WO2017164357A1 - Alkyl-modified carboxyl group-containing copolymer - Google Patents

Alkyl-modified carboxyl group-containing copolymer Download PDF

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Publication number
WO2017164357A1
WO2017164357A1 PCT/JP2017/011952 JP2017011952W WO2017164357A1 WO 2017164357 A1 WO2017164357 A1 WO 2017164357A1 JP 2017011952 W JP2017011952 W JP 2017011952W WO 2017164357 A1 WO2017164357 A1 WO 2017164357A1
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alkyl
mass
carboxyl group
modified carboxyl
containing copolymer
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PCT/JP2017/011952
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French (fr)
Japanese (ja)
Inventor
梨絵 中島
亮輔 村上
慎郷 井澤
慧 西口
美有 池田
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住友精化株式会社
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Publication of WO2017164357A1 publication Critical patent/WO2017164357A1/en

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    • 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

Definitions

  • the present invention relates to an alkyl-modified carboxyl group-containing copolymer, an emulsion stabilizer containing the copolymer, and an emulsion containing the copolymer.
  • a thickener for cosmetics for example, a moisturizer for emulsifiers, an emulsifier, and a suspension stabilizer
  • various co-polymers containing (meth) acrylic acid and (meth) acrylic acid alkyl ester as monomers are used.
  • a polymer is used.
  • examples of such a copolymer include a reaction product of a specific amount of an olefinically unsaturated carboxylic acid monomer and a specific amount of (meth) acrylic acid alkyl ester (the alkyl group has 10 to 30 carbon atoms).
  • a thing for example, refer to patent documents 1) is known.
  • Such a copolymer is also used as a stabilizer for stabilizing an O / W emulsion of a water-soluble component and an oil-soluble component in cosmetics and the like.
  • a conventional copolymer as a stabilizer, there is a problem that the O / W emulsion is separated into a water-soluble component and an oil-soluble component over time. For this reason, it is required to further improve the stability of the emulsion such that the O / W emulsion is difficult to separate into a water-soluble component and an oil-soluble component over time.
  • An object of the present invention is to provide an alkyl-modified carboxyl group-containing copolymer capable of improving the stability of an emulsion, an emulsion stabilizer containing the copolymer, and an emulsion containing the copolymer.
  • an alkyl-modified carboxyl group-containing copolymer in the range of 000 mPa ⁇ s to 7,500 mPa ⁇ s can improve the stability of an emulsion (particularly, an O / W emulsion).
  • the present invention provides an invention having the following configuration.
  • Item 1 100 parts by weight of (meth) acrylic acid (a), 1.0 to 5.0 parts by weight of (meth) acrylic acid alkyl ester (b) having an alkyl group having 18 to 24 carbon atoms, and an ethylenically unsaturated group
  • the viscosity of the 1% by weight neutralized viscous liquid of the copolymer is 20,000 mPa ⁇ s to 40,000 mPa ⁇ s at 25 ° C.
  • Viscosity when 1.0 part by mass of sodium chloride is added to 100 parts by mass of the 1% by weight neutralized viscous liquid is 4,000 mPa ⁇ s to 7,500 mPa ⁇ s at 25 ° C.
  • An alkyl-modified carboxyl group-containing copolymer Item 2.
  • the compound (c) having two or more ethylenically unsaturated groups is at least one selected from the group consisting of pentaerythritol polyallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, and polyallyl saccharose.
  • An emulsion stabilizer comprising the alkyl-modified carboxyl group-containing copolymer according to any one of Items 1 to 3.
  • the present invention can provide an alkyl-modified carboxyl group-containing copolymer capable of improving the stability of an emulsion, an emulsion stabilizer containing the copolymer, and an emulsion containing the copolymer.
  • the alkyl-modified carboxyl group-containing copolymer of the present invention comprises (meth) acrylic acid (a) 100 parts by mass and (meth) acrylic acid alkyl ester (b) 1.0 which has 18 to 24 carbon atoms in the alkyl group. It is a copolymer of a monomer containing -5.0 parts by mass and 0.45 parts by mass or more of the compound (c) having two or more ethylenically unsaturated groups, and further 1 mass of the copolymer.
  • % Neutralized viscous liquid has a viscosity of 20,000 mPa ⁇ s to 40,000 mPa ⁇ s at 25 ° C., and 1.0 part by mass with respect to 100 parts by mass of the 1% by mass neutralized viscous liquid. Viscosity when sodium chloride is added is 4,000 mPa ⁇ s to 7,500 mPa ⁇ s at 25 ° C.
  • the alkyl-modified carboxyl group-containing copolymer of the present invention, the emulsion stabilizer containing the copolymer, and the emulsion containing the copolymer will be described in detail.
  • the “acrylic acid and methacrylic acid” are collectively referred to as “(meth) acrylic acid”.
  • the “neutralized viscous liquid” means an alkyl-modified carboxyl group-containing copolymer so that the pH of the aqueous dispersion of the alkyl-modified carboxyl group-containing copolymer is 6.5 to 7.5. It means a viscous liquid obtained by mixing an aqueous solution of sodium hydroxide with a combined aqueous dispersion.
  • the “1% by mass neutralized viscous liquid” means a neutralized viscous liquid in which the proportion of the alkyl-modified carboxyl group-containing copolymer is 1% by mass.
  • the alkyl-modified carboxyl group-containing copolymer of the present invention comprises (meth) acrylic acid (hereinafter sometimes referred to as component (a)) and a (meth) acrylic acid alkyl ester having an alkyl group having 18 to 24 carbon atoms. It is a copolymer of a compound (hereinafter sometimes referred to as component (b)) and a compound having two or more ethylenically unsaturated groups (hereinafter sometimes referred to as component (c)). That is, the alkyl-modified carboxyl group-containing copolymer of the present invention is a polymer obtained by copolymerizing at least components (a), (b), and (c).
  • (meth) acrylic acid (component (a)) at least one of acrylic acid and methacrylic acid can be used.
  • the alkyl group (meth) acrylic acid alkyl ester (component (b)) having an alkyl group with 18 to 24 carbon atoms reacts (meth) acrylic acid with a higher alcohol having an alkyl group with 18 to 24 carbon atoms.
  • component (b) include stearyl (meth) acrylate, eicosanyl (meth) acrylate, behenyl (meth) acrylate, and tetracosanyl (meth) acrylate.
  • stearyl methacrylate, eicosanyl methacrylate, behenyl methacrylate, tetracosanyl methacrylate and the like are preferably used from the viewpoint of obtaining higher stability of the emulsion of the water-soluble component and the oil-soluble component.
  • component (b) constituting the monomer one type may be used, or two or more types may be used.
