WO2021206042A1 - 粘性組成物 - Google Patents

粘性組成物 Download PDF

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Publication number
WO2021206042A1
WO2021206042A1 PCT/JP2021/014462 JP2021014462W WO2021206042A1 WO 2021206042 A1 WO2021206042 A1 WO 2021206042A1 JP 2021014462 W JP2021014462 W JP 2021014462W WO 2021206042 A1 WO2021206042 A1 WO 2021206042A1
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Prior art keywords
water
mass
allyl ether
polymer
acid
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PCT/JP2021/014462
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English (en)
French (fr)
Japanese (ja)
Inventor
山口　博史
友佳 境
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Sumitomo Seika Chemicals Co Ltd
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Sumitomo Seika Chemicals Co Ltd
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Priority to JP2022514056A priority Critical patent/JPWO2021206042A1/ja
Priority to CN202180025908.6A priority patent/CN115380072A/zh
Priority to EP21785484.3A priority patent/EP4134400A1/en
Priority to US17/916,903 priority patent/US20230149286A1/en
Publication of WO2021206042A1 publication Critical patent/WO2021206042A1/ja
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/02—Homopolymers or copolymers of esters
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/48—Thickener, Thickening system

Definitions

  • the present disclosure relates to a viscous composition or the like.
  • a polymer obtained by polymerizing a water-soluble unsaturated carboxylic acid monomer in the presence of water-soluble sucrose allyl ether is known to be useful as, for example, a thickener for cosmetics (for example, Patent Documents). 1).
  • the present inventors combine a composition containing a polymer obtained by polymerizing a water-soluble unsaturated carboxylic acid monomer in the presence of water-soluble sucrose allyl ether with a pH adjuster commonly used in the cosmetics field (for example,). It has been found that when an attempt is made to adjust the pH to a low pH (for example, pH 5.2 or less) by adding a low molecular weight organic acid compound), the viscosity of the composition is rapidly lost. As described above, the composition is useful as a viscous cosmetic composition, etc. However, if the viscosity is lost when the pH is lowered, cosmetic applications requiring a low pH (for example, astringent cosmetics, peeling gels, etc.) It is difficult to use the composition while maintaining the desired viscosity.
  • a pH adjuster commonly used in the cosmetics field
  • the present inventors further studied in order to find a method capable of lowering the pH while suppressing the decrease in the viscosity of the composition.
  • the present inventors instead of using a pH adjuster (for example, a low molecular weight organic acid compound) commonly used in the cosmetics field, perform specific cross-linking.
  • a pH adjuster for example, a low molecular weight organic acid compound
  • the acrylic acid-based polymer crosslinked with the agent it was found that the pH of the polymer-containing composition could be lowered while suppressing the decrease in viscosity, and further improvements were made.
  • the present disclosure includes, for example, the subjects described in the following sections.
  • Item 1. A polymer obtained by polymerizing a water-soluble unsaturated carboxylic acid monomer in the presence of water-soluble sucrose allyl ether.
  • B A polymer obtained by polymerizing at least acrylic acid and / or methacrylic acid in the presence of pentaerythritol allyl ether, and the amount of the pentaerythritol allyl ether is 100 parts by mass of the acrylic acid and / or methacrylic acid. Containing polymer and water, which is 0.1 parts by mass or more, pH 5.2 or less, Viscosity of 1000 mPa ⁇ s or more, Composition.
  • the water-soluble unsaturated carboxylic acid monomer in (A) is at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, and itaconic acid.
  • Item 2. The composition according to Item 1.
  • Item 3. Item 2.
  • Item 4. Item 2.
  • Item 6. Item 2. The item 1 to 5, wherein the amount of the water-soluble sucrose allyl ether in (A) is 0.01 to 1 part by mass with respect to 100 parts by mass of the water-soluble unsaturated carboxylic acid monomer. Composition.
  • Item 7. Item 2. The composition according to any one of Items 1 to 6, wherein (B) is the following (B-1) and / or (B-2).
