is 0.5-10 parts by mass of a (meth)acrylic acid alkyl ester in which the alkyl group has a C number of 10-30; and (B) ascorbic acid or a derivative thereof.

Description

粘性組成物Viscous composition
　本開示は、粘性を有する組成物等に関する。 The present disclosure relates to a viscous composition or the like.
　アスコルビン酸は様々な用途（例えば化粧品や食品）の組成物に用いられる成分である。 Ascorbic acid is an ingredient used in compositions for various uses (for example, cosmetics and foods).
国際公開第２００７／０５５３５４号International Publication No. 2007/055354
　本発明者らは、粘性組成物にアスコルビン酸又はその誘導体を配合すると、粘度が著しく低下してしまうことを見いだした。そこで、アスコルビン酸又はその誘導体を配合したとしても粘度の低下が起こり難い粘性組成物、及び、アスコルビン酸又はその誘導体を含有しつつも適切な粘度を有する粘性組成物を提供する方法を見いだすべく、検討を行った。 The present inventors have found that when ascorbic acid or a derivative thereof is added to a viscous composition, the viscosity is significantly reduced. Therefore, in order to find a method for providing a viscous composition in which the viscosity is unlikely to decrease even if ascorbic acid or a derivative thereof is blended, and a viscous composition containing ascorbic acid or a derivative thereof and having an appropriate viscosity. Study was carried out.
　本発明者らは、特許文献１（国際公開第２００７／０５５３５４号）において開示される、アルキル変性カルボキシル基含有水溶性共重合体の中でも、特定の共重合体を特定量用いて調製した粘性組成物は、アスコルビン酸又はその誘導体を配合したとしても、粘度の低下が起こり難い可能性を見いだし、さらに検討を重ねた。 The present inventors have a viscous composition prepared by using a specific amount of a specific copolymer among the alkyl-modified carboxyl group-containing water-soluble copolymers disclosed in Patent Document 1 (International Publication No. 2007/055354). We have found that even if ascorbic acid or a derivative thereof is blended in the product, it is unlikely that the viscosity will decrease, and further studies have been conducted.
　本開示は例えば以下の項に記載の主題を包含する。
項１．
（Ａ）次の（ｉ）、（ｉｉ）、及び（ｉｉｉ）：
　　（ｉ）（メタ）アクリル酸１００質量部
　　（ｉｉ）エチレン性不飽和基を２個以上有する化合物０．０１～１質量部
　　（ｉｉｉ）アルキル基の炭素数が１０～３０である（メタ）アクリル酸アルキルエステル０．５～１０質量部
を重合して得られるポリマーを０．３質量％以上、並びに
（Ｂ）アスコルビン酸又はその誘導体
を含有する組成物。
項２．
前記（ｉｉ）が、
エチレン性不飽和基を２個以上有する化合物０．０１～０．２質量部
である、
項１に記載の組成物。
項３．
前記エチレン性不飽和基を２個以上有する化合物が、ペンタエリスリトールアリルエーテルである、項１又は２に記載の組成物。
項４．
粘度が５０００ｍＰａ・ｓ以上である、項１～３のいずれかに記載の組成物。
項５．
前記（Ｂ）を２．５質量％以上含有する、項１～４のいずれかに記載の組成物。
項６．
アスコルビン酸の誘導体が、アスコルビン酸塩、アスコルビン酸配糖体、アスコルビン酸リン酸塩、脂肪酸アスコルビル、アスコルビルエチル、アスコルビン酸－リン酸－脂肪酸、及びグリセリルオクチルアスコルビン酸からなる群より選択される少なくとも１種である、
項１～５のいずれかに記載の組成物。
項７．
前記（ｉｉ）が、
エチレン性不飽和基を２個以上有する化合物０．０１～０．２質量部
であり、
前記エチレン性不飽和基を２個以上有する化合物が、ペンタエリスリトールアリルエーテルであり、
粘度が５０００ｍＰａ・ｓ以上であり、
前記（Ｂ）を２．５質量％以上含有し、
前記（Ｂ）が、アスコルビン酸、アスコルビン酸塩、アスコルビン酸配糖体、及びアスコルビン酸リン酸塩からなる群より選択される少なくとも１種である、
項１に記載の組成物。
項８．
（Ａ）次の（ｉ）、（ｉｉ）、及び（ｉｉｉ）：
　　（ｉ）（メタ）アクリル酸１００質量部
　　（ｉｉ）エチレン性不飽和基を２個以上有する化合物０．０１～１質量部
　　（ｉｉｉ）アルキル基の炭素数が１０～３０である（メタ）アクリル酸アルキルエステル０．５～１０質量部
を重合して得られるポリマー
を含有する、
アスコルビン酸又はその誘導体を２．５質量％以上含有する粘性組成物調製用の増粘剤。 The present disclosure includes, for example, the subjects described in the following sections.
Item 1.
(A) The following (i), (ii), and (iii):
(I) 100 parts by mass of (meth) acrylic acid (ii) Compound having two or more ethylenically unsaturated groups 0.01 to 1 part by mass (iii) (meth) acrylic having an alkyl group having 10 to 30 carbon atoms A composition containing 0.3% by mass or more of a polymer obtained by polymerizing 0.5 to 10 parts by mass of an acid alkyl ester, and (B) ascorbic acid or a derivative thereof.
Item 2.
The above (ii) is
A compound having two or more ethylenically unsaturated groups, 0.01 to 0.2 parts by mass.
Item 2. The composition according to Item 1.
Item 3.
Item 2. The composition according to Item 1 or 2, wherein the compound having two or more ethylenically unsaturated groups is pentaerythritol allyl ether.
Item 4.
Item 2. The composition according to any one of Items 1 to 3, which has a viscosity of 5000 mPa · s or more.
Item 5.
Item 2. The composition according to any one of Items 1 to 4, which contains 2.5% by mass or more of the above (B).
Item 6.
At least one ascorbic acid derivative selected from the group consisting of ascorbic acid salt, ascorbic acid glycoside, ascorbic acid phosphate, fatty acid ascorbyl, ascorbyl ethyl, ascorbic acid-phosphate-fatty acid, and glyceryl octyl ascorbic acid. Seed,
Item 8. The composition according to any one of Items 1 to 5.
Item 7.
The above (ii) is
The compound having two or more ethylenically unsaturated groups is 0.01 to 0.2 parts by mass.
The compound having two or more ethylenically unsaturated groups is pentaerythritol allyl ether.
The viscosity is 5000 mPa · s or more,
Containing 2.5% by mass or more of the above (B),
(B) is at least one selected from the group consisting of ascorbic acid, ascorbic acid salt, ascorbic acid glycoside, and ascorbic acid phosphate.
Item 2. The composition according to Item 1.
Item 8.
(A) The following (i), (ii), and (iii):
(I) 100 parts by mass of (meth) acrylic acid (ii) Compound having two or more ethylenically unsaturated groups 0.01 to 1 part by mass (iii) (meth) acrylic having an alkyl group having 10 to 30 carbon atoms Contains a polymer obtained by polymerizing 0.5 to 10 parts by mass of an acid alkyl ester.
A thickener for preparing a viscous composition containing 2.5% by mass or more of ascorbic acid or a derivative thereof.
　アスコルビン酸又はその誘導体を含有しつつも適切な粘度を有する組成物が提供される。 A composition containing ascorbic acid or a derivative thereof and having an appropriate viscosity is provided.
各種ポリマーおよびアスコルビン酸誘導体を含有する粘性組成物の粘度測定結果を示す。The viscosity measurement result of the viscous composition containing various polymers and ascorbic acid derivatives is shown. 各種ポリマーおよびアスコルビン酸誘導体を含有する粘性組成物のＵＶ透過率測定結果を示す。The UV transmittance measurement result of the viscous composition containing various polymers and ascorbic acid derivatives is shown.
　以下、本開示に包含される各実施形態について、さらに詳細に説明する。本開示は、特定のポリマー及びアスコルビン酸又はその誘導体を含有する組成物、及びその用途、並びにその製造方法等を好ましく包含するが、これらに限定されるわけではなく、本開示は本明細書に開示され当業者が認識できる全てを包含する。 Hereinafter, each embodiment included in the present disclosure will be described in more detail. The present disclosure preferably includes, but is not limited to, a composition containing a specific polymer and ascorbic acid or a derivative thereof, its use, a method for producing the same, and the like, and the present disclosure is described herein. Includes everything disclosed and recognizable to those skilled in the art.
　本開示に包含される組成物は、（Ａ）次の（ｉ）、（ｉｉ）、及び（ｉｉｉ）を重合して得られるポリマー（「ポリマー（Ａ）」ということがある）、並びに（Ｂ）アスコルビン酸又はその誘導体（「成分（Ｂ）」ということがある）を含有する。 The compositions included in the present disclosure include (A) a polymer obtained by polymerizing the following (i), (ii), and (iii) (sometimes referred to as "polymer (A)"), and (B. ) Contains ascorbic acid or a derivative thereof (sometimes referred to as "component (B)").
　（ｉ）（メタ）アクリル酸１００質量部
　（ｉｉ）エチレン性不飽和基を２個以上有する化合物０．０１～１質量部
　（ｉｉｉ）アルキル基の炭素数が１０～３０である（メタ）アクリル酸アルキルエステル０．５～１０質量部 (I) 100 parts by mass of (meth) acrylic acid (ii) Compound having two or more ethylenically unsaturated groups 0.01 to 1 part by mass (iii) (meth) acrylic having an alkyl group having 10 to 30 carbon atoms Acid alkyl ester 0.5-10 parts by mass
　本明細書において、「（メタ）アクリル」とは、アクリル及び／又はメタクリルを意味する。（メタ）アクリル酸として、アクリル酸及びメタクリル酸のいずれか一方を単独で使用してもよく、またこれらの双方を組み合わせて使用してもよい。 In the present specification, "(meth) acrylic" means acrylic and / or methacryl. As the (meth) acrylic acid, either one of acrylic acid and methacrylic acid may be used alone, or both of them may be used in combination.