  • component (b) for example, trade name Blemmer VMA-70 manufactured by Nippon Oil & Fats Co., Ltd. (stearyl methacrylate is 10 to 20 parts by mass, eicosanyl methacrylate is 10 parts by mass)
  • stearyl methacrylate is 10 to 20 parts by mass
  • eicosanyl methacrylate is 10 parts by mass
  • To 20 parts by mass 59 to 80 parts by mass of behenyl methacrylate, and 1 part by mass or less of tetracosanyl methacrylate) can be used.
  • the proportion of component (b) in the alkyl-modified carboxyl group-containing copolymer of the present invention is 1 to 5 parts by mass with respect to 100 parts by mass of (meth) acrylic acid (component (a)). From the viewpoint of further improving the stability of the emulsion, the ratio of the component (b) is preferably 1 part by mass to 3 parts by mass with respect to 100 parts by mass of the component (a). When the proportion of component (b) is less than 1 part by mass relative to 100 parts by mass of component (a), the alkyl-modified carboxyl group-containing copolymer may be insufficient in stabilizing the emulsion. There is.
  • the alkyl-modified carboxyl group-containing copolymer when the proportion of the component (b) exceeds 5 parts by mass with respect to 100 parts by mass of the component (a), when the alkyl-modified carboxyl group-containing copolymer is dispersed in water (for example, water-soluble component and oil-soluble As a stabilizer for the emulsion of the component, the alkyl-modified carboxyl group-containing copolymer may be agglomerated when the copolymer is dispersed in water.
  • water for example, water-soluble component and oil-soluble As a stabilizer for the emulsion of the component
  • the compound having two or more ethylenically unsaturated groups is a compound having two or more ethylenically unsaturated groups having polymerizability.
  • Preferred specific examples of the component (c) include pentaerythritol polyallyl ethers such as pentaerythritol diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, polyallyl saccharose and the like. is there.
  • the component (c) one type may be used, or two or more types may be used.
  • the component (c) is composed of pentaerythritol polyallyl ether, diethylene glycol diallyl ether, polyethylene because the viscosity of the neutralized viscous liquid of the alkyl-modified carboxyl group-containing copolymer can be easily adjusted within a predetermined range. It preferably contains at least one selected from the group consisting of glycol diallyl ether and polyallyl saccharose.
  • the proportion of component (c) in the alkyl-modified carboxyl group-containing copolymer of the present invention is 0.45 parts by mass or more with respect to 100 parts by mass of (meth) acrylic acid (component (a)). From the viewpoint of further improving the stability of the emulsion, the ratio of the component (c) is preferably 0.47 parts by mass or more. When the proportion of component (c) is less than 0.45 parts by mass, the effect of stabilizing the emulsion over time by the alkyl-modified carboxyl group-containing copolymer may be insufficient.
  • the proportion of the component (c) is preferably 10 parts by mass or less, preferably 3 parts by mass or less with respect to 100 parts by mass of (meth) acrylic acid (component (a)). Is more preferable.
  • the proportion of the component (c) is 10 parts by mass or less, the resulting alkyl-modified carboxyl group-containing copolymer is dispersed in water (for example, as a stabilizer for an emulsion of a water-soluble component and an oil-soluble component, When the copolymer is dispersed in water), the alkyl-modified carboxyl group-containing copolymer can be prevented from agglomerating.
  • the alkyl-modified carboxyl group-containing copolymer of the present invention includes monomers (components) other than the components (a), (b), and (c).
  • (A), (b), and (c) another monomer copolymerizable with at least one kind) may be copolymerized.
  • the viscosity of the 1% by weight neutralized viscous liquid of the alkyl-modified carboxyl group-containing copolymer of the present invention (hereinafter sometimes referred to as “1% viscosity”) is 20,000 mPa ⁇ s to 40,000 mPa at 25 ° C. -Within the range of s From the viewpoint of further improving the stability of the emulsion of the water-soluble component and the oil-soluble component, the 1% viscosity is preferably in the range of 25,000 mPa ⁇ s to 35,000 mPa ⁇ s.
  • 1% viscosity means a value measured by the method described in [Evaluation Method] in the Examples.
  • the viscosity (hereinafter referred to as “salt-resistant viscosity” when 1.0 part by mass of sodium chloride is added to 100 parts by mass of the 1% by mass neutralized viscous liquid.
  • the salt-resistant viscosity is preferably in the range of 4,500 mPa ⁇ s to 7,000 mPa ⁇ s.
  • salt-resistant viscosity When the salt-resistant viscosity is less than 4,000 mPa ⁇ s or more than 7,500 mPa ⁇ s, the emulsion is easily separated.
  • salt-resistant viscosity means the value measured by the method as described in [Evaluation method] of an Example.
  • the 1% viscosity of the alkyl-modified carboxyl group-containing copolymer of the present invention can be controlled by, for example, increasing or decreasing the ratio of the compound having two or more ethylenically unsaturated groups (component (c)). Specifically, the 1% viscosity of the alkyl-modified carboxyl group-containing copolymer can be increased by increasing the proportion of the component (c) constituting the copolymer. Moreover, the 1% viscosity of the alkyl-modified carboxyl group-containing copolymer can be lowered by reducing the proportion of the component (c).
  • the salt-resistant viscosity of the alkyl-modified carboxyl group-containing copolymer of the present invention can be controlled by, for example, the concentration of all monomers used for polymerization with respect to the solvent and the reaction temperature. Specifically, the salt-resistant viscosity of the alkyl-modified carboxyl group-containing copolymer can be increased by increasing the concentration of all monomers used in the polymerization with respect to the solvent or by decreasing the polymerization temperature. Moreover, the salt-resistant viscosity of the alkyl-modified carboxyl group-containing copolymer can be lowered by lowering the concentration or raising the polymerization temperature.
  • the method for producing the alkyl-modified carboxyl group-containing copolymer of the present invention is not particularly limited, and a raw material containing at least the aforementioned components (a), (b), and (c) and a polymerization initiator are added to the solvent. There is a method in which a solution is heated and polymerized while stirring under an inert gas atmosphere.
  • the inert gas for making the inert gas atmosphere is not particularly limited, and examples thereof include nitrogen gas and argon gas.
  • the solvent dissolves at least the components (a), (b), and (c), but does not dissolve the alkyl-modified carboxyl group-containing copolymer to be formed and does not inhibit the copolymerization reaction.
  • the 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, Examples include ethyl methyl ketone and isobutyl methyl ketone.
  • a solvent may be used by 1 type and may be used in combination of 2 or more type.
  • these solvents normal hexane, normal heptane, cyclohexane, ethylene dichloride, ethyl acetate, and the like are preferably used from the viewpoint of stable quality and easy availability.