  • (B) A polymer obtained by polymerizing a water-soluble unsaturated carboxylic acid monomer in the presence of pentaerythritol allyl ether, wherein the amount of the pentaerythritol allyl ether is the water-soluble unsaturated carboxylic acid monomer 100. Containing polymers that are 0.1 parts by mass or more relative to parts by weight, (A) For a composition containing a polymer obtained by polymerizing a water-soluble unsaturated carboxylic acid monomer in the presence of water-soluble sucrose allyl ether. pH regulator.
  • composition containing a polymer obtained by polymerizing a water-soluble unsaturated carboxylic acid monomer in the presence of water-soluble sucrose allyl ether, and having a low pH and high viscosity.
  • the present disclosure describes a composition containing a polymer obtained by polymerizing a water-soluble unsaturated carboxylic acid monomer in the presence of water-soluble sucrose allyl ether, and having a low pH and high viscosity, its use, and its use. Production methods and the like are preferably included, but not limited thereto, and the present disclosure includes all disclosed in the present specification and recognized by those skilled in the art.
  • compositions included in the present disclosure are (A) a polymer obtained by polymerizing a water-soluble unsaturated carboxylic acid monomer in the presence of water-soluble sucrose allyl ether, and (B) in the presence of pentaerythritol allyl ether. It is a polymer obtained by polymerizing at least acrylic acid and / or methacrylic acid, and the amount of the pentaerythritol allyl ether is 0.1 part by mass or more with respect to 100 parts by mass of the acrylic acid and / or methacrylic acid. , Polymers, and water. The pH is 5.2 or less and the viscosity is 1000 mPa ⁇ s or more.
  • the composition included in the present disclosure may be referred to as "the composition of the present disclosure”.
  • the polymer (A) is a polymer obtained by polymerizing a water-soluble unsaturated carboxylic acid monomer in the presence of water-soluble sucrose allyl ether.
  • the polymer can be obtained, for example, by a method including a step of polymerizing a water-soluble unsaturated carboxylic acid monomer by a suspension polymerization method in the presence of water-soluble sucrose allyl ether.
  • suspension polymerization methods a reverse phase suspension in which an aqueous phase droplet containing a water-soluble unsaturated carboxylic acid monomer, a water-soluble sucrose allyl ether and water is dispersed in a hydrophobic solvent is subjected to a polymerization reaction.
  • the polymerization method is preferable.
  • the water-soluble sucrose allyl ether can act as a water-soluble cross-linking agent.
  • the water-soluble unsaturated carboxylic acid monomer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, and itaconic acid. Of these, acrylic acid and methacrylic acid are preferable.
  • the water-soluble unsaturated carboxylic acid monomer may be used alone or in combination of two or more.
  • the degree of etherification of the water-soluble sucrose allyl ether is preferably 1.8 to 3.5, more preferably 2.0 to 3.2. This degree of etherification is the average value of the molar ratio of allyl ether groups to sucrose.
  • the degree of etherification can be calculated from the amount of acetic anhydride consumed by reacting the hydroxyl groups remaining in the sucrose allyl ether with acetic anhydride in pyridine.
  • the water-soluble sucrose allyl ether can be obtained, for example, by adding sodium hydroxide as a catalyst to an aqueous sucrose solution, converting sucrose into alkaline sucrose, and then dropping allyl bromide for etherification. can. At this time, by adjusting the amount of allyl bromide in the range of 2 to 6 times mol, preferably 2 to 5 times mol, of sucrose, water-soluble sucrose allyl ether can be efficiently obtained. ..
  • the reaction temperature for etherification is, for example, about 80 ° C. Usually, the reaction is completed about 3 hours after the allyl bromide is added dropwise.
  • Water-soluble sucrose allyl ether can be recovered by adding alcohol to the aqueous phase separated from the reaction solution, filtering out the precipitated salts, and then distilling off excess alcohol and water.