　アルキル基の炭素数が１０～３０（１０、１１、１２、１３、１４、１５、１６、１７、１８、１９、２０、２１、２２、２３、２４、２５、２６、２７、２８、２９、又は３０）である（メタ）アクリル酸アルキルエステルとは、（メタ）アクリル酸と、アルキル基の炭素数が１０～３０である高級アルコールとのエステルである。当該アルキル基の炭素数は、例えば１２～３０、１４～２８、１６～２６、又は１８～２４であることがより好ましい。このような（メタ）アクリル酸アルキルエステルとしては、特に制限されないが、例えば、（メタ）アクリル酸とステアリルアルコールとのエステル、（メタ）アクリル酸とエイコサノールとのエステル、（メタ）アクリル酸とベヘニルアルコールとのエステル、及び（メタ）アクリル酸とテトラコサノールとのエステル等が挙げられる。これらの（メタ）アクリル酸アルキルエステルの中でも、好ましくは、メタクリル酸ステアリル、メタクリル酸エイコサニル、メタクリル酸ベヘニル、及びメタクリル酸テトラコサニルが挙げられる。これらの（メタ）アクリル酸アルキルエステルは、それぞれ単独で使用してもよく、また２種以上を組み合わせて用いてもよい。また、このような（メタ）アクリル酸アルキルエステルとしては、例えば、日本油脂株式会社製の商品名ブレンマーＶＭＡ７０、ブレンマーＳＭＡ等の市販品を用いてもよい。 Alkyl groups have 10 to 30 carbon atoms (10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, Alternatively, the (meth) acrylic acid alkyl ester of 30) is an ester of (meth) acrylic acid and a higher alcohol having an alkyl group having 10 to 30 carbon atoms. The alkyl group preferably has, for example, 12 to 30, 14 to 28, 16 to 26, or 18 to 24 carbon atoms. Such (meth) acrylic acid alkyl ester is not particularly limited, and is, for example, an ester of (meth) acrylic acid and stearyl alcohol, an ester of (meth) acrylic acid and eicosanol, and (meth) acrylic acid and behenyl alcohol. And an ester of (meth) acrylic acid and tetracosanol. Among these (meth) acrylic acid alkyl esters, preferably stearyl methacrylate, eicosanyl methacrylate, behenyl methacrylate, and tetracosanyl methacrylate can be mentioned. These (meth) acrylic acid alkyl esters may be used alone or in combination of two or more. Further, as such a (meth) acrylic acid alkyl ester, for example, commercially available products such as NOF Corporation's trade name Blemmer VMA70 and Brenmer SMA may be used.
　前記（メタ）アクリル酸アルキルエステルの使用量は、（メタ）アクリル酸１００質量部に対して、０．５～１０質量部であり、好ましくは０．５～７．５質量部、０．５～５質量部、又は１～５質量部であり、より好ましくは１～３質量部である。 The amount of the (meth) acrylic acid alkyl ester used is 0.5 to 10 parts by mass, preferably 0.5 to 7.5 parts by mass, 0.5 parts by mass with respect to 100 parts by mass of (meth) acrylic acid. It is ~ 5 parts by mass, or 1 to 5 parts by mass, and more preferably 1 to 3 parts by mass.
　また、前記エチレン性不飽和基を２個以上有する化合物としては、特に限定されないが、例えば、エチレングリコール、プロピレングリコール、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、グリセリン、ポリグリセリン、トリメチロールプロパン、ペンタエリスリトール、サッカロース、ソルビトール等のポリオールの２置換以上のアクリル酸エステル類；前記ポリオールの２置換以上のアリルエーテル類；フタル酸ジアリル、リン酸トリアリル、メタクリル酸アリル、テトラアリルオキシエタン、トリアリルシアヌレート、アジピン酸ジビニル、クロトン酸ビニル、１，５－ヘキサジエン、ジビニルベンゼン、ポリアリルサッカロース等が挙げられる。これらのエチレン性不飽和基を２個以上有する化合物の中でも、好ましくは、ショ糖アリルエーテル、ペンタエリスリトールアリルエーテル（中でもペンタエリスリトールトリアリルエーテル、ペンタエリスリトールテトラアリルエーテルが好ましい）、テトラアリルオキシエタン、リン酸トリアリル、及びポリアリルサッカロースが挙げられ、中でもショ糖アリルエーテル、ペンタエリスリトールアリルエーテルがより好ましく、ペンタエリスリトールアリルエーテルが特に好ましい。これらのエチレン性不飽和基を２個以上有する化合物は、それぞれ単独で使用してもよく、また２種以上を組み合わせて用いてもよい。 The compound having two or more ethylenically unsaturated groups is not particularly limited, but for example, ethylene glycol, propylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, polyglycerin, trimethylolpropane, penta. Acrylic acid esters with two or more substitutions of polyols such as erythritol, saccharose, and sorbitol; allyl ethers with two or more substitutions of the polyols; diallyl phthalate, triallyl phosphate, allyl methacrylate, tetraallyloxyethane, triallyl cyanurate. , Divinyl adipate, vinyl crotonic acid, 1,5-hexadiene, divinylbenzene, polyallyl saccharose and the like. Among these compounds having two or more ethylenically unsaturated groups, sucrose allyl ether, pentaerythritol allyl ether (particularly pentaerythritol triallyl ether and pentaerythritol tetraallyl ether are preferable), tetraallyl oxyethane, and the like. Examples thereof include triallyl phosphate and polyallyl saccharose, among which sucrose allyl ether and pentaerythritol allyl ether are more preferable, and pentaerythritol allyl ether is particularly preferable. These compounds having two or more ethylenically unsaturated groups may be used alone or in combination of two or more.
　前記エチレン性不飽和基を２個以上有する化合物の使用量は、（メタ）アクリル酸１００質量部に対して、０．０１～１質量部である。当該範囲の上限または下限は、例えば、０．０２、０．０３、０．０４、０．０５、０．０６、０．０７、０．０８、０．０９、０．１、０．１５、０．２、０．２５、０．３、０．３５、０．４、０．４５、０．５、０．５５、０．６、０．６５、０．７、０．７５、０．８、０．８５、０．９、又は０．９５質量部であってもよい。例えば、当該範囲は０．０２～０．８質量部程度であってもよい。 The amount of the compound having two or more ethylenically unsaturated groups used is 0.01 to 1 part by mass with respect to 100 parts by mass of (meth) acrylic acid. The upper or lower limit of the range is, for example, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0. It may be 8, 0.85, 0.9, or 0.95 parts by mass. For example, the range may be about 0.02 to 0.8 parts by mass.
　特に限定されるわけではないが、ポリマー（Ａ）におけるエチレン性不飽和基を２個以上有する化合物使用量が比較的少ない方が、本開示の組成物の透明性が改善される効果が奏されるため、好ましい。特に、本開示の組成物を化粧品分野等に利用する場合、透明性は見た目の問題であって化粧品の効果に直接影響を与える特徴ではないものの、一定数の需要者は組成物が透明であることを好むと考えられるからである。この観点からは、エチレン性不飽和基を２個以上有する化合物の使用量は、（メタ）アクリル酸１００質量部に対して、例えば０．０１～０．２質量部程度であることが好ましい。 Although not particularly limited, when the amount of the compound having two or more ethylenically unsaturated groups in the polymer (A) used is relatively small, the effect of improving the transparency of the composition of the present disclosure is exhibited. Therefore, it is preferable. In particular, when the composition of the present disclosure is used in the field of cosmetics, etc., transparency is a problem of appearance and is not a feature that directly affects the effect of cosmetics, but the composition is transparent for a certain number of consumers. This is because they are considered to like it. From this viewpoint, the amount of the compound having two or more ethylenically unsaturated groups is preferably about 0.01 to 0.2 parts by mass with respect to 100 parts by mass of (meth) acrylic acid.
　本開示の共重合体の製造において、（ｉ）と（ｉｉ）と（ｉｉｉ）と重合する方法としては、特に限定されず、例えば、これらをラジカル重合開始剤の存在下に重合溶媒中で重合させる方法等が挙げられる。 In the production of the copolymers of the present disclosure, the method of polymerizing (i), (ii) and (iii) is not particularly limited, and for example, these are polymerized in a polymerization solvent in the presence of a radical polymerization initiator. There is a method of making it.
　前記ラジカル重合開始剤としては、特に限定されず、例えば、α，α'－アゾビスイソブチロニトリル、２，２'－アゾビス－２，４－ジメチルバレロニトリル、２，２'－アゾビスメチルイソブチレート、２，２’－アゾビス（２－メチルプロピオンアミジン）２塩酸塩、過酸化ベンゾイル、ラウロイルパーオキサイド、クメンハイドロパーオキサイド、第三級ブチルハイドロパーオキサイド等が挙げられる。これらのラジカル重合開始剤は、それぞれ単独で使用してもよく、また２種以上を組み合わせて用いてもよい。 The radical polymerization initiator is not particularly limited, and is, for example, α, α'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobismethyl. Examples thereof include isobutyrate, 2,2'-azobis (2-methylpropionamidine) dihydrochloride, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tertiary butyl hydroperoxide and the like. These radical polymerization initiators may be used alone or in combination of two or more.
　前記ラジカル重合開始剤の使用量としては、特に制限されないが、例えば、（メタ）アクリル酸１００質量部に対して、０．０１～０．４５質量部が好ましく、０．０１～０．３５質量部がより好ましい。 The amount of the radical polymerization initiator used is not particularly limited, but is preferably 0.01 to 0.45 parts by mass and 0.01 to 0.35 parts by mass with respect to 100 parts by mass of (meth) acrylic acid, for example. The portion is more preferable.
　重合方法としては、例えば沈殿重合や逆相懸濁重合を好ましく用いることができる。またさらに、逆相懸濁重合を、ポリオキシエチレン鎖を有するノニオン性界面活性剤が配合された重合溶媒中で行ってもよい。 As the polymerization method, for example, precipitation polymerization or reverse phase suspension polymerization can be preferably used. Furthermore, reverse phase suspension polymerization may be carried out in a polymerization solvent containing a nonionic surfactant having a polyoxyethylene chain.
　当該ポリオキシエチレン鎖を有するノニオン性界面活性剤としては、例えば多価アルコール脂肪酸エステルエチレンオキサイド付加物、ヒドロキシ脂肪酸とエチレンオキサイドとのブロック共重合体、及びポリオキシエチレンヒマシ油等が好ましく挙げられる。 Preferred examples of the nonionic surfactant having the polyoxyethylene chain include polyhydric alcohol fatty acid ester ethylene oxide adduct, block copolymer of hydroxy fatty acid and ethylene oxide, and polyoxyethylene castor oil.