  • the amount of the solvent used is 100 parts by weight of component (a) from the viewpoint of adjusting the salt-resistant viscosity of the alkyl-modified carboxyl group-containing copolymer to the above range, from the viewpoint of improving the stirring operability, and from the viewpoint of economy. On the other hand, it is preferably 300 to 5,000 parts by mass.
  • a radical polymerization initiator for example, a radical polymerization initiator is preferable.
  • the polymerization initiator include ⁇ , ⁇ ′-azoisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, dimethyl-2,2′-azobisisobutyrate, peroxide Examples include benzoyl, lauroyl peroxide, cumene hydroperoxide, and tertiary butyl hydroperoxide.
  • a polymerization initiator may be used by 1 type and may be used in combination of 2 or more types.
  • the amount of the polymerization initiator used is preferably 0.01 parts by mass to 0.45 parts by mass, more preferably 0.01 parts by mass with respect to 100 parts by mass of the component (a) from the viewpoint of keeping the reaction rate moderately. Is 0.35 parts by mass.
  • the polymerization temperature is preferably about 50 ° C. to 90 ° C., more preferably about 55 ° C. to 85 ° C. from the viewpoint of keeping the polymerization rate moderate.
  • the polymerization time varies depending on the polymerization temperature and the like, but is usually about 0.5 to 10 hours.
  • the slurry liquid after polymerization is heated to, for example, 80 ° C. to 130 ° C. to remove the solvent, whereby the alkyl-modified carboxyl group-containing copolymer of the present invention is removed. Coalescence can be obtained.
  • the alkyl-modified carboxyl group-containing copolymer of the present invention By using the alkyl-modified carboxyl group-containing copolymer of the present invention, a highly stable emulsion (in particular, an O / W emulsion) can be obtained. Therefore, the emulsion stabilizer containing the alkyl-modified carboxyl group-containing copolymer of the present invention as an essential component is useful as a stabilizer for emulsions (particularly, O / W emulsions).
  • the emulsion stabilizer of the present invention is characterized by containing the above-mentioned alkyl-modified carboxyl group-containing copolymer of the present invention.
  • the emulsion stabilizer of the present invention may be formed only from the alkyl-modified carboxyl group-containing copolymer of the present invention.
  • the emulsion of the present invention is characterized by including the alkyl-modified carboxyl group-containing copolymer of the present invention. That is, the emulsion of the present invention contains the alkyl-modified carboxyl group-containing copolymer of the present invention as an emulsion stabilizer.
  • the content of the alkyl-modified carboxyl group-containing copolymer of the present invention in the emulsion of the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass from the viewpoint of improving the stability of the emulsion. To 1% by mass.
  • the emulsion of the present invention is an emulsion of a water-soluble component and an oil-soluble component, and particularly preferably an O / W type emulsion.
  • the water-soluble component may be any component that is soluble in water.
  • known ingredients blended in cosmetics such as lower alcohols, polyhydric alcohols, water-soluble polymers, water-soluble surfactants, humectants, medicinal ingredients, pH adjusters, antioxidants, and coloring materials are added to water. can do.
  • the oil-soluble component may be any component that can be separated from water to form an emulsion.
  • known components blended in cosmetics such as hydrocarbons, esters and higher fatty acids can be used as oil-soluble components.
  • the emulsion of the present invention can be a cosmetic containing a cosmetic ingredient.
  • Example 1 In a 500 mL four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube and cooling tube, 45 g of acrylic acid, Blemmer VMA70 (manufactured by NOF Corporation: 10-20 parts by mass of stearyl methacrylate, eicosanyl methacrylate) 0.99 g of a mixture of 10 to 20 parts by mass, 59 to 80 parts by mass of behenyl methacrylate and 1 part by mass or less of tetracosanyl methacrylate), pentaerythritol polyallyl ether (pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) Mixture) 0.203 g, normal heptane 163.2 g, ethyl acetate 54 g and 2,2′-azobismethylisobutyrate 0.025 g were charged.
  • Blemmer VMA70 manufactured by NOF Corporation: 10-20
  • Example 2 In Example 1, except that the amount of pentaerythritol polyallyl ether (a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) was changed to 0.225 g, a white powder form was obtained. 44 g of an alkyl-modified carboxyl group-containing copolymer was obtained.
  • Example 3 In Example 1, a white powder form was obtained in the same manner as in Example 1 except that the amount of pentaerythritol polyallyl ether (a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) was changed to 0.248 g. 43 g of an alkyl-modified carboxyl group-containing copolymer was obtained.
  • pentaerythritol polyallyl ether a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether
  • Example 4 In Example 1, except that the amount of pentaerythritol polyallyl ether (a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) was changed to 0.270 g, a white powder form was obtained. 43 g of an alkyl-modified carboxyl group-containing copolymer was obtained.
  • Example 5 In Example 1, except that the usage amount of pentaerythritol polyallyl ether (a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) was changed to 0.225 g and the usage amount of Blemmer VMA70 was changed to 0.45 g. In the same manner as in Example 1, 44 g of a white powdery alkyl-modified carboxyl group-containing copolymer was obtained.
  • pentaerythritol polyallyl ether a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether
  • Example 6 In Example 1, except that the usage amount of pentaerythritol polyallyl ether (a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) was changed to 0.225 g and the usage amount of Blemmer VMA70 was changed to 2.25 g. In the same manner as in Example 1, 45 g of a white powdery alkyl-modified carboxyl group-containing copolymer was obtained.
  • pentaerythritol polyallyl ether a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether
  • Example 7 A 500 mL five-necked flask equipped with a stirrer, a thermometer, a nitrogen blowing tube, an addition device, and a cooling tube was prepared.
  • Bremer VMA70 manufactured by NOF Corporation: 10-20 parts by mass of stearyl methacrylate, 10-20 parts by mass of eicosanyl methacrylate, 59-80 parts by mass of behenyl methacrylate, and 1 part by mass or less of tetracosanyl methacrylate 1.1 g of mixture, 104 g of normal heptane, 35 g of ethyl acetate, and 0.030 g of 2,2′-azobismethylisobutyrate, and 50 g of acrylic acid and pentaerythritol polyallyl ether (pentaerythritol triallyl) were added to the addition apparatus.
  • the contents of the flask were stirred for 1 hour in an oil bath set so that the temperature of the contents of the flask was 70 to 73 ° C. Thereafter, the set temperature of the oil bath was set to 110 ° C., the flask was heated, and normal heptane and ethyl acetate were removed from the flask. Thereafter, the contents of the flask were transferred to a vacuum dryer (Yamato, vacuum dry oven DP33), the oven set temperature was set to 115 ° C., the set pressure was set to 10 mmHg and dried for 8 hours, 49 g of an alkyl-modified carboxyl group-containing copolymer was obtained.