  • hydrophobic solvent used for reverse phase suspension polymerization for example, a petroleum hydrocarbon solvent selected from aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons is used.
  • aliphatic hydrocarbon include n-pentane, n-hexane and n-heptane.
  • alicyclic hydrocarbon include cyclopentane, methylcyclopentane, cyclohexane and methylcyclohexane.
  • aromatic hydrocarbons include benzene, toluene and xylene.
  • At least one hydrophobic solvent selected from n-hexane, n-heptane, cyclohexane and toluene is preferably used as an industrial general purpose solvent.
  • the ratio of the hydrophobic solvent is, for example, 100 to 200 parts by mass with respect to 100 parts by mass of the aqueous phase containing the water-soluble unsaturated carboxylic acid monomer and the like.
  • the aqueous phase containing a water-soluble unsaturated carboxylic acid monomer or the like, or the hydrophobic solvent may contain other components such as a surfactant and a radical initiator.
  • Surfactants are mainly used to stabilize the suspension state during polymerization.
  • the surfactant is not particularly limited as long as it is usually used in reverse phase suspension polymerization.
  • one or more surfactants selected from polyoxyethylene alkyl phenyl ether sulfates are used.
  • the amount of the surfactant is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the water-soluble unsaturated carboxylic acid monomer.
  • a small amount of surfactant may cause some problems in the stability of the suspension state during polymerization, and a large amount of surfactant tends to be economically disadvantageous.
  • the radical initiator is not particularly limited as long as it is used for ordinary radical polymerization, but potassium persulfate, ammonium persulfate, sodium persulfate, an azo-based initiator and the like are preferably used.
  • potassium persulfate, ammonium persulfate, sodium persulfate, an azo-based initiator and the like are preferably used.
  • 2,2'-azobis (2-methylpropionamidine) dihydrochloride can be used as the radical initiator.
  • the amount of the radical initiator is preferably 0.01 to 0.5% by mass, more preferably 0.02 to 0.2% by mass, based on the water-soluble unsaturated carboxylic acid monomer.
  • the amount of the radical initiator is within this range, the polymerization reaction can proceed more efficiently, and the obtained polymer is more excellent in thickening when used as a hydrophilic thickener.
  • the size of the droplets containing the water-soluble unsaturated carboxylic acid monomer and the like is closely related to the size of the obtained polymer particles.
  • a polymer of an appropriate size can be polymerized by performing reverse phase suspension polymerization at a stirring speed of 800 to 1000 rpm. It is likely that particles can be obtained.
  • the stirring speed during the polymerization reaction and controlling the size of the polymer particles (resin particles)
  • the medium particle size of the obtained resin particles can be adjusted. For example, resin particles having a size of 5 to 30 ⁇ m can be obtained.
  • the shape of the polymer particles thus obtained is spherical and is retained even in an aqueous liquid or a viscous substance such as cosmetics. Therefore, cosmetics using the polymer particles are good in various properties, touch and usability. It is thought to have an effect.
  • the medium particle size of the particles is the medium particle size of the volume average particle size measured by the laser diffraction method in which the particles are dispersed in n-hexane.
  • a measuring device laser diffraction type particle size distribution measuring device
  • SALD-2000A manufactured by Shimadzu Corporation
  • the medium particle size of the particles is preferably 5 to 30 ⁇ m, more preferably 5 to 25 ⁇ m, and even more preferably 6 to 20 ⁇ m.
  • the polymerization reaction temperature is, for example, 50 to 80 ° C.
  • the reaction time is, for example, 30 minutes to 3 hours.
  • the bath temperature can be adjusted to 60 ° C. to start the polymerization reaction.
  • the start of the polymerization reaction can be confirmed from the fact that the temperature inside the reaction vessel rises to about 70 ° C. due to the heat of polymerization.
  • the polymerization reaction is usually completed by carrying out the aging reaction for about 30 minutes to 3 hours.
  • the reaction may not be completed sufficiently and the amount of remaining water-soluble unsaturated carboxylic acid monomer may increase.