　多価アルコール脂肪酸エステルエチレンオキサイド付加物としては、ポリオキシエチレン硬化ヒマシ油と多価アルコール脂肪酸とのエステル化合物が好ましく挙げられる。また、ここでの多価アルコール脂肪酸としては、炭素数１４～２４（１４、１５、１６、１７、１８、１９、２０、２１、２２、２３、又は２４）の飽和若しくは不飽和の多価（特に２価）アルコール脂肪酸が好ましく、より具体的には、イソパルミチン酸、イソステアリン酸、イソオレイン酸等が好ましく挙げられる。ポリオキシエチレン硬化ヒマシ油と多価アルコール脂肪酸とのエステル化合物における、ポリオキシエチレンの酸化エチレン平均付加モル数としては、特に制限はされないが例えば２０～１００程度、又は３０～７０程度が挙げられる。ポリオキシエチレン硬化ヒマシ油と多価アルコール脂肪酸とのエステル化合物として特に好ましいものとして、イソステアリン酸ポリオキシエチレン硬化ヒマシ油が挙げられる。 As the polyhydric alcohol fatty acid ester ethylene oxide adduct, an ester compound of polyoxyethylene hydrogenated castor oil and polyhydric alcohol fatty acid is preferably mentioned. Further, the polyhydric alcohol fatty acid here is a saturated or unsaturated polyvalent (14, 15, 16, 17, 18, 19, 20, 21, 22, 23, or 24) having 14 to 24 carbon atoms (14, 15, 16, 17, 18, 19, 20, 21, 22, 23, or 24). In particular, divalent) alcohol fatty acids are preferable, and more specifically, isopalmitic acid, isostearic acid, isooleic acid and the like are preferably mentioned. The average number of moles of ethylene oxide added to polyoxyethylene in the ester compound of the polyoxyethylene hydrogenated castor oil and the polyhydric alcohol fatty acid is not particularly limited, and examples thereof include about 20 to 100 or about 30 to 70. Particularly preferable as an ester compound of polyoxyethylene hydrogenated castor oil and polyhydric alcohol fatty acid is polyoxyethylene hydrogenated castor oil isostearate.
　ポリオキシエチレンヒマシ油としては、酸化エチレンの付加モル数が２～１０程度のものが好ましく、２～５程度のものがさらに好ましい。 The polyoxyethylene castor oil preferably has an addition mole number of ethylene oxide of about 2 to 10, and more preferably about 2 to 5.
　ヒドロキシ脂肪酸とエチレンオキサイドとのブロック共重合体とは、言い換えれば、ポリヒドロキシ脂肪酸とポリオキシエチレンとからなる共重合体とも言える。ポリヒドロキシ脂肪酸の脂肪酸としては、炭素数１４～２２程度の脂肪酸が好ましく、ミリスチン酸、パルミチン酸、ステアリン酸等が好ましく挙げられ、ヒドロキシ脂肪酸としては、ヒドロキシミリスチン酸、ヒドロキシパルミチン酸、ヒドロキシステアリン酸等が好ましく挙げられ、特にヒドロキシステアリン酸が好ましい。ヒドロキシステアリン酸としては、１２－ヒドロキシステアリン酸が特に好ましい。ポリヒドロキシ脂肪酸としては、ポリヒドロキシステアリン酸が特に好ましい。ヒドロキシ脂肪酸とエチレンオキサイドとのブロック共重合体としては、１２－ヒドロキシステアリン酸とエチレンオキサイドとのブロック共重合体が特に好ましい。 In other words, the block copolymer of hydroxy fatty acid and ethylene oxide can be said to be a copolymer composed of polyhydroxy fatty acid and polyoxyethylene. The fatty acid of the polyhydroxy fatty acid is preferably a fatty acid having about 14 to 22 carbon atoms, preferably myristic acid, palmitic acid, stearic acid and the like, and examples of the hydroxy fatty acid are hydroxymyristic acid, hydroxypalmitic acid, hydroxystearic acid and the like. Is preferable, and hydroxystearic acid is particularly preferable. As the hydroxystearic acid, 12-hydroxystearic acid is particularly preferable. As the polyhydroxy fatty acid, polyhydroxystearic acid is particularly preferable. As the block copolymer of hydroxy fatty acid and ethylene oxide, a block copolymer of 12-hydroxystearic acid and ethylene oxide is particularly preferable.
　当該ポリオキシエチレン鎖を有するノニオン性界面活性剤は、１種単独で又は２種以上を組み合わせて用いることができる。 The nonionic surfactant having the polyoxyethylene chain can be used alone or in combination of two or more.
　当該ポリオキシエチレン鎖を有するノニオン性界面活性剤の使用量は、（ｉ）（メタ）アクリル酸１００質量部に対して、０．５～１０質量部程度が好ましい。当該質量部範囲の下限は、例えば０．７５、１．０、１．２５、又は１．５程度であってもよく、また、当該質量部範囲の上限は、例えば９．５、９、８．５、８、７．５、７、６．５、６、又は５．５程度であってもよい。例えば、１～７．５質量部程度がより好ましい。 The amount of the nonionic surfactant having the polyoxyethylene chain used is preferably about 0.5 to 10 parts by mass with respect to 100 parts by mass of (i) (meth) acrylic acid. The lower limit of the mass range may be, for example, about 0.75, 1.0, 1.25, or 1.5, and the upper limit of the mass range may be, for example, 9.5, 9, 8. It may be about 5.5, 8, 7.5, 7, 6.5, 6, or 5.5. For example, about 1 to 7.5 parts by mass is more preferable.
　また、前記重合溶媒としては、特に限定されないが、（メタ）アクリル酸、前記（メタ）アクリル酸アルキルエステル、及びエチレン性不飽和基を２個以上有する化合物を溶解し、かつ得られるポリマー（Ａ）を溶解しない溶媒であることが好ましい。このような重合溶媒の具体例としては、ノルマルペンタン、ノルマルヘキサン、ノルマルヘプタン、ノルマルオクタン、イソオクタン、シクロペンタン、メチルシクロペンタン、シクロヘキサン、メチルシクロヘキサン、ベンゼン、トルエン、キシレン、クロロベンゼン、エチレンジクロライド、酢酸エチル、酢酸イソプロピル、エチルメチルケトン、イソブチルメチルケトン等が挙げられる。これらの重合溶媒の中でも、品質が安定しており入手が容易であるという観点から、好ましくは、エチレンジクロライド、ノルマルヘキサン、ノルマルヘプタン、酢酸エチルが挙げられる。これらの重合溶媒は、それぞれ単独で使用してもよく、また２種以上を組み合わせて用いてもよい。 The polymerization solvent is not particularly limited, but is a polymer (A) obtained by dissolving (meth) acrylic acid, the (meth) acrylic acid alkyl ester, and a compound having two or more ethylenically unsaturated groups. ) Is preferably a solvent that does not dissolve. Specific examples of such a polymerization solvent include normal pentane, normal hexane, normal heptane, normal octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, chlorobenzene, ethylene dichloride, ethyl acetate. , Isopropyl acetate, ethyl methyl ketone, isobutyl methyl ketone and the like. Among these polymerization solvents, ethylene dichloride, normal hexane, normal heptane, and ethyl acetate are preferable from the viewpoint of stable quality and easy availability. These polymerization solvents may be used alone or in combination of two or more.
　前記重合溶媒の使用量としては、特に制限されないが、例えば、（メタ）アクリル酸１００質量部に対して、２００～１００００質量部が好ましく、３００～２０００質量部がより好ましい。重合溶媒を上記範囲内で使用することにより、重合反応が進行しても、アルキル変性カルボキシル基含有水溶性共重合体が凝集するのを好ましく抑制して均一に撹拌させ、且つ重合反応をより効率的に進行させることが可能になる。 The amount of the polymerization solvent used is not particularly limited, but for example, it is preferably 200 to 10000 parts by mass and more preferably 300 to 2000 parts by mass with respect to 100 parts by mass of (meth) acrylic acid. By using the polymerization solvent within the above range, even if the polymerization reaction proceeds, the alkyl-modified carboxyl group-containing water-soluble copolymer is preferably suppressed from agglomeration and uniformly stirred, and the polymerization reaction is made more efficient. It becomes possible to proceed in a targeted manner.
　また、上記重合反応を行う際の雰囲気については、重合反応が可能であることを限度として特に制限されないが、例えば、窒素ガス、アルゴンガス等の不活性ガス雰囲気が挙げられる。 The atmosphere when the polymerization reaction is carried out is not particularly limited as long as the polymerization reaction is possible, and examples thereof include an inert gas atmosphere such as nitrogen gas and argon gas.
　上記重合反応を行う際の反応温度は、重合反応が可能であることを限度として特に制限されないが、例えば、５０～９０℃が好ましく、５５～７５℃がより好ましい。このような反応温度で重合反応を行うことにより、反応溶液の粘度上昇を好ましく抑制し、反応制御をより容易にすることができ、更に得られるポリマー（Ａ）の嵩密度を好ましく制御することができる。 The reaction temperature at the time of carrying out the above polymerization reaction is not particularly limited as long as the polymerization reaction is possible, but for example, it is preferably 50 to 90 ° C, more preferably 55 to 75 ° C. By carrying out the polymerization reaction at such a reaction temperature, it is possible to preferably suppress an increase in the viscosity of the reaction solution, facilitate reaction control, and preferably control the bulk density of the obtained polymer (A). can.
　上記重合反応を行う際の反応時間は、反応温度によって異なるので一概には決定することはできないが、通常、２～１０時間である。 The reaction time for carrying out the above polymerization reaction varies depending on the reaction temperature and cannot be unconditionally determined, but is usually 2 to 10 hours.
　反応終了後は、例えば、反応溶液を８０～１３０℃に加熱し、重合溶媒を除去することにより白色微粉末のポリマー（Ａ）を単離することができる。 After completion of the reaction, for example, the reaction solution can be heated to 80 to 130 ° C. to remove the polymerization solvent, whereby the white fine powder polymer (A) can be isolated.
　アスコルビン酸の誘導体としては、例えばアスコルビン酸塩、アスコルビン酸配糖体、アスコルビン酸リン酸塩、脂肪酸アスコルビル（脂肪酸とアスコルビン酸とのエステル）、アスコルビルエチル、アスコルビン酸－リン酸－脂肪酸、グリセリルオクチルアスコルビン酸等が挙げられる。アスコルビン酸塩としては、アスコルビン酸ナトリウム、アスコルビン酸カルシウムが挙げられる。アスコルビン酸配糖体としては、アスコルビン酸グルコシドが好ましく挙げられ、より具体的には、アスコルビン酸２－グルコシド、アスコルビン酸６－グルコシド等が挙げられる。アスコルビン酸リン酸塩としては、例えばアスコルビン酸リン酸ナトリウムやアスコルビン酸リン酸マグネシウムが挙げられる。脂肪酸アスコルビルとしては、例えばパルミチン酸アスコルビル、ステアリン酸アスコルビル、イソパルミチン酸アスコルビル等が挙げられる。アスコルビン酸－リン酸－脂肪酸としては、例えばアスコルビン酸－２リン酸－６パルミチン酸等が挙げられる。アスコルビン酸又はその誘導体は、１種単独で又は２種以上を組み合わせて用いることができる。特に限定はされないが、アスコルビン酸又はその誘導体としては、アスコルビン酸又はその配糖体が好ましい。 Derivatives of ascorbic acid include, for example, ascorbate, ascorbic acid glycoside, ascorbic acid phosphate, fatty acid ascorbyl (ester of fatty acid and ascorbic acid), ascorbyl ethyl, ascorbic acid-phosphate-fatty acid, glyceryl octyl ascorbin. Acids and the like can be mentioned. Examples of ascorbic acid salt include sodium ascorbate and calcium ascorbate. Ascorbic acid glycosides are preferably ascorbic acid glucosides, and more specifically, ascorbic acid 2-glucosides, ascorbic acid 6-glucosides and the like can be mentioned. Examples of the ascorbate phosphate include sodium ascorbate phosphate and magnesium ascorbate phosphate. Examples of the fatty acid ascorbyl include ascorbyl palmitate, ascorbyl stearate, and ascorbyl isopalmitate. Examples of the ascorbic acid-phosphoric acid-fatty acid include ascorbic acid-2 phosphoric acid-6 palmitic acid and the like. Ascorbic acid or a derivative thereof can be used alone or in combination of two or more. Although not particularly limited, ascorbic acid or a glycoside thereof is preferable as ascorbic acid or a derivative thereof.