  • a vacuum dryer Yamamoto, vacuum dry oven DP33
  • Example 8 In Example 7, except that the amount of pentaerythritol polyallyl ether (a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) charged in the addition apparatus was changed to 0.263 g, the same as in Example 7. As a result, 47 g of a white powdery alkyl-modified carboxyl group-containing copolymer was obtained.
  • pentaerythritol polyallyl ether a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether
  • Example 9 In Example 7, the amount of pentaerythritol polyallyl ether (a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) charged in the addition apparatus was changed to 0.25 g, and 1.5 g instead of 1.1 g of Bremer VMA70. 49 g of a white powdery alkyl-modified carboxyl group-containing copolymer was obtained in the same manner as in Example 7 except that the stearyl methacrylate was used.
  • pentaerythritol polyallyl ether a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether
  • Example 7 (Comparative Example 1) In Example 7, the amount of normal heptane charged in the reaction vessel was 82 g, the amount of ethyl acetate used was 27 g, and the pentaerythritol polyallyl ether (mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) charged in the addition device was used. ) was changed to 0.25 g in the same manner as in Example 7 to obtain 47 g of a white powdery alkyl-modified carboxyl group-containing copolymer.
  • Example 7 (Comparative Example 2) In Example 7, after the start of dropping, the setting of the oil bath was changed so that the temperature of the contents in the flask would be 76 to 79 ° C., and after the dropping of the mixture charged in the addition apparatus was completed, 46 g of a white powdery alkyl-modified carboxyl group-containing copolymer was obtained in the same manner as in Example 7 except that the setting of the oil bath was changed so that the temperature of the contents was 76 to 79 ° C.
  • Example 7 (Comparative Example 3) In Example 7, the amount of normal heptane charged in the reaction vessel was changed to 82 g, the amount of ethyl acetate used was changed to 27 g, and after the addition was started, the temperature of the contents in the flask was 67-70 ° C. After changing the setting of the oil bath and dropping of the mixture charged in the adding device is completed, the setting of the oil bath is changed so that the temperature of the contents in the flask becomes 67 to 70 ° C., and the stirring time is set to 2.5 hours A white powdery alkyl-modified carboxyl group-containing copolymer 47 g was obtained in the same manner as in Example 7 except for the change.
  • Example 4 In Example 1, the amount of pentaerythritol polyallyl ether (a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) was changed to 0.27 g, and the temperature of the contents was 79 to 84 after the dropping was started. Set the oil bath to °C and after the addition of the mixture charged in the addition device is completed, set the oil bath so that the temperature of the flask contents is 79 to 84 °C and set the contents of the flask for 1 hour. Except that the product was stirred, 42 g of a white powdery alkyl-modified carboxyl group-containing copolymer was obtained in the same manner as in Example 1.
  • pentaerythritol polyallyl ether a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether
  • Example 5 (Comparative Example 5) In Example 1, except that the amount of pentaerythritol polyallyl ether (a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) was changed to 0.18 g, a white powder form was obtained. 43 g of an alkyl-modified carboxyl group-containing copolymer was obtained.
  • pentaerythritol polyallyl ether a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether
  • Example 6 (Comparative Example 6) In Example 1, except that the usage amount of pentaerythritol polyallyl ether (a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) was changed to 0.225 g, and the usage amount of Blemmer VMA70 was changed to 0.225 g. In the same manner as in Example 1, 42 g of a white powdery alkyl-modified carboxyl group-containing copolymer was obtained.
  • pentaerythritol polyallyl ether a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether
  • Example 7 (Comparative Example 7) In Example 1, except that the usage amount of pentaerythritol polyallyl ether (a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) was changed to 0.225 g, and the usage amount of Blemmer VMA70 was changed to 2.475 g. In the same manner as in Example 1, 42 g of a white powdery alkyl-modified carboxyl group-containing copolymer was obtained.
  • pentaerythritol polyallyl ether a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether

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Abstract

To provide an alkyl-modified carboxyl group-containing copolymer capable of stabilizing an emulsion of a water-soluble component and an oil-soluble component. The alkyl-modified carboxyl group-containing copolymer includes a monomer containing 100 parts by mass of (meth)acrylic acid (a), 1.0-5.0 parts by mass of a (meth)acrylic acid alkyl ester (b) the alkyl group of which has 18-24 carbon atoms, and 0.45 parts by mass or more of a compound (c) having two or more ethylenically unsaturated groups, wherein a 1-mass% neutralized viscous liquid of the copolymer has a viscosity of 20,000-40,000 mPa·s at 25°C, and when 1.0 parts by mass of sodium chloride is added to 100 parts by mass of the 1-mass% neutralized viscous liquid, the resultant viscous liquid has a viscosity of 4,000-7,500 mPa·s at 25°C.

Description

アルキル変性カルボキシル基含有共重合体Alkyl-modified carboxyl group-containing copolymer
　本発明は、アルキル変性カルボキシル基含有共重合体、当該共重合体を含むエマルジョン安定化剤、及び当該共重合体を含むエマルジョンに関する。 The present invention relates to an alkyl-modified carboxyl group-containing copolymer, an emulsion stabilizer containing the copolymer, and an emulsion containing the copolymer.
　従来、例えば、化粧品用の増粘剤、パップ剤用の保湿剤、乳化剤、および懸濁安定剤には、（メタ）アクリル酸と（メタ）アクリル酸アルキルエステルを単量体とした種々の共重合体が用いられている。このような共重合体としては、例えば、特定量のオレフィン系不飽和カルボン酸単量体と、特定量の（メタ）アクリル酸アルキルエステル（アルキル基の炭素数が１０～３０）との反応生成物（例えば、特許文献１を参照）が知られている。 Conventionally, for example, as a thickener for cosmetics, a moisturizer for emulsifiers, an emulsifier, and a suspension stabilizer, various co-polymers containing (meth) acrylic acid and (meth) acrylic acid alkyl ester as monomers are used. A polymer is used. Examples of such a copolymer include a reaction product of a specific amount of an olefinically unsaturated carboxylic acid monomer and a specific amount of (meth) acrylic acid alkyl ester (the alkyl group has 10 to 30 carbon atoms). A thing (for example, refer to patent documents 1) is known.