  • the product can be obtained by raising the bath temperature to distill off water and a petroleum-based hydrocarbon solvent in the reaction vessel.
  • the degree of neutralization of the polymer can be easily adjusted by neutralizing the carboxyl group of the water-soluble unsaturated carboxylic 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 the water-soluble unsaturated carboxylic 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 a water-soluble unsaturated carboxylic acid monomer in advance, a method of neutralizing a polymer obtained by polymerization, and the like.
  • the degree of neutralization of the polymer (A) is not particularly limited, but is preferably 70% or less or 60% or less, more preferably 50% or less or 45% or less, still more preferably 40% or less.
  • the amount of the water-soluble sucrose allyl ether used is not particularly limited, but is preferably 0.01 to 1 part by mass, preferably 0.05 to 0.8 parts by mass with respect to 100 parts by mass of the water-soluble unsaturated carboxylic acid monomer. Parts are more preferable, and 0.1 to 0.6 parts by mass are even more preferable.
  • the particles of the polymer (A) absorb water and swell in the composition of the present disclosure, so that the medium particle size thereof is preferably about 8 to 10 times that before compounding. ..
  • the medium particle size of the absorbed particles is preferably about 40 to 300 ⁇ m, more preferably about 50 to 250 ⁇ m.
  • the medium particle size is the medium particle size of the volume average particle size measured by the laser diffraction method.
  • a measuring device laser diffraction type particle size distribution measuring device
  • SALD-2000A manufactured by Shimadzu Corporation
  • the polymer (B) is a polymer obtained by polymerizing at least acrylic acid and / or methacrylic acid in the presence of pentaerythritol allyl ether.
  • acrylic acid and / or methacrylic acid means that either one of acrylic acid and methacrylic acid may be used alone, or both of them may be used in combination. It is synonymous with "(meth) acrylic acid”.
  • the polymer (B) can be obtained, for example, by a method including a step of polymerizing at least (meth) acrylic acid in the presence of pentaerythritol allyl ether.
  • the amount of pentaerythritol allyl ether used is 0.1 part by mass or more of pentaerythritol allyl ether with respect to 100 parts by mass of (meth) acrylic acid.
  • Adjusting the pH of the composition may cause a decrease in the viscosity of the composition at a low pH, which is not preferable. It is preferably about 0.1 to 2 parts by mass.
  • the upper or lower limit of the range is, for example, 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, 0.951, 1.1, 1.2, 1.3, 1.4, 1.5, 1. It may be 6, 1.7, 1.8, or 1.9 parts by mass. For example, it may be 0.1 to 1 part by mass or 0.2 to 0.9 part by mass.
  • pentaerythritol allyl ether can act as a cross-linking agent.
  • a (meth) acrylic acid alkyl ester having an alkyl group having 10 to 30 carbon atoms a polymer obtained by polymerizing (meth) acrylic acid and a (meth) acrylic acid alkyl ester having an alkyl group having 10 to 30 carbon atoms in the presence of pentaerythritol allyl ether is preferably used as the polymer (B).
  • the amount of the (meth) acrylic acid alkyl ester having 10 to 30 carbon atoms in the alkyl group can be, for example, about 0.5 to 5 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid.
  • the amount of the (meth) acrylic acid alkyl ester used is 0.5 to 10 parts by mass, preferably 0.5 to 5 parts by mass or 1 to 5 parts by mass with respect to 100 parts by mass of (meth) acrylic acid. It is more preferably 1 to 3 parts by mass.
  • 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.
  • Examples of the polymerization method for preparing the polymer (B) include a method of polymerizing in a polymerization solvent in the presence of a radical polymerization initiator.
  • 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.
  • the polymer (B) for example, the following polymers (B-1) and (B-2) are preferably used.