　なお、アクリル酸及び／又はメタクリル酸のカルボキシル基をアルカリにより中和することにより、ポリマー（Ａ）の中和度を容易に調整することができる。ここでの中和度とは、アクリル酸及び／又はメタクリル酸のカルボキシル基の総モル数に対する中和された基のモル数の割合を言う。中和に用いられるアルカリとしては、例えば水酸化ナトリウム、水酸化カリウム、トリエタノールアミン、ジイソプロピルアミン、等が挙げられる。中和の方法としては特に限定されず、例えば、予めアクリル酸及び／又はメタクリル酸を中和する方法、重合により得られたポリマーを中和する方法等が挙げられる。 The degree of neutralization of the polymer (A) can be easily adjusted by neutralizing the carboxyl group of acrylic acid and / or methacrylic acid with an alkali. The degree of neutralization here refers to the ratio of the number of moles of neutralized groups to the total number of moles of carboxyl groups of acrylic acid and / or methacrylic acid. Examples of the alkali used for neutralization include sodium hydroxide, potassium hydroxide, triethanolamine, diisopropylamine and the like. The neutralization method is not particularly limited, and examples thereof include a method of neutralizing acrylic acid and / or methacrylic acid in advance, a method of neutralizing a polymer obtained by polymerization, and the like.
　特に制限されるわけではないが、ポリマー（Ａ）の中和度は、例えば０～８０％が好ましく、１０～６０％がより好ましく、２０～５０％がさらに好ましい。 Although not particularly limited, the degree of neutralization of the polymer (A) is, for example, preferably 0 to 80%, more preferably 10 to 60%, and even more preferably 20 to 50%.
　本開示の組成物にはさらに水が含まれることが好ましい。含まれる水は、特に制限されず、例えば水道水、蒸留水、イオン交換水等を用いることができる。 It is preferable that the composition of the present disclosure further contains water. The water contained is not particularly limited, and for example, tap water, distilled water, ion-exchanged water, or the like can be used.
　本開示の組成物は、必要に応じて更にｐＨ調整剤を含んでいてもよい。ｐＨ調整剤は、好ましくは組成物ｐＨを中性付近に調製するために用いることができる。本開示の組成物は、例えばｐＨが６～８程度であることが好ましい。当該ｐＨ範囲の上限又は下限は６．１、６．２、６．３、６．４、６．５、６．６、６．７、６．８、６．９、７、７．１、７．２、７．３、７．４、７．５、７．６、７．７、７．８、又は７．９であってもよい。例えば当該ｐＨ範囲は６．５～７程度であってもよい。 The composition of the present disclosure may further contain a pH adjuster, if necessary. A pH regulator can preferably be used to adjust the pH of the composition to near neutral. The composition of the present disclosure preferably has a pH of, for example, about 6 to 8. The upper or lower limit of the pH range is 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, It may be 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, or 7.9. For example, the pH range may be about 6.5 to 7.
　ｐＨ調整剤としては、公知のｐＨ調整剤を用いることができ、化粧品分野又は食品分野において公知のｐＨ調整剤が好ましい。例えば、水酸化ナトリウム、水酸化カリウム等を挙げることができる。 As the pH adjuster, a known pH adjuster can be used, and a pH adjuster known in the cosmetics field or the food field is preferable. For example, sodium hydroxide, potassium hydroxide and the like can be mentioned.
　本開示の組成物の粘度は、好ましくは５０００ｍＰａ・ｓ以上であり、例えば５０００～５００００ｍＰａ・ｓ程度がより好ましい。当該範囲の上限又は下限は、例えば、５５００、６０００、６５００、７０００、７５００、８０００、８５００、９０００、９５００、１００００、１１０００、１２０００、１３０００、１４０００、１５０００、１６０００、１７０００、１８０００、１９０００、２００００、２１０００、２２０００、２３０００、２４０００、２５０００、２６０００、２７０００、２８０００、２９０００、３００００、３１０００、３２０００、３３０００、３４０００、３５０００、３６０００、３７０００、３８０００、３９０００、４００００、４１０００、４２０００、４３０００、４４０００、４５０００、４６０００、４７０００、４８０００、又は４９０００ｍＰａ・ｓであってもよい。例えば、当該範囲は、５５００～４００００ｍＰａ・ｓ程度又は６０００～３００００ｍＰａ・ｓ程度であってもよい。粘度は、ＢＨ型回転粘度計を用いて測定される。具体的には、スピンドルローターの回転速度を毎分２０回転として、２５℃において、ローターの回転を開始してから１分後の粘度の値を読み取ることで測定される。なお、測定に使用するローターは、目安として、２０００ｍＰａ・ｓ未満の場合はローターＮｏ．３、２０００ｍＰａ・ｓ以上５０００ｍＰａ・ｓ未満の場合はローターＮｏ．４、５０００ｍＰａ・ｓ以上１５０００ｍＰａ・ｓ未満の場合はローターＮｏ．５、１５０００ｍＰａ・ｓ以上４００００ｍＰａ・ｓ未満の場合はローターＮｏ．６、４００００ｍＰａ・ｓ以上の場合はローターＮｏ．７である。また、必要に応じて、当該粘度測定の前に、各粘性組成物を遠心する（例えば２０００ｒｐｍ×１０～２０分）ことで脱泡してから用いることもできる。 The viscosity of the composition of the present disclosure is preferably 5000 mPa · s or more, and more preferably about 5000 to 50,000 mPa · s, for example. The upper or lower limit of the range is, for example, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, 21000, 22000, 23000, 24000, 25000, 26000, 27000, 28000, 29000, 30000, 31000, 32000, 33000, 34000, 35000, 36000, 37000, 38000, 39000, 40000, 41000, 42000, 43000, 44000, 45000, It may be 46000, 47000, 48000, or 49000 mPa · s. For example, the range may be about 5500 to 40,000 mPa · s or about 6000 to 30000 mPa · s. Viscosity is measured using a BH type rotational viscometer. Specifically, it is measured by reading the viscosity value 1 minute after the start of rotation of the rotor at 25 ° C., assuming that the rotation speed of the spindle rotor is 20 rotations per minute. As a guide, if the rotor used for measurement is less than 2000 mPa · s, the rotor No. In the case of 3, 2000 mPa · s or more and less than 5000 mPa · s, the rotor No. If it is 45,000 mPa · s or more and less than 15,000 mPa · s, the rotor No. In the case of 5, 15,000 mPa · s or more and less than 40,000 mPa · s, the rotor No. In the case of 6, 40,000 mPa · s or more, the rotor No. 7. Further, if necessary, before the viscosity measurement, each viscous composition can be used after defoaming by centrifuging (for example, 2000 rpm × 10 to 20 minutes).
　本開示の組成物において、ポリマー（Ａ）は０．３質量％以上含有されることが好ましく、０．４又は０．５質量％以上含有されることがより好ましい。また、本開示の組成物は、上述したように、（Ｂ）成分を含有するにもかかわらず、（Ｂ）成分を含有しない場合と比べて粘度が低下し難いという特徴を有するところ、（Ｂ）成分を含有しない場合における粘度がそもそも比較的高くない場合には、（Ｂ）成分を配合したとしても粘度低下幅は小さいので、本開示の組成物の効果が十分に奏されないという見方もできる。この観点からすると、組成物においてポリマー（Ａ）含有量が０．２質量％以下であることは好ましくない。０．２質量％以下の含有量であると、（Ｂ）成分を含有しない場合における粘度がそもそも比較的高くないため、本開示の組成物の効果が十分に奏されないということができるからである。 In the composition of the present disclosure, the polymer (A) is preferably contained in an amount of 0.3% by mass or more, more preferably 0.4 or 0.5% by mass or more. Further, as described above, the composition of the present disclosure has a characteristic that the viscosity is less likely to decrease as compared with the case where the component (B) is not contained, although the composition contains the component (B). ) When the viscosity is not relatively high when the component (B) is not contained, the amount of decrease in viscosity is small even if the component (B) is blended, so that it can be considered that the effect of the composition of the present disclosure is not sufficiently exhibited. .. From this point of view, it is not preferable that the polymer (A) content in the composition is 0.2% by mass or less. When the content is 0.2% by mass or less, the viscosity when the component (B) is not contained is not relatively high in the first place, so that it can be said that the effect of the composition of the present disclosure is not sufficiently exhibited. ..
　本開示の組成物の効果を損なわない範囲であれば、ポリマー（Ａ）含有量上限は特に制限されない。例えば、５質量％以下が例示される。当該ポリマー（Ａ）含有量範囲（０．３～５質量％）の上限又は下限は、例えば、０．４、０．５、０．６、０．７、０．８、０．９、１、１．１、１．２、１．３、１．４、１．５、１．６、１．７、１．８、１．９、２、２．１、２．２、２．３、２．４、２．５、２．６、２．７、２．８、２．９、３．３．１、３．２、３．３、３．４、３．５、３．６、３．７、３．８、３．９、４、４．１、４．２、４．３、４．４、４．５、４．６、４．７、４．８、又は４．９質量％であってもよい。例えば、当該範囲は０．４～４．５又は０．５～４質量％程度であってもよい。 The upper limit of the polymer (A) content is not particularly limited as long as the effect of the composition of the present disclosure is not impaired. For example, 5% by mass or less is exemplified. The upper or lower limit of the polymer (A) content range (0.3 to 5% by mass) is, for example, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 , 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3 2, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.3.1, 3.2, 3.3, 3.4, 3.5, 3.6 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, or 4. It may be 9% by mass. For example, the range may be about 0.4 to 4.5 or 0.5 to 4% by mass.