特開昭５１－６１９０号公報Japanese Patent Laid-Open No. 51-6190
　このような共重合体は、化粧品等では水溶成分と油溶成分とのＯ／Ｗエマルジョンを安定化させるための安定化剤としても使用されている。しかしながら、従来の共重合体を安定化剤とした化粧品等においては、時間が経過したときにＯ／Ｗエマルジョンが水溶成分と油溶成分とに分離するなどの問題がある。このため、時間が経過したときにＯ／Ｗエマルジョンが水溶成分と油溶成分とに分離しにくいというエマルジョンの安定性をさらに向上させることが求められる。 Such a copolymer is also used as a stabilizer for stabilizing an O / W emulsion of a water-soluble component and an oil-soluble component in cosmetics and the like. However, in cosmetics and the like using a conventional copolymer as a stabilizer, there is a problem that the O / W emulsion is separated into a water-soluble component and an oil-soluble component over time. For this reason, it is required to further improve the stability of the emulsion such that the O / W emulsion is difficult to separate into a water-soluble component and an oil-soluble component over time.
　本発明の目的は、エマルジョンの安定性を向上できるアルキル変性カルボキシル基含有共重合体、当該共重合体を含むエマルジョン安定化剤、及び共重合体を含むエマルジョンを提供することである。 An object of the present invention is to provide an alkyl-modified carboxyl group-containing copolymer capable of improving the stability of an emulsion, an emulsion stabilizer containing the copolymer, and an emulsion containing the copolymer.
　本発明者らは、上記課題を解決するために鋭意検討した。その結果、（メタ）アクリル酸（ａ）１００質量部と、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（ｂ）１．０～５．０質量部と、エチレン性不飽和基を２個以上有する化合物（ｃ）０．４５質量部以上とを含む単量体の共重合体であって、当該共重合体の１質量％中和粘稠液の粘度が２０，０００ｍＰａ・ｓ～４０，０００ｍＰａ・ｓの範囲内にあり、かつ、当該１質量％中和粘稠液１００質量部に対して１．０質量部の塩化ナトリウムを添加したときの粘度が、４，０００ｍＰａ・ｓ～７，５００ｍＰａ・ｓの範囲内であるアルキル変性カルボキシル基含有共重合体は、エマルジョン（特に、Ｏ／Ｗ型エマルジョン）の安定性を向上できることを見出した。 The present inventors diligently studied to solve the above problems. As a result, 100 parts by mass of (meth) acrylic acid (a), 1.0 to 5.0 parts by mass of (meth) acrylic acid alkyl ester (b) having an alkyl group having 18 to 24 carbon atoms, ethylenic properties A monomer copolymer containing at least 0.45 parts by mass of the compound (c) having two or more unsaturated groups, wherein the viscosity of the 1% by weight neutralized viscous liquid of the copolymer is 20, The viscosity when 1.0 part by mass of sodium chloride is added to 100 parts by mass of the 1% by mass neutralized viscous liquid is in the range of 000 mPa · s to 40,000 mPa · s. It has been found that an alkyl-modified carboxyl group-containing copolymer in the range of 000 mPa · s to 7,500 mPa · s can improve the stability of an emulsion (particularly, an O / W emulsion).
　すなわち、本発明は、下記の構成を備える発明を提供する。
項１．　（メタ）アクリル酸（ａ）１００質量部と、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（ｂ）１．０～５．０質量部と、エチレン性不飽和基を２個以上有する化合物（ｃ）０．４５質量部以上とを含む単量体の共重合体であり、
　前記共重合体の１質量％中和粘稠液の粘度が、２５℃において、２０，０００ｍＰａ・ｓ～４０，０００ｍＰａ・ｓであり、
　前記１質量％中和粘稠液１００質量部に対して１．０質量部の塩化ナトリウムを添加したときの粘度が、２５℃において、４，０００ｍＰａ・ｓ～７，５００ｍＰａ・ｓである、
　アルキル変性カルボキシル基含有共重合体。
項２．　前記エチレン性不飽和基を２個以上有する化合物（ｃ）が、ペンタエリスリトールポリアリルエーテル、ジエチレングリコールジアリルエーテル、ポリエチレングリコールジアリルエーテル、及びポリアリルサッカロースからなる群より選ばれた少なくとも１種である、項１に記載のアルキル変性カルボキシル基含有共重合体。
項３．　前記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（ｂ）が、（メタ）アクリル酸ステアリルを含む、項１または２に記載のアルキル変性カルボキシル基含有共重合体。
項４．　項１～３のいずれかに記載のアルキル変性カルボキシル基含有共重合体を含む、エマルジョン安定化剤。
項５．　項１～３のいずれかに記載のアルキル変性カルボキシル基含有共重合体を含む、エマルジョン。 That is, the present invention provides an invention having the following configuration.
Item 1. 100 parts by weight of (meth) acrylic acid (a), 1.0 to 5.0 parts by weight of (meth) acrylic acid alkyl ester (b) having an alkyl group having 18 to 24 carbon atoms, and an ethylenically unsaturated group A copolymer of monomers containing at least 0.45 parts by mass of the compound (c) having two or more of
The viscosity of the 1% by weight neutralized viscous liquid of the copolymer is 20,000 mPa · s to 40,000 mPa · s at 25 ° C.,
Viscosity when 1.0 part by mass of sodium chloride is added to 100 parts by mass of the 1% by weight neutralized viscous liquid is 4,000 mPa · s to 7,500 mPa · s at 25 ° C.
An alkyl-modified carboxyl group-containing copolymer.
Item 2. The compound (c) having two or more ethylenically unsaturated groups is at least one selected from the group consisting of pentaerythritol polyallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, and polyallyl saccharose. 2. The alkyl-modified carboxyl group-containing copolymer according to 1.
Item 3. Item 3. The alkyl-modified carboxyl group-containing copolymer according to Item 1 or 2, wherein the alkyl group (meth) acrylic acid alkyl ester (b) having 18 to 24 carbon atoms includes stearyl (meth) acrylate.
Item 4. Item 5. An emulsion stabilizer comprising the alkyl-modified carboxyl group-containing copolymer according to any one of Items 1 to 3.
Item 5. Item 5. An emulsion comprising the alkyl-modified carboxyl group-containing copolymer according to any one of Items 1 to 3.
　本発明は、エマルジョンの安定性を向上できるアルキル変性カルボキシル基含有共重合体、当該共重合体を含むエマルジョン安定化剤、及び当該共重合体を含むエマルジョンを提供できる。 The present invention can provide an alkyl-modified carboxyl group-containing copolymer capable of improving the stability of an emulsion, an emulsion stabilizer containing the copolymer, and an emulsion containing the copolymer.