  • the polymer (B) can be preferably prepared by precipitation polymerization or reverse phase suspension polymerization. Furthermore, 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 solvent that dissolves (meth) acrylic acid, the (meth) acrylic acid alkyl ester, and pentaerythritol allyl ether, and does not dissolve the obtained polymer (B). Is preferable.
  • 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.
  • 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 is preferably 200 to 10000 parts by mass, more preferably 300 to 2000 parts by mass with respect to 100 parts by mass of (meth) acrylic acid.
  • 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 when carrying out the above-mentioned 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 (B). 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.
  • the reaction solution is heated to 80 to 130 ° C. to remove the polymerization solvent, whereby the white fine powder polymer (B) can be isolated.
  • the degree of neutralization of the polymer 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 neutralization degree of the polymer (B) is preferably lower than the neutralization degree of the polymer (A).
  • the degree of neutralization of the polymer (A) is preferably higher than the degree of neutralization of the polymer (B). This is lower than the neutralization degree of the polymer (A) when adjusting the pH of the polymer (A) -containing composition with the polymer (B), especially when it is desired to lower the pH of the polymer (A) -containing composition. This is because it is preferable to use the polymer (B) having a degree of neutralization.
  • the degree of neutralization of the polymer (B) is, for example, preferably 70% or less or 60% or less, more preferably 50% or less or 45% or less, still more preferably 40% or less. Those that are not neutralized (neutralization degree 0%) are also preferable.
  • the water contained in the composition of the present disclosure is not particularly limited, and for example, tap water, distilled water, ion-exchanged water, or the like can be used.
  • the pH of the composition of the present disclosure is 5.2 or less, preferably about 3.5 to 5.2, for example.
  • the upper or lower limit of the range is, for example, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4. It may be 6, 4.7, 4.8, 4.9, 5, or 5.1.
  • the pH may be about 4 to 5.1. pH is measured using a pH meter.
  • the viscosity of the composition of the present disclosure is 1000 mPa ⁇ s or more, preferably about 1000 to 50,000 mPa ⁇ s, for example.
  • the upper or lower limit of the range is, for example, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 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, It may be 38000, 39000, 40000, 41000, 42000, 43000, 44000, 45000, 46000, 47000, 48000, or 49000 mPa ⁇ s.
  • the range may be 1500 to 39000 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).
  • 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.
  • n-heptane 330 g was placed in a 2 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube, and a maleic anhydride-modified ethylene-propylene copolymer (Mitsui Chemicals Co., Ltd.) Company, High Wax 1105A) 1.0g and HLB3 sucrose stearic acid ester (Mitsubishi Chemical Foods Co., Ltd., Ryoto Sugar Ester S-370) 1.0g as a surfactant, and this is added to n-heptane. Dispersed and dissolved.
  • a maleic anhydride-modified ethylene-propylene copolymer Mitsubishi Chemicals Co., Ltd.
  • HLB3 sucrose stearic acid ester Mitsubishi Chemical Foods Co., Ltd., Ryoto Sugar Ester S-370
  • the water-soluble unsaturated carboxylic acid monomer aqueous solution prepared above was added thereto.
  • the bath temperature was maintained at 60 ° C., and the stirring speed was 1000, while nitrogen gas was blown into the solution to replace the nitrogen in the system in order to remove the atmosphere in the reaction vessel, the raw materials, and the oxygen present in the solvent.
  • the mixture was stirred at rotation / minute and polymerized by the reverse phase suspension polymerization method over 1 hour.
  • water and n-heptane were distilled off, and 67 g of a resin powder having a degree of neutralization of 0%, which is a polymer of acrylic acid and a sodium salt thereof and crosslinked with water-soluble sucrose allyl ether.
  • the resin may be referred to as polymer 2).
  • n-heptane 330 g was placed in a 2 L separable flask equipped with a stirrer, a reflux cooling tube, a dropping funnel and a nitrogen gas introduction tube, and a surfactant, maleic anhydride-modified ethylene-propylene co-weight.
  • a surfactant maleic anhydride-modified ethylene-propylene co-weight.