　本開示の組成物において、成分（Ｂ）は２．５質量％以上含有されることが好ましく、３質量％以上含有されることがより好ましい。また、成分（Ｂ）の含有量上限は、本発明の効果が損なわれない範囲であれば、特に制限されない。例えば、１５質量％が例示される。当該成分（Ｂ）含有量範囲（２．５～１５質量％）の上限又は下限は、例えば、３、３．５、４、４．５、５、５．５、６、６．５、７、７．５、８、８．５、９、９．５、１０、１０．５、１１、１１．５、１２、１２．５、１３、１３．５、１４、又は１４．５質量％であってもよい。例えば、当該範囲は３～１０質量％程度であってもよい。 In the composition of the present disclosure, the component (B) is preferably contained in an amount of 2.5% by mass or more, and more preferably 3% by mass or more. Further, the upper limit of the content of the component (B) is not particularly limited as long as the effect of the present invention is not impaired. For example, 15% by mass is exemplified. The upper or lower limit of the component (B) content range (2.5 to 15% by mass) is, for example, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7. , 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, or 14.5% by mass There may be. For example, the range may be about 3 to 10% by mass.
　本開示の組成物は、公知の方法又は公知の方法から極めて容易に想到できる方法により調製することができる。例えば、ポリマー（Ａ）、成分（Ｂ）、及び水、並びに、必要に応じてｐＨ調整剤及びその他の成分を適宜混合することにより調製することができる。 The compositions of the present disclosure can be prepared by a known method or a method that can be very easily conceived from a known method. For example, it can be prepared by appropriately mixing the polymer (A), the component (B), and water, and if necessary, a pH adjuster and other components.
　本開示の組成物は、例えば化粧料組成物として有用である。 The composition of the present disclosure is useful, for example, as a cosmetic composition.
　本開示の組成物は、効果を損なわない範囲で上記成分以外の成分を含有していてもよく、例えば化粧品分野で公知の成分を含有していてもよい。例えば、効果を損なわない範囲で、増粘剤を含有していてもよい。増粘剤としては、例えばヒドロキシエチルセルロース、キサンタンガム等の多糖類系水溶性高分子、カルボキシビニルポリマー、アルキル変性カルボキシビニルポリマー等が挙げられる。またさらに、例えば、粉末成分、液体油脂、固体油脂、ロウ、炭化水素油、高級脂肪酸、高級アルコール、エステル油、シリコーン油、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤、非イオン界面活性剤、保湿剤、水溶性高分子、皮膜剤、紫外線吸収剤、金属イオン封鎖剤、低級アルコール、多価アルコール、糖、アミノ酸、有機アミン、高分子エマルジョン、ｐＨ調整剤、皮膚栄養剤、ビタミン、酸化防止剤、酸化防止助剤、香料等を含有していてもよい。 The composition of the present disclosure may contain a component other than the above components as long as the effect is not impaired, and may contain, for example, a component known in the cosmetics field. For example, a thickener may be contained as long as the effect is not impaired. Examples of the thickener include polysaccharide-based water-soluble polymers such as hydroxyethyl cellulose and xanthan gum, carboxyvinyl polymers, and alkyl-modified carboxyvinyl polymers. Furthermore, for example, powder components, liquid fats and oils, solid fats and oils, waxes, hydrocarbon oils, higher fatty acids, higher alcohols, ester oils, silicone oils, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants. Activators, moisturizers, water-soluble polymers, film agents, UV absorbers, metal ion blockers, lower alcohols, polyhydric alcohols, sugars, amino acids, organic amines, polymer emulsions, pH adjusters, skin nutrients, vitamins , Antioxidants, antioxidant aids, fragrances and the like may be contained.
　本開示の組成物を化粧品分野において用いる場合、その形態は特に限定されないが、例えば、薬用クリーム、化粧水、乳液、美容液、クリーム、クリームパック、マッサージクリーム、クレンジングクリーム、クレンジングジェル、ジェルクリーム、洗顔フォーム、保湿ジェル、ヘアーセッティングジェル、日焼け止め、スタイリングジェル、アイライナー、マスカラ、口紅及びファンデーション等が挙げられる。 When the composition of the present disclosure is used in the field of cosmetics, its form is not particularly limited, but for example, medicated cream, lotion, milky lotion, beauty essence, cream, cream pack, massage cream, cleansing cream, cleansing gel, gel cream, etc. Examples include facial cleansing foams, moisturizing gels, hair setting gels, sunscreens, styling gels, eyeliners, mascara, lipsticks and foundations.
　本開示は、また、アスコルビン酸又はその誘導体を含有する粘性組成物調製用の増粘剤も好ましく包含する。当該増粘剤は、ポリマー（Ａ）を含んでなる。また、当該増粘剤は、好ましくはアスコルビン酸又はその誘導体を２．５質量％以上含有する粘性組成物調製用である。その他、本開示の組成物について上述した内容は、全て当該増粘剤についても当てはまり得る。 The present disclosure also preferably includes a thickener for preparing a viscous composition containing ascorbic acid or a derivative thereof. The thickener comprises the polymer (A). The thickener is preferably for preparing a viscous composition containing 2.5% by mass or more of ascorbic acid or a derivative thereof. In addition, all the above-mentioned contents regarding the compositions of the present disclosure may also apply to the thickener.
　なお、本明細書において「含む」とは、「本質的にからなる」と、「からなる」をも包含する（The term "comprising" includes "consisting essentially of” and "consisting of."）。また、本開示は、本明細書に説明した構成要件を任意の組み合わせを全て包含する。 In this specification, "including" also includes "consisting of" and "consisting of" (The term "comprising" includes "consisting essentially of" and "consisting of."). The present disclosure also includes all combinations of the constituent requirements described herein.
　また、上述した本開示の各実施形態について説明した各種特性（性質、構造、機能等）は、本開示に包含される主題を特定するにあたり、どのように組み合わせられてもよい。すなわち、本開示には、本明細書に記載される組み合わせ可能な各特性のあらゆる組み合わせからなる主題が全て包含される。 Further, the various characteristics (property, structure, function, etc.) described for each embodiment of the present disclosure described above may be combined in any way in specifying the subject matter included in the present disclosure. That is, the present disclosure includes all subjects consisting of any combination of each combinable property described herein.
　以下、例を示して本開示の実施形態をより具体的に説明するが、本開示の実施形態は下記の例に限定されるものではない。 Hereinafter, embodiments of the present disclosure will be described in more detail with reference to examples, but the embodiments of the present disclosure are not limited to the following examples.
ポリマーの調製
［製造例１］
　攪拌機、温度計、窒素吹き込み管および冷却管を備えた５００ｍＬ容の四つ口フラスコに、アクリル酸４５ｇ（０．６２５モル）、ブレンマーＶＭＡ７０（日本油脂株式会社製：メタクリル酸ステアリルが１０～２０質量部、メタクリル酸エイコサニルが１０～２０質量部、メタクリル酸ベヘニルが５９～８０質量部およびメタクリル酸テトラコサニルの含有量が１質量部以下の混合物）１．３５ｇ、ペンタエリトリトールテトラアリルエーテル０．０２ｇ、ノルマルヘキサン１５０ｇおよび２，２’－アゾビスメチルイソブチレート０．０８１ｇ（０．０００３５モル）を仕込んだ。溶液を撹拌して均一に混合した後、反応容器（四つ口フラスコ）の上部空間、原料および溶媒中に存在している酸素を除去するために、溶液中に窒素ガスを吹き込んだ。次いで、窒素雰囲気下、６０～６５℃に保持して４時間反応させた。反応終了後、生成したスラリーを９０℃に加熱して、ノルマルヘキサンを留去し、さらに、１１０℃、１０ｍｍＨｇにて８時間減圧乾燥することにより、白色微粉末状のアルキル変性カルボキシル基含有水溶性共重合体４３ｇを得た。以下当該共重合体をポリマー１と表記することがある。 Polymer preparation [Production Example 1]
45 g (0.625 mol) of acrylic acid, Blemmer VMA70 (manufactured by Nippon Oil & Fats Co., Ltd .: 10 to 20 mass of stearyl methacrylate) in a 500 mL four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube and cooling tube. 1.35 g, pentaerythritol tetraallyl ether 0.02 g, normal 150 g of hexane and 0.081 g (0.00035 mol) of 2,2'-azobismethylisobutyrate were charged. After stirring and uniformly mixing the solution, nitrogen gas was blown into the solution to remove oxygen present in the upper space of the reaction vessel (four-necked flask), raw materials and solvent. Then, it was kept at 60 to 65 ° C. under a nitrogen atmosphere and reacted for 4 hours. After completion of the reaction, the produced slurry was heated to 90 ° C. to distill off normal hexane, and further dried under reduced pressure at 110 ° C. and 10 mmHg for 8 hours to obtain a white fine powder of alkyl-modified carboxyl group-containing water-soluble material. 43 g of the copolymer was obtained. Hereinafter, the copolymer may be referred to as polymer 1.