　本発明のアルキル変性カルボキシル基含有共重合体は、（メタ）アクリル酸（ａ）１００質量部と、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（ｂ）１．０～５．０質量部と、エチレン性不飽和基を２個以上有する化合物（ｃ）０．４５質量部以上とを含む単量体の共重合体であり、さらに、当該共重合体の１質量％中和粘稠液の粘度が、２５℃において、２０，０００ｍＰａ・ｓ～４０，０００ｍＰａ・ｓであり、かつ、当該１質量％中和粘稠液１００質量部に対して１．０質量部の塩化ナトリウムを添加したときの粘度が、２５℃において、４，０００ｍＰａ・ｓ～７，５００ｍＰａ・ｓであることを特徴とする。以下、本発明のアルキル変性カルボキシル基含有共重合体、当該共重合体を含むエマルジョン安定化剤、及び当該共重合体を含むエマルジョンについて、詳述する。 The alkyl-modified carboxyl group-containing copolymer of the present invention comprises (meth) acrylic acid (a) 100 parts by mass and (meth) acrylic acid alkyl ester (b) 1.0 which has 18 to 24 carbon atoms in the alkyl group. It is a copolymer of a monomer containing -5.0 parts by mass and 0.45 parts by mass or more of the compound (c) having two or more ethylenically unsaturated groups, and further 1 mass of the copolymer. % Neutralized viscous liquid has a viscosity of 20,000 mPa · s to 40,000 mPa · s at 25 ° C., and 1.0 part by mass with respect to 100 parts by mass of the 1% by mass neutralized viscous liquid. Viscosity when sodium chloride is added is 4,000 mPa · s to 7,500 mPa · s at 25 ° C. Hereinafter, the alkyl-modified carboxyl group-containing copolymer of the present invention, the emulsion stabilizer containing the copolymer, and the emulsion containing the copolymer will be described in detail.
　なお、本発明において、「アクリル酸及びメタクリル酸」を総称して「（メタ）アクリル酸」という。また、本発明において、「中和粘稠液」とは、アルキル変性カルボキシル基含有共重合体の水分散液のｐＨが６．５～７．５となるように、アルキル変性カルボキシル基含有共重合体の水分散液に水酸化ナトリウムの水溶液を混合して得られた粘性液体を意味する。また、本発明において、「１質量％中和粘稠液」とは、アルキル変性カルボキシル基含有共重合体の割合が１質量％である中和粘稠液を意味する。 In the present invention, “acrylic acid and methacrylic acid” are collectively referred to as “(meth) acrylic acid”. In the present invention, the “neutralized viscous liquid” means an alkyl-modified carboxyl group-containing copolymer so that the pH of the aqueous dispersion of the alkyl-modified carboxyl group-containing copolymer is 6.5 to 7.5. It means a viscous liquid obtained by mixing an aqueous solution of sodium hydroxide with a combined aqueous dispersion. In the present invention, the “1% by mass neutralized viscous liquid” means a neutralized viscous liquid in which the proportion of the alkyl-modified carboxyl group-containing copolymer is 1% by mass.
　本発明のアルキル変性カルボキシル基含有共重合体は、（メタ）アクリル酸（以下、成分（ａ）ということがある）と、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（以下、成分（ｂ）ということがある）と、エチレン性不飽和基を２個以上有する化合物（以下、成分（ｃ）ということがある）との共重合体である。すなわち、本発明のアルキル変性カルボキシル基含有共重合体は、少なくとも、成分（ａ）、（ｂ）、及び（ｃ）を共重合した重合体である。 The alkyl-modified carboxyl group-containing copolymer of the present invention comprises (meth) acrylic acid (hereinafter sometimes referred to as component (a)) and a (meth) acrylic acid alkyl ester having an alkyl group having 18 to 24 carbon atoms. It is a copolymer of a compound (hereinafter sometimes referred to as component (b)) and a compound having two or more ethylenically unsaturated groups (hereinafter sometimes referred to as component (c)). That is, the alkyl-modified carboxyl group-containing copolymer of the present invention is a polymer obtained by copolymerizing at least components (a), (b), and (c).
　本発明において、（メタ）アクリル酸（成分（ａ））としては、アクリル酸及びメタクリル酸の少なくとも一方を使用することができる。 In the present invention, as (meth) acrylic acid (component (a)), at least one of acrylic acid and methacrylic acid can be used.
　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（成分（ｂ））は、（メタ）アクリル酸と、アルキル基の炭素数が１８～２４である高級アルコールとを反応させて得られるエステルである。成分（ｂ）の具体例としては、（メタ）アクリル酸ステアリル、（メタ）アクリル酸エイコサニル、（メタ）アクリル酸ベヘニル、（メタ）アクリル酸テトラコサニルなどがある。これらの成分（ｂ）の中でも、水溶成分と油溶成分とのエマルジョンのより高い安定性を得る観点から、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等が好適に用いられる。 The alkyl group (meth) acrylic acid alkyl ester (component (b)) having an alkyl group with 18 to 24 carbon atoms reacts (meth) acrylic acid with a higher alcohol having an alkyl group with 18 to 24 carbon atoms. The resulting ester. Specific examples of component (b) include stearyl (meth) acrylate, eicosanyl (meth) acrylate, behenyl (meth) acrylate, and tetracosanyl (meth) acrylate. Among these components (b), stearyl methacrylate, eicosanyl methacrylate, behenyl methacrylate, tetracosanyl methacrylate and the like are preferably used from the viewpoint of obtaining higher stability of the emulsion of the water-soluble component and the oil-soluble component.
　本発明のアルキル変性カルボキシル基含有共重合体において、単量体を構成している成分（ｂ）は、１種類を用いてもよいし、２種類以上を用いてもよい。成分（ｂ）を２種類以上用いて共重合するときは、例えば、日本油脂株式会社製の商品名ブレンマーＶＭＡ－７０（メタクリル酸ステアリルが１０質量部～２０質量部、メタクリル酸エイコサニルが１０質量部～２０質量部、メタクリル酸ベヘニルが５９質量部～８０質量部及びメタクリル酸テトラコサニルが１質量部以下の混合物）を用いることができる。 In the alkyl-modified carboxyl group-containing copolymer of the present invention, as the component (b) constituting the monomer, one type may be used, or two or more types may be used. When copolymerizing using two or more types of component (b), for example, trade name Blemmer VMA-70 manufactured by Nippon Oil & Fats Co., Ltd. (stearyl methacrylate is 10 to 20 parts by mass, eicosanyl methacrylate is 10 parts by mass) To 20 parts by mass, 59 to 80 parts by mass of behenyl methacrylate, and 1 part by mass or less of tetracosanyl methacrylate) can be used.