  • 1.0 g of coalescence Mitsubishi Chemicals Co., Ltd., High Wax 1105A
  • HLB3 sucrose stearic acid ester Mitsubishi Chemical Foods Co., Ltd., Ryoto Sugar Ester S-370
  • the water-soluble ethylene unsaturated monomer aqueous solution prepared above was added thereto.
  • the bath temperature was maintained at 60 ° C., and the stirring speed was 1000, while nitrogen gas was blown into the solution to replace the nitrogen in the system in order to remove the atmosphere in the reaction vessel, the raw materials, and the oxygen present in the solvent.
  • the mixture was stirred at rotation / minute and polymerized by the reverse phase suspension polymerization method over 1 hour.
  • water and n-heptane were distilled off, and 71 g of a resin powder having a degree of neutralization of 20%, which is a polymer of acrylic acid and a sodium salt thereof and crosslinked with water-soluble sucrose allyl ether.
  • the resin may be referred to as polymer 3).
  • each resin (polymers 2 to 7) was mixed with water to prepare each aqueous liquid (concentration 0.5% by mass).
  • each resin contained a sodium acrylate salt as a monomer unit
  • the mass% of the resin was calculated based on the mass of the monomer unit of acrylic acid.
  • the pH of each aqueous solution containing the polymers 3 to 7 was 4.8 to 7.0.
  • the pH was adjusted to 6.0 using a predetermined amount of 6% by mass sodium hydroxide aqueous solution as a neutralizing agent, and the resin concentration was 0.5% by mass. And said.
  • Polymer preparation (B) [Manufacturing example a] 45 g (0.625 mol) of acrylic acid, 0.27 g of pentaerythritol tetraallyl ether (PETA), 150 g of n-hexane in a 500 mL four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube and cooling tube. And 0.081 g (0.00035 mol) of 2,2'-azobismethylisobutyrate were 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.
  • PETA pentaerythritol tetraallyl ether
  • the carboxyvinyl polymer may be referred to as polymer a.
  • the uncrosslinked acrylic polymer was purchased and used. Specifically, "polyacrylic acid 5,000" and “polyacrylic acid 25,000” manufactured by Wako Pure Chemical Industries, Ltd. were purchased and used.
  • the former is an uncrosslinked polyacrylic acid having a weight average molecular weight of 5000
  • the latter is an uncrosslinked polyacrylic acid having a weight average molecular weight of 25,000.
  • the former may be referred to as polymer d
  • the latter may be referred to as polymer e.
  • 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 f.
  • each of the polymers a to f was dissolved / dispersed in ion-exchanged water so as to have a concentration of 0.5% by mass to obtain an aqueous polymer solution. Further, separately, the polymer 4 was mixed with ion-exchanged water at a concentration of 0.5% by mass to prepare a gel. To 100 g of the gel, 10 g of each polymer (polymers a to f) 0.5% by mass aqueous solution was sequentially added and mixed to prepare viscous compositions having different pH. Further, 1 g, 2 g, or 5 g of an aqueous citric acid solution (1% by mass) was added to 100 g of the gel to prepare viscous compositions having different pH.
  • the viscosity and pH of each of the obtained viscous compositions were 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. 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. The pH was measured using a pH meter. The results are shown in FIG.
  • a low molecular weight organic acid compound is used to adjust (particularly lower) the pH of the polymer obtained by polymerizing a water-soluble unsaturated carboxylic acid monomer in the presence of water-soluble sucrose allyl ether.
  • the viscosity did not decrease when a polymer obtained by polymerizing at least acrylic acid and / or methacrylic acid in the presence of pentaerythritol allyl ether was used.
  • the amount of pentaerythritol allyl ether is based on 100 parts by mass of the acrylic acid and / or methacrylic acid. It was also found that the effect is difficult to obtain unless it is about 0.1 part by mass or more.

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JPH10298541A (ja) * 1997-03-13 1998-11-10 B F Goodrich Co:The 改善された抗凍結性流体
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