［製造例２］
　攪拌器、温度計、窒素吹き込み管及び冷却管を備えた５００ｍＬ（ミリリットル）容の四つ口フラスコに、アクリル酸４５ｇ、アルキル基の炭素数が１８～２４である（メタ）アクリル酸アルキルエステルとしてブレンマーＶＭＡ７０（日油株式会社製、メタクリル酸ステアリルが１０～２０質量部、メタクリル酸エイコサニルが１０～２０質量部、メタクリル酸ベヘニルが５９～８０質量部及びメタクリル酸テトラコサニルの含有率が１質量％以下の混合物）１．３５ｇ、エチレン性不飽和基を少なくとも２個有する化合物としてペンタエリスリトールテトラアリルエーテル０．０２ｇ、ラジカル重合開始剤として２，２’－アゾビス（イソ酪酸メチル）０．１１６ｇ、及び反応溶媒としてノルマルヘキサン２３０．９ｇを仕込んだ。引き続き、溶液を均一に攪拌、混合した後、反応容器（四つ口フラスコ）の上部空間、原料及び反応溶媒中に存在している酸素を除去するために、溶液中に窒素ガスを吹き込んだ。次いで、窒素雰囲気下、溶液を６０～６５℃まで加熱した。溶液の温度が６０℃に到達してから２時間後にノニオン性界面活性剤として１２－ヒドロキシステアリン酸とポリオキシエチレンのブロック共重合体（クローダ製、Ｈｙｐｅｒｍｅｒ　Ｂ２４６）０．９ｇを反応容器に投入した。その後、溶液の温度が６０℃に到達してから３時間６０～６５℃に保持した。その後、生成したスラリーを１００℃に加熱して、ノルマルヘキサンを留去し、さらに加熱装置の設定温度を１１５℃に設定して、減圧装置の設定圧力を１０ｍｍＨｇに設定して、８時間乾燥し、アルキル変性カルボキシル基含有共重合体の白色微粒子４１ｇを得た。以下当該共重合体をポリマー２と表記することがある。 [Manufacturing Example 2]
As a (meth) acrylic acid alkyl ester having 45 g of acrylic acid and an alkyl group having 18 to 24 carbon atoms in a 500 mL (milliliter) four-necked flask equipped with a stirrer, a thermometer, a nitrogen blowing tube and a cooling tube. Blemmer VMA70 (manufactured by Nichiyu Co., Ltd., stearyl methacrylate by 10 to 20 parts by mass, eikosanyl methacrylate by 10 to 20 parts by mass, behenyl methacrylate by 59 to 80 parts by mass, and tetracosanyl methacrylate by 1% by mass or less. 1.35 g of the mixture, 0.02 g of pentaerythritol tetraallyl ether as a compound having at least two ethylenically unsaturated groups, 0.116 g of 2,2'-azobis (methyl isobutyrate) as a radical polymerization initiator, and reaction. 230.9 g of normal hexane was charged as a solvent. Subsequently, after the solution was uniformly stirred and mixed, nitrogen gas was blown into the solution in order to remove oxygen present in the upper space of the reaction vessel (four-necked flask), the raw material and the reaction solvent. The solution was then heated to 60-65 ° C. under a nitrogen atmosphere. Two hours after the temperature of the solution reached 60 ° C., 0.9 g of a block copolymer of 12-hydroxystearic acid and polyoxyethylene (Hypermer B246 manufactured by Croda) was charged into the reaction vessel as a nonionic surfactant. .. Then, after the temperature of the solution reached 60 ° C., it was kept at 60 to 65 ° C. for 3 hours. Then, the generated slurry is heated to 100 ° C., normal hexane is distilled off, the set temperature of the heating device is set to 115 ° C., the set pressure of the decompression device is set to 10 mmHg, and the mixture is dried for 8 hours. , 41 g of white fine particles of an alkyl-modified carboxyl group-containing copolymer was obtained. Hereinafter, the copolymer may be referred to as polymer 2.
［製造例３］
　攪拌機、温度計、窒素吹き込み管および冷却管を備えた５００ｍＬ容の四つ口フラスコに、アクリル酸４５ｇ（０．６２５モル）、ブレンマーＶＭＡ７０（日本油脂株式会社製：メタクリル酸ステアリルが１０～２０質量部、メタクリル酸エイコサニルが１０～２０質量部、メタクリル酸ベヘニルが５９～８０質量部およびメタクリル酸テトラコサニルの含有量が１質量部以下の混合物）２．２５ｇ、ペンタエリトリトールテトラアリルエーテル０．０２ｇ、ノルマルヘキサン１５０ｇおよび２，２’－アゾビスメチルイソブチレート０．０８１ｇ（０．０００３５モル）を仕込んだ。溶液を撹拌して均一に混合した後、反応容器（四つ口フラスコ）の上部空間、原料および溶媒中に存在している酸素を除去するために、溶液中に窒素ガスを吹き込んだ。次いで、窒素雰囲気下、６０～６５℃に保持して４時間反応させた。反応終了後、生成したスラリーを９０℃に加熱して、ノルマルヘキサンを留去し、さらに、１１０℃、１０ｍｍＨｇにて８時間減圧乾燥することにより、白色微粉末状のアルキル変性カルボキシル基含有水溶性共重合体４３ｇを得た。以下当該共重合体をポリマー３と表記することがある。 [Manufacturing Example 3]
45 g (0.625 mol) of acrylic acid, Blemmer VMA70 (manufactured by Nippon Oil & Fats Co., Ltd .: 10 to 20 mass of stearyl methacrylate) in a 500 mL four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube and cooling tube. 2.25 g, pentaerythritol tetraallyl ether 0.02 g, normal 150 g of hexane and 0.081 g (0.00035 mol) of 2,2'-azobismethylisobutyrate were charged. After stirring and uniformly mixing the solution, nitrogen gas was blown into the solution to remove oxygen present in the upper space of the reaction vessel (four-necked flask), raw materials and solvent. Then, it was kept at 60 to 65 ° C. under a nitrogen atmosphere and reacted for 4 hours. After completion of the reaction, the produced slurry was heated to 90 ° C. to distill off normal hexane, and further dried under reduced pressure at 110 ° C. and 10 mmHg for 8 hours to obtain a white fine powder of alkyl-modified carboxyl group-containing water-soluble material. 43 g of the copolymer was obtained. Hereinafter, the copolymer may be referred to as polymer 3.
［製造例４］
　攪拌機、温度計、窒素吹き込み管及び冷却管を備えた５００ｍＬ（ミリリットル）容の四つ口フラスコに、アクリル酸４０ｇ、ブレンマーＶＭＡ－７０（日油株式会社製、メタクリル酸ステアリルが１０～２０質量部、メタクリル酸エイコサニルが１０～２０質量部、メタクリル酸ベヘニルが５９～８０質量部及びメタクリル酸テトラコサニルの含有率が１質量％以下の混合物）０．８８ｇ、ペンタエリスリトールテトラアリルエーテル０．２２ｇ、２，２’－アゾビス（イソ酪酸メチル）０．１１６ｇ、及びノルマルヘキサン２３０．９ｇを仕込んだ。溶液を撹拌して均一に混合した後、反応容器（四つ口フラスコ）の上部空間、原料及び反応溶媒中に存在している酸素を除去するために、溶液中に窒素ガスを吹き込んだ。次いで、窒素雰囲気下、６０～６５℃まで加熱した。その後、３時間６０～６５℃に保持した。６０～６５℃で１時間程度、保持した時点で、ノルマルヘキサン２．０ｇにポリオキシエチレンヒマシ油（日光ケミカル（株）製、商品名：ＣＯ－３、エチレンオキシド３モル付加物）０．２６ｇとトリイソステアリン酸ポリオキシエチレン硬化ヒマシ油（日本エマルジョン（株）製、商品名：ＲＷＩＳ－３５０、エチレンオキシド５０モル付加物）０．９８ｇとを溶解させたものを、反応容器に投入した。その後、生成したスラリーを１００℃に加熱して、ノルマルヘキサンを留去し、さらに１１５℃、１０ｍｍＨｇの条件で、８時間減圧乾燥することにより、白色微粉末のアルキル変性カルボキシル基含有水溶性共重合体３８ｇを得た。以下当該共重合体をポリマー４と表記することがある。 [Manufacturing Example 4]
40 g of acrylic acid, Blemmer VMA-70 (manufactured by Nichiyu Co., Ltd., 10 to 20 parts by mass of stearyl methacrylate) in a 500 mL (milliliter) four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube and cooling tube. , 10 to 20 parts by mass of eicosanyl methacrylate, 59 to 80 parts by mass of behenyl methacrylate, and a mixture containing tetracosanyl methacrylate in a content of 1% by mass or less) 0.88 g, pentaerythritol tetraallyl ether 0.22 g, 2, 0.116 g of 2'-azobis (methyl isobutyrate) and 230.9 g of normal hexane were charged. After stirring the solution and mixing it uniformly, nitrogen gas was blown into the solution to remove oxygen present in the upper space of the reaction vessel (four-necked flask), the raw material and the reaction solvent. Then, it was heated to 60-65 ° C. under a nitrogen atmosphere. Then, it was kept at 60-65 ° C. for 3 hours. When it was held at 60 to 65 ° C. for about 1 hour, 2.0 g of normal hexane and 0.26 g of polyoxyethylene castor oil (manufactured by Nikko Chemical Co., Ltd., trade name: CO-3, 3 mol adduct of ethylene oxide) were added. 0.98 g of polyoxyethylene hydrogenated castor oil triisostearate (manufactured by Nippon Emulsion Co., Ltd., trade name: RWIS-350, 50 mol of ethylene oxide adduct) was dissolved and put into a reaction vessel. Then, the produced slurry was heated to 100 ° C. to distill off normal hexane, and further dried under reduced pressure for 8 hours at 115 ° C. and 10 mmHg to obtain an alkyl-modified carboxyl group-containing water-soluble copolymer of fine white powder. A coalescence of 38 g was obtained. Hereinafter, the copolymer may be referred to as polymer 4.
［製造例５］
　攪拌機、温度計、窒素吹き込み管及び冷却管を備えた５００ｍＬ（ミリリットル）容の四つ口フラスコに、アクリル酸４０ｇ、ブレンマーＶＭＡ－７０（日油株式会社製、メタクリル酸ステアリルが１０～２０質量部、メタクリル酸エイコサニルが１０～２０質量部、メタクリル酸ベヘニルが５９～８０質量部及びメタクリル酸テトラコサニルの含有率が１質量％以下の混合物）０．４ｇ、ペンタエリスリトールテトラアリルエーテル０．１９ｇ、２，２’－アゾビス（イソ酪酸メチル）０．１１６ｇ、及びノルマルヘキサン２３０．９ｇを仕込んだ。溶液を撹拌して均一に混合した後、反応容器（四つ口フラスコ）の上部空間、原料及び反応溶媒中に存在している酸素を除去するために、溶液中に窒素ガスを吹き込んだ。次いで、窒素雰囲気下、６０～６５℃まで加熱した。その後、３時間６０～６５℃に保持した。６０～６５℃で１時間程度、保持した時点で、ノルマルヘキサン２．０ｇに１２－ヒドロキシステアリン酸とポリオキシエチレンのブロック共重合体（クローダ製、Ｈｙｐｅｒｍｅｒ　Ｂ２４６）１．６ｇを溶解させたものを、反応容器に投入した。その後、生成したスラリーを１００℃に加熱して、ノルマルヘキサンを留去し、さらに１１５℃、１０ｍｍＨｇの条件で、８時間減圧乾燥することにより、白色微粉末のアルキル変性カルボキシル基含有水溶性共重合体３９ｇを得た。以下当該共重合体をポリマー５と表記することがある。 [Manufacturing Example 5]
40 g of acrylic acid, Blemmer VMA-70 (manufactured by Nichiyu Co., Ltd., 10 to 20 parts by mass of stearyl methacrylate) in a 500 mL (milliliter) four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube and cooling tube. , 10 to 20 parts by mass of eicosanyl methacrylate, 59 to 80 parts by mass of behenyl methacrylate, and a mixture containing tetracosanyl methacrylate in a content of 1% by mass or less) 0.4 g, pentaerythritol tetraallyl ether 0.19 g, 2, 0.116 g of 2'-azobis (methyl isobutyrate) and 230.9 g of normal hexane were charged. After stirring the solution and mixing it uniformly, nitrogen gas was blown into the solution to remove oxygen present in the upper space of the reaction vessel (four-necked flask), the raw material and the reaction solvent. Then, it was heated to 60-65 ° C. under a nitrogen atmosphere. Then, it was kept at 60-65 ° C. for 3 hours. After holding at 60 to 65 ° C. for about 1 hour, 1.6 g of a block copolymer of 12-hydroxystearic acid and polyoxyethylene (Hypermer B246 manufactured by Croda) was dissolved in 2.0 g of normal hexane. , Put into a reaction vessel. Then, the produced slurry was heated to 100 ° C. to distill off normal hexane, and further dried under reduced pressure for 8 hours at 115 ° C. and 10 mmHg to obtain an alkyl-modified carboxyl group-containing water-soluble copolymer of fine white powder. A coalescence of 39 g was obtained. Hereinafter, the copolymer may be referred to as polymer 5.