　本発明のアルキル変性カルボキシル基含有共重合体における成分（ｂ）の割合は、（メタ）アクリル酸（成分（ａ））１００質量部に対して、１質量部～５質量部である。エマルジョンの安定性をより高める観点からは、成分（ｂ）の割合は、成分（ａ）１００質量部に対して、１質量部～３質量部が好ましい。なお、成分（ｂ）の割合が、成分（ａ）１００質量部に対して１質量部未満であるときには、アルキル変性カルボキシル基含有共重合体がエマルジョンを安定化させる効果が不十分になる可能性がある。一方、成分（ｂ）の割合が、成分（ａ）１００質量部に対して５質量部を超えるときには、アルキル変性カルボキシル基含有共重合体を水に分散させた際（例えば、水溶成分と油溶成分のエマルジョンの安定化剤として、当該共重合体を水に分散させた際）にアルキル変性カルボキシル基含有共重合体が塊状化する可能性がある。 The proportion of component (b) in the alkyl-modified carboxyl group-containing copolymer of the present invention is 1 to 5 parts by mass with respect to 100 parts by mass of (meth) acrylic acid (component (a)). From the viewpoint of further improving the stability of the emulsion, the ratio of the component (b) is preferably 1 part by mass to 3 parts by mass with respect to 100 parts by mass of the component (a). When the proportion of component (b) is less than 1 part by mass relative to 100 parts by mass of component (a), the alkyl-modified carboxyl group-containing copolymer may be insufficient in stabilizing the emulsion. There is. On the other hand, when the proportion of the component (b) exceeds 5 parts by mass with respect to 100 parts by mass of the component (a), when the alkyl-modified carboxyl group-containing copolymer is dispersed in water (for example, water-soluble component and oil-soluble As a stabilizer for the emulsion of the component, the alkyl-modified carboxyl group-containing copolymer may be agglomerated when the copolymer is dispersed in water.
　エチレン性不飽和基を２個以上有する化合物（成分（ｃ））は、重合性を有するエチレン性不飽和基を２個以上有する化合物である。成分（ｃ）の好ましい具体例としては、ペンタエリスリトールジアリルエーテル、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等のペンタエリスリトールポリアリルエーテルや、ジエチレングリコールジアリルエーテル、ポリエチレングリコールジアリルエーテル、ポリアリルサッカロース等がある。成分（ｃ）は、１種類を用いてもよいし、２種類以上を用いてもよい。アルキル変性カルボキシル基含有共重合体の中和粘稠液の粘度を所定の範囲により容易に調整できるという理由から、これらの中でも、成分（ｃ）は、ペンタエリスリトールポリアリルエーテル、ジエチレングリコールジアリルエーテル、ポリエチレングリコールジアリルエーテル、及びポリアリルサッカロースからなる群より選ばれた少なくとも１種を含んでいることが好ましい。 The compound having two or more ethylenically unsaturated groups (component (c)) is a compound having two or more ethylenically unsaturated groups having polymerizability. Preferred specific examples of the component (c) include pentaerythritol polyallyl ethers such as pentaerythritol diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, polyallyl saccharose and the like. is there. As the component (c), one type may be used, or two or more types may be used. Among these, the component (c) is composed of pentaerythritol polyallyl ether, diethylene glycol diallyl ether, polyethylene because the viscosity of the neutralized viscous liquid of the alkyl-modified carboxyl group-containing copolymer can be easily adjusted within a predetermined range. It preferably contains at least one selected from the group consisting of glycol diallyl ether and polyallyl saccharose.
　本発明のアルキル変性カルボキシル基含有共重合体における成分（ｃ）の割合は、（メタ）アクリル酸（成分（ａ））１００質量部に対して、０．４５質量部以上である。エマルジョンの安定性をより高める観点からは、成分（ｃ）の割合は、０．４７質量部以上が好ましい。成分（ｃ）の割合が、０．４５質量部未満である場合、アルキル変性カルボキシル基含有共重合体がエマルジョンを経時的に安定化させる効果が不十分になる可能性がある。また、エマルジョンの安定性をより高める観点からは、成分（ｃ）の割合は、（メタ）アクリル酸（成分（ａ））１００質量部に対して、１０質量部以下が好ましく、３質量部以下がより好ましい。成分（ｃ）の割合が１０質量部以下であることにより、得られるアルキル変性カルボキシル基含有共重合体を水に分散させる際（例えば、水溶成分と油溶成分のエマルジョンの安定化剤として、当該共重合体を水に分散させた際）にアルキル変性カルボキシル基含有共重合体が塊状化することを抑制することができる。 The proportion of component (c) in the alkyl-modified carboxyl group-containing copolymer of the present invention is 0.45 parts by mass or more with respect to 100 parts by mass of (meth) acrylic acid (component (a)). From the viewpoint of further improving the stability of the emulsion, the ratio of the component (c) is preferably 0.47 parts by mass or more. When the proportion of component (c) is less than 0.45 parts by mass, the effect of stabilizing the emulsion over time by the alkyl-modified carboxyl group-containing copolymer may be insufficient. Further, from the viewpoint of further improving the stability of the emulsion, the proportion of the component (c) is preferably 10 parts by mass or less, preferably 3 parts by mass or less with respect to 100 parts by mass of (meth) acrylic acid (component (a)). Is more preferable. When the proportion of the component (c) is 10 parts by mass or less, the resulting alkyl-modified carboxyl group-containing copolymer is dispersed in water (for example, as a stabilizer for an emulsion of a water-soluble component and an oil-soluble component, When the copolymer is dispersed in water), the alkyl-modified carboxyl group-containing copolymer can be prevented from agglomerating.
　本発明のアルキル変性カルボキシル基含有共重合体は、成分（ａ）、（ｂ）、及び（ｃ）に加えて、成分（ａ）、（ｂ）、及び（ｃ）以外の単量体（成分（ａ）、（ｂ）、及び（ｃ）の少なくとも１種と共重合可能な他の単量体）を共重合させてもよい。 In addition to the components (a), (b), and (c), the alkyl-modified carboxyl group-containing copolymer of the present invention includes monomers (components) other than the components (a), (b), and (c). (A), (b), and (c) another monomer copolymerizable with at least one kind) may be copolymerized.
　本発明のアルキル変性カルボキシル基含有共重合体の１質量％中和粘稠液の粘度（以下、「１％粘度」ということがある）は、２５℃において、２０，０００ｍＰａ・ｓ～４０，０００ｍＰａ・ｓの範囲内にある。水溶成分と油溶成分とのエマルジョンの安定性をより高める観点からは、当該１％粘度は、２５，０００ｍＰａ・ｓ～３５，０００ｍＰａ・ｓの範囲内にあることが好ましい。なお、１％粘度が２０，０００ｍＰａ・ｓ未満のときは、アルキル変性カルボキシル基含有共重合体を使用したエマルジョンが分離するまでの時間が短くなる。一方、前記１％粘度が４０，０００ｍＰａ・ｓを超えるときは、エマルジョンが分離するまでの時間が短くなる。なお、当該「１％粘度」は、実施例の［評価方法］に記載の方法で測定した値を意味する。 The viscosity of the 1% by weight neutralized viscous liquid of the alkyl-modified carboxyl group-containing copolymer of the present invention (hereinafter sometimes referred to as “1% viscosity”) is 20,000 mPa · s to 40,000 mPa at 25 ° C. -Within the range of s From the viewpoint of further improving the stability of the emulsion of the water-soluble component and the oil-soluble component, the 1% viscosity is preferably in the range of 25,000 mPa · s to 35,000 mPa · s. When the 1% viscosity is less than 20,000 mPa · s, the time until the emulsion using the alkyl-modified carboxyl group-containing copolymer is separated is shortened. On the other hand, when the 1% viscosity exceeds 40,000 mPa · s, the time until the emulsion is separated is shortened. The “1% viscosity” means a value measured by the method described in [Evaluation Method] in the Examples.