［製造例６］
　撹拌機、温度計、窒素吹き込み管及び冷却管を取り付けた５００ｍＬ容の四つ口フラスコに、アクリル酸４５ｇ（０．６２５モル）、ペンタエリスリトールテトラアリルエーテル０．２７ｇ、ｎ－ヘキサン１５０ｇ及び２，２’－アゾビスメチルイソブチレート０．０８１ｇ（０．０００３５モル）を入れ、反応液を調製した。溶液を撹拌して均一に混合した後、反応容器の上部空間、原料及び溶媒中に存在している酸素を除去するために溶液中に窒素ガスを吹き込んだ。次いで、窒素雰囲気下、反応液を６０～６５℃に保持して４時間反応させた。反応終了後、生成したスラリーを９０℃に加熱して、ｎ－ヘキサンを留去し、さらに、１１０℃、１０ｍｍＨｇにて８時間減圧乾燥することにより、カルボキシビニルポリマー４２ｇを得た。以下当該カルボキシビニルポリマーをポリマー６と表記することがある。 [Manufacturing Example 6]
45 g (0.625 mol) of acrylic acid, 0.27 g of pentaerythritol tetraallyl ether, 150 g of n-hexane and 2, in a 500 mL four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube and cooling tube. 0.081 g (0.00035 mol) of 2'-azobismethylisobutyrate was added to prepare a reaction solution. After stirring the solution and mixing it uniformly, nitrogen gas was blown into the solution to remove oxygen present in the upper space of the reaction vessel, the raw material and the solvent. Then, the reaction solution was kept at 60 to 65 ° C. under a nitrogen atmosphere and reacted for 4 hours. After completion of the reaction, the produced slurry was heated to 90 ° C. to distill off n-hexane, and further dried under reduced pressure at 110 ° C. and 10 mmHg for 8 hours to obtain 42 g of a carboxyvinyl polymer. Hereinafter, the carboxyvinyl polymer may be referred to as polymer 6.
［製造例７］
　攪拌機、温度計、窒素吹き込み管及び冷却管を備えた５００ｍＬ（ミリリットル）容の四つ口フラスコに、アクリル酸４０ｇ、ペンタエリスリトールテトラアリルエーテル０．２２ｇ、２，２’－アゾビス（イソ酪酸メチル）０．１１６ｇ、及びノルマルヘキサン２３０．９ｇを仕込んだ。溶液を撹拌して均一に混合した後、反応容器（四つ口フラスコ）の上部空間、原料及び反応溶媒中に存在している酸素を除去するために、溶液中に窒素ガスを吹き込んだ。次いで、窒素雰囲気下、６０～６５℃まで加熱した。その後、３時間６０～６５℃に保持した。６０～６５℃で１時間程度、保持した時点で、ノルマルヘキサン２．０ｇに１２－ヒドロキシステアリン酸とポリオキシエチレンのブロック共重合体（クローダ製、Ｈｙｐｅｒｍｅｒ　Ｂ２４６）２．０ｇを溶解させたものを、反応容器に投入した。その後、生成したスラリーを１００℃に加熱して、ノルマルヘキサンを留去し、さらに１１５℃、１０ｍｍＨｇの条件で、８時間減圧乾燥することにより、白色微粉末のカルボキシビニルポリマー３８ｇを得た。以下当該カルボキシビニルポリマーをポリマー７と表記することがある。 [Manufacturing Example 7]
40 g of acrylic acid, 0.22 g of pentaerythritol tetraallyl ether, 2,2'-azobis (methyl isobutyrate) in a 500 mL (milliliter) four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube and cooling tube. 0.116 g and 230.9 g of normal hexane were charged. After stirring the solution and mixing it uniformly, nitrogen gas was blown into the solution to remove oxygen present in the upper space of the reaction vessel (four-necked flask), the raw material and the reaction solvent. Then, it was heated to 60-65 ° C. under a nitrogen atmosphere. Then, it was kept at 60-65 ° C. for 3 hours. After holding at 60 to 65 ° C. for about 1 hour, 2.0 g of a block copolymer of 12-hydroxystearic acid and polyoxyethylene (Hypermer B246 manufactured by Croda) was dissolved in 2.0 g of normal hexane. , Put into a reaction vessel. Then, the produced slurry was heated to 100 ° C., normal hexane was distilled off, and the slurry was further dried under reduced pressure at 115 ° C. and 10 mmHg for 8 hours to obtain 38 g of a fine white carboxyvinyl polymer. Hereinafter, the carboxyvinyl polymer may be referred to as polymer 7.
粘性組成物の調製及び評価
　ポリマー１～７、及びアスコルビン酸配糖体（アスコルビン酸２－グルコシド）を用いて、各ポリマー濃度が１質量％、アスコルビン酸配糖体濃度が０～５質量％となるよう、イオン交換水に溶解／分散させ、粘性組成物を得た。必要に応じてＮａＯＨを用いてｐＨを６．５～６．８に調整した（ｐＨメーターを使用）。より具体的には、アスコルビン酸配糖体をイオン交換水に溶解させ、そこへ別途調製した２％ポリマー水分散体を５０ｇ加え、６％ＮａＯＨ水溶液をｐＨが６．５～６．８になるまで加え、最後に系の全重量が１００ｇになるようにイオン交換水を加えて、各粘性組成物を調製した。 Preparation and evaluation of viscous compositions Using polymers 1 to 7 and ascorbic acid glycosides (ascorbic acid 2-glucoside), the concentration of each polymer was 1% by mass and the concentration of ascorbic acid glycosides was 0 to 5% by mass. It was dissolved / dispersed in ion-exchanged water so as to obtain a viscous composition. The pH was adjusted to 6.5-6.8 with NaOH as needed (using a pH meter). More specifically, the ascorbic acid glycoside is dissolved in ion-exchanged water, 50 g of a separately prepared 2% polymer aqueous dispersion is added thereto, and the pH of a 6% NaOH aqueous solution becomes 6.5 to 6.8. Finally, ion-exchanged water was added so that the total weight of the system was 100 g, and each viscous composition was prepared.
　得られた粘性組成物の組成及び各ポリマーの組成を表１にまとめて示す。なお、ＰＥＴＡはペンタエリスリトールテトラアリルエーテルを示す。 Table 1 summarizes the composition of the obtained viscous composition and the composition of each polymer. PETA represents pentaerythritol tetraallyl ether.
　得られた各粘性組成物の粘度を測定した。粘度は、ＢＨ型回転粘度計を用いて測定した。スピンドルローターの回転速度を毎分２０回転として、２５℃において、ローターの回転を開始してから１分後の粘度の値を読み取った。ローターＮｏ．３、Ｎｏ．４、Ｎｏ．５、Ｎｏ．６又はＮｏ．７を使用した。なお、当該粘度測定の前に、各粘性組成物を遠心する（２０００ｒｐｍ×１０～２０分）ことで脱泡してから用いた。 The viscosity of each of the obtained viscous compositions was measured. The viscosity was measured using a BH type rotational viscometer. Assuming that the rotation speed of the spindle rotor was 20 rotations per minute, the viscosity value 1 minute after the start of rotation of the rotor was read at 25 ° C. Rotor No. 3, No. 4, No. 5, No. 6 or No. 7 was used. Before the viscosity measurement, each viscous composition was defoamed by centrifugation (2000 rpm × 10 to 20 minutes) before use.
　また、得られた各粘性組成物の透明性を評価した。具体的には、ＵＶ（４２５ｎｍ）透過率（％Ｔ）を測定した。 In addition, the transparency of each of the obtained viscous compositions was evaluated. Specifically, the UV (425 nm) transmittance (% T) was measured.
＜透過率測定方法＞
　島津製作所社製の分光光度計（型番：ＵＶ－１８５０）を用い、評価サンプルの透過率を測定した。まずサンプルをＵＶ測定用のセル（光路長１ｃｍ）に入れ、遠心分離器にて毎分２，０００回転で５分間の操作により脱泡した。脱泡が完了していない場合は遠心分離機にて同様の操作を行い、泡が完全に試料上部から抜けることを確認した。その後、試料を分光光度計にセットし、測定波長を４２５ｎｍとして透過率を測定した。なお、蒸留水を透過率１００％になるように校正した。 <Transmittance measurement method>
The transmittance of the evaluation sample was measured using a spectrophotometer (model number: UV-1850) manufactured by Shimadzu Corporation. First, the sample was placed in a cell for UV measurement (optical path length 1 cm), and defoamed by a centrifuge at 2,000 rpm for 5 minutes. When the defoaming was not completed, the same operation was performed with a centrifuge, and it was confirmed that the bubbles were completely removed from the upper part of the sample. Then, the sample was set in a spectrophotometer, and the transmittance was measured with the measurement wavelength set to 425 nm. Distilled water was calibrated so as to have a transmittance of 100%.
　粘度測定結果を図１に、ＵＶ（４２５ｎｍ）透過率測定結果を図２に、それぞれ示す。 The viscosity measurement result is shown in FIG. 1, and the UV (425 nm) transmittance measurement result is shown in FIG. 2, respectively.
　粘度については、アスコルビン酸配糖体が３質量％配合されたときに、５０００ｍＰａ・ｓ以上である組成物を○、それ以外を×と評価した。また、透明性については、アスコルビン酸配糖体が３質量％配合されたときに、ＵＶ（４２５ｎｍ）透過率が８０（％Ｔ）以上である組成物を○、それ以外を×と評価した。当該評価を、表１にあわせて示す。 Regarding the viscosity, when 3% by mass of ascorbic acid glycoside was blended, the composition having 5000 mPa · s or more was evaluated as ◯, and the other compositions were evaluated as ×. Regarding the transparency, when 3% by mass of the ascorbic acid glycoside was blended, the composition having a UV (425 nm) transmittance of 80 (% T) or more was evaluated as ◯, and the other compositions were evaluated as x. The evaluation is shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　なお、ポリマー３について、上記と同様にして、ポリマー濃度を０．６質量％又は０．８質量％、アスコルビン酸配糖体濃度を３質量％とした粘性組成物を調製し、粘度及びＵＶ（４２５ｎｍ）透過率を測定したところ、ポリマー濃度０．６質量％では、粘度７６５０ｍＰａ・ｓ、ＵＶ透過率９７．２（％Ｔ）であり、ポリマー濃度０．８質量％では、粘度１６０００ｍＰａ・ｓ、ＵＶ透過率９７．３（％Ｔ）であった。 For the polymer 3, a viscous composition having a polymer concentration of 0.6% by mass or 0.8% by mass and an ascorbic acid glycoside concentration of 3% by mass was prepared in the same manner as described above, and the viscosity and UV ( When the transmittance (425 nm) was measured, the viscosity was 7650 mPa · s and the UV transmittance was 97.2 (% T) at a polymer concentration of 0.6% by mass, and the viscosity was 16000 mPa · s at a polymer concentration of 0.8% by mass. The UV transmittance was 97.3 (% T).
　また、ポリマー１及び２について、上記と同様にして、ポリマー濃度１質量％、アスコルビン酸配糖体濃度を７質量％とした粘性組成物を調製し、粘度を測定したところ、ポリマー１含有粘性組成物では粘度５，８００ｍＰａ・ｓ、ポリマー２含有粘性組成物では粘度１３，６００ｍＰａ・ｓであった。 Further, with respect to the polymers 1 and 2, a viscous composition having a polymer concentration of 1% by mass and an ascorbic acid glycoside concentration of 7% by mass was prepared in the same manner as described above, and the viscosity was measured. The product had a viscosity of 5,800 mPa · s, and the polymer 2-containing viscous composition had a viscosity of 13,600 mPa · s.
　なお、アスコルビン酸配糖体に代えてＬ－アスコルビン酸リン酸マグネシウム（リン酸Ｌ－アスコルビルマグネシウム）を用いた以外は、実施例１と同様にして粘性組成物（実施例ａ）を調製し、粘度及びＵＶ（４２５ｎｍ）透過率を測定したところ、粘度１２，６００ｍＰａ・ｓ、ＵＶ透過率９４．７（％Ｔ）であった。 A viscous composition (Example a) was prepared in the same manner as in Example 1 except that magnesium L-ascorbic acid phosphate (L-ascorbic magnesium phosphate) was used instead of the ascorbic acid glycoside. When the viscosity and UV (425 nm) transmittance were measured, the viscosity was 12,600 mPa · s and the UV transmittance was 94.7 (% T).
　また、アスコルビン酸配糖体に代えてＬ－アスコルビン酸リン酸マグネシウム（リン酸Ｌ－アスコルビルマグネシウム）又はＬ－アスコルビン酸ナトリウムを用いた以外は、実施例２と同様にして粘性組成物（前者を用いた組成物：実施例ｂ１、後者を用いた組成物：実施例ｂ２）を調製し、粘度及びＵＶ（４２５ｎｍ）透過率を測定したところ、Ｌ－アスコルビン酸リン酸マグネシウムを用いた組成物では粘度１６，６００ｍＰａ・ｓ、ＵＶ透過率９６．４（％Ｔ）であり、Ｌ－アスコルビン酸ナトリウムを用いた組成物では粘度５，１６０ｍＰａ・ｓ、ＵＶ透過率９０．６（％Ｔ）であった。  Further, the viscous composition (the former is the same as in Example 2) except that magnesium L-ascorbic acid phosphate (L-ascorbic magnesium phosphate) or sodium L-ascorbic acid was used instead of the ascorbic acid glycoside. The composition used: Example b1, the composition using the latter: Example b2) was prepared, and the viscosity and UV (425 nm) permeability were measured. As a result, the composition using magnesium L-ascorbic acid phosphate was used. The viscosity was 16,600 mPa · s and the UV transmission rate was 96.4 (% T), and the composition using sodium L-ascorbic acid had a viscosity of 5,160 mPa · s and a UV transmission rate of 90.6 (% T). rice field.

Claims (8)

  1. （Ａ）次の（ｉ）、（ｉｉ）、及び（ｉｉｉ）：
    　　（ｉ）（メタ）アクリル酸１００質量部
    　　（ｉｉ）エチレン性不飽和基を２個以上有する化合物０．０１～１質量部
    　　（ｉｉｉ）アルキル基の炭素数が１０～３０である（メタ）アクリル酸アルキルエステル０．５～１０質量部
    を重合して得られるポリマーを０．３質量％以上、並びに
    （Ｂ）アスコルビン酸又はその誘導体
    を含有する組成物。     (A) The following (i), (ii), and (iii):
    (I) 100 parts by mass of (meth) acrylic acid (ii) Compound having two or more ethylenically unsaturated groups 0.01 to 1 part by mass (iii) (meth) acrylic having an alkyl group having 10 to 30 carbon atoms A composition containing 0.3% by mass or more of a polymer obtained by polymerizing 0.5 to 10 parts by mass of an acid alkyl ester, and (B) ascorbic acid or a derivative thereof.
  2. 前記（ｉｉ）が、
    エチレン性不飽和基を２個以上有する化合物０．０１～０．２質量部
    である、
    請求項１に記載の組成物。     The above (ii) is
    A compound having two or more ethylenically unsaturated groups, 0.01 to 0.2 parts by mass.
    The composition according to claim 1.
  3. 前記エチレン性不飽和基を２個以上有する化合物が、ペンタエリスリトールアリルエーテルである、請求項１又は２に記載の組成物。 The composition according to claim 1 or 2, wherein the compound having two or more ethylenically unsaturated groups is pentaerythritol allyl ether.
  4. 粘度が５０００ｍＰａ・ｓ以上である、請求項１～３のいずれかに記載の組成物。 The composition according to any one of claims 1 to 3, which has a viscosity of 5000 mPa · s or more.
  5. 前記（Ｂ）を２．５質量％以上含有する、請求項１～４のいずれかに記載の組成物。 The composition according to any one of claims 1 to 4, which contains 2.5% by mass or more of the above (B).
  6. アスコルビン酸の誘導体が、アスコルビン酸塩、アスコルビン酸配糖体、アスコルビン酸リン酸塩、脂肪酸アスコルビル、アスコルビルエチル、アスコルビン酸－リン酸－脂肪酸、及びグリセリルオクチルアスコルビン酸からなる群より選択される少なくとも１種である、
    請求項１～５のいずれかに記載の組成物。     At least one ascorbic acid derivative selected from the group consisting of ascorbic acid salt, ascorbic acid glycoside, ascorbic acid phosphate, fatty acid ascorbyl, ascorbyl ethyl, ascorbic acid-phosphate-fatty acid, and glyceryl octyl ascorbic acid. Seed,
    The composition according to any one of claims 1 to 5.
  7. 前記（ｉｉ）が、
    エチレン性不飽和基を２個以上有する化合物０．０１～０．２質量部
    であり、
    前記エチレン性不飽和基を２個以上有する化合物が、ペンタエリスリトールアリルエーテルであり、
    粘度が５０００ｍＰａ・ｓ以上であり、
    前記（Ｂ）を２．５質量％以上含有し、
    前記（Ｂ）が、アスコルビン酸、アスコルビン酸塩、アスコルビン酸配糖体、及びアスコルビン酸リン酸塩からなる群より選択される少なくとも１種である、
    請求項１に記載の組成物。     The above (ii) is
    The compound having two or more ethylenically unsaturated groups is 0.01 to 0.2 parts by mass.
    The compound having two or more ethylenically unsaturated groups is pentaerythritol allyl ether.
    The viscosity is 5000 mPa · s or more,
    Containing 2.5% by mass or more of the above (B),
    (B) is at least one selected from the group consisting of ascorbic acid, ascorbic acid salt, ascorbic acid glycoside, and ascorbic acid phosphate.
    The composition according to claim 1.
  8. （Ａ）次の（ｉ）、（ｉｉ）、及び（ｉｉｉ）：
    　　（ｉ）（メタ）アクリル酸１００質量部
    　　（ｉｉ）エチレン性不飽和基を２個以上有する化合物０．０１～１質量部
    　　（ｉｉｉ）アルキル基の炭素数が１０～３０である（メタ）アクリル酸アルキルエステル０．５～１０質量部
    を重合して得られるポリマー
    を含有する、
    アスコルビン酸又はその誘導体を２．５質量％以上含有する粘性組成物調製用の増粘剤。     (A) The following (i), (ii), and (iii):
    (I) 100 parts by mass of (meth) acrylic acid (ii) Compound having two or more ethylenically unsaturated groups 0.01 to 1 part by mass (iii) (meth) acrylic having an alkyl group having 10 to 30 carbon atoms Contains a polymer obtained by polymerizing 0.5 to 10 parts by mass of an acid alkyl ester.
    A thickener for preparing a viscous composition containing 2.5% by mass or more of ascorbic acid or a derivative thereof.
PCT/JP2021/010729 2020-03-31 2021-03-17 Viscous composition WO2021200136A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007055354A1 (en) * 2005-11-14 2007-05-18 Sumitomo Seika Chemicals Co., Ltd. Water-soluble copolymer having alkyl-modified carboxyl group
WO2009084469A1 (en) * 2007-12-28 2009-07-09 Sumitomo Seika Chemicals Co., Ltd. (meth)acrylic acid/alkyl (meth)acrylate ester copolymer and cosmetic preparation containing the same
JP2011213676A (en) * 2010-03-31 2011-10-27 Kose Corp O/w-type emulsion composition
JP2012188385A (en) * 2011-03-10 2012-10-04 Nippon Menaade Keshohin Kk Cosmetic for eyelash
JP2015172028A (en) * 2014-02-20 2015-10-01 住友精化株式会社 cosmetic
JP2019069919A (en) * 2017-10-10 2019-05-09 共栄化学工業株式会社 Gelatinous composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007055354A1 (en) * 2005-11-14 2007-05-18 Sumitomo Seika Chemicals Co., Ltd. Water-soluble copolymer having alkyl-modified carboxyl group
WO2009084469A1 (en) * 2007-12-28 2009-07-09 Sumitomo Seika Chemicals Co., Ltd. (meth)acrylic acid/alkyl (meth)acrylate ester copolymer and cosmetic preparation containing the same
JP2011213676A (en) * 2010-03-31 2011-10-27 Kose Corp O/w-type emulsion composition
JP2012188385A (en) * 2011-03-10 2012-10-04 Nippon Menaade Keshohin Kk Cosmetic for eyelash
JP2015172028A (en) * 2014-02-20 2015-10-01 住友精化株式会社 cosmetic
JP2019069919A (en) * 2017-10-10 2019-05-09 共栄化学工業株式会社 Gelatinous composition

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