　さらに、本発明のアルキル変性カルボキシル基含有共重合体においては、当該１質量％中和粘稠液１００質量部に対して１．０質量部の塩化ナトリウムを添加したときの粘度（以下「耐塩粘度」ということがある）が、２５℃において、４，０００ｍＰａ・ｓ～７，５００ｍＰａ・ｓの範囲内にある。エマルジョンの安定性をより高める観点からは、当該耐塩粘度は、４，５００ｍＰａ・ｓ～７，０００ｍＰａ・ｓの範囲内にあることが好ましい。耐塩粘度が４，０００ｍＰａ・ｓ未満、または７，５００ｍＰａ・ｓを超えるときは、エマルジョンが分離しやすくなる。なお、当該「耐塩粘度」は、実施例の［評価方法］に記載の方法で測定した値を意味する。 Furthermore, in the alkyl-modified carboxyl group-containing copolymer of the present invention, the viscosity (hereinafter referred to as “salt-resistant viscosity” when 1.0 part by mass of sodium chloride is added to 100 parts by mass of the 1% by mass neutralized viscous liquid. In the range of 4,000 mPa · s to 7,500 mPa · s at 25 ° C. From the viewpoint of further improving the stability of the emulsion, the salt-resistant viscosity is preferably in the range of 4,500 mPa · s to 7,000 mPa · s. When the salt-resistant viscosity is less than 4,000 mPa · s or more than 7,500 mPa · s, the emulsion is easily separated. In addition, the said "salt-resistant viscosity" means the value measured by the method as described in [Evaluation method] of an Example.
　本発明のアルキル変性カルボキシル基含有共重合体の１％粘度は、例えば、エチレン性不飽和基を２個以上有する化合物（成分（ｃ））の割合の増減によって制御することができる。具体的には、共重合体を構成している成分（ｃ）の割合を増やすことでアルキル変性カルボキシル基含有共重合体の１％粘度を高めることができる。また、成分（ｃ）の割合を少なくすることでアルキル変性カルボキシル基含有共重合体の１％粘度を低くできる。 The 1% viscosity of the alkyl-modified carboxyl group-containing copolymer of the present invention can be controlled by, for example, increasing or decreasing the ratio of the compound having two or more ethylenically unsaturated groups (component (c)). Specifically, the 1% viscosity of the alkyl-modified carboxyl group-containing copolymer can be increased by increasing the proportion of the component (c) constituting the copolymer. Moreover, the 1% viscosity of the alkyl-modified carboxyl group-containing copolymer can be lowered by reducing the proportion of the component (c).
　本発明のアルキル変性カルボキシル基含有共重合体の耐塩粘度は、例えば、重合に使用する全ての単量体の溶媒に対する濃度、反応温度によって制御することができる。具体的には、重合に使用する全ての単量体の溶媒に対する濃度を高くすることや、重合温度を低くすることでアルキル変性カルボキシル基含有共重合体の耐塩粘度を高めることができる。また、該濃度を低くすることや、重合温度を高くすることでアルキル変性カルボキシル基含有共重合体の耐塩粘度を低くすることができる。 The salt-resistant viscosity of the alkyl-modified carboxyl group-containing copolymer of the present invention can be controlled by, for example, the concentration of all monomers used for polymerization with respect to the solvent and the reaction temperature. Specifically, the salt-resistant viscosity of the alkyl-modified carboxyl group-containing copolymer can be increased by increasing the concentration of all monomers used in the polymerization with respect to the solvent or by decreasing the polymerization temperature. Moreover, the salt-resistant viscosity of the alkyl-modified carboxyl group-containing copolymer can be lowered by lowering the concentration or raising the polymerization temperature.
　本発明のアルキル変性カルボキシル基含有共重合体の製造方法としては、特に制限されず、少なくとも前述の成分（ａ）、（ｂ）、及び（ｃ）を含む原料並びに重合開始剤を溶媒に添加した溶液を、不活性ガス素雰囲気下で攪拌しながら加熱して重合する方法等がある。 The method for producing the alkyl-modified carboxyl group-containing copolymer of the present invention is not particularly limited, and a raw material containing at least the aforementioned components (a), (b), and (c) and a polymerization initiator are added to the solvent. There is a method in which a solution is heated and polymerized while stirring under an inert gas atmosphere.
　不活性ガス雰囲気とするための不活性ガスとしては、特に制限されないが、窒素ガス、アルゴンガスなどがある。 The inert gas for making the inert gas atmosphere is not particularly limited, and examples thereof include nitrogen gas and argon gas.
　また、溶媒は、少なくとも成分（ａ）、（ｂ）、及び（ｃ）は溶解するが、生成するアルキル変性カルボキシル基含有共重合体は溶解せず、かつ、共重合反応を阻害しなければ、特に限定されない。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などがある。溶媒は、１種類で使用してもよいし、２種類以上を組み合わせて使用してもよい。これらの溶媒の中でも、品質が安定しており、入手が容易である観点から、ノルマルヘキサン、ノルマルヘプタン、シクロヘキサン、エチレンジクロライド、酢酸エチルなどが好適に用いられる。 Further, the solvent dissolves at least the components (a), (b), and (c), but does not dissolve the alkyl-modified carboxyl group-containing copolymer to be formed and does not inhibit the copolymerization reaction. There is no particular limitation. Specific examples of the 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, Examples include ethyl methyl ketone and isobutyl methyl ketone. A solvent may be used by 1 type and may be used in combination of 2 or more type. Among these solvents, normal hexane, normal heptane, cyclohexane, ethylene dichloride, ethyl acetate, and the like are preferably used from the viewpoint of stable quality and easy availability.
　溶媒の使用量は、アルキル変性カルボキシル基含有共重合体の耐塩粘度を上記の範囲に調整する観点や、撹拌操作性を向上させる観点、経済性の観点等から、成分（ａ）１００質量部に対して、３００質量部～５，０００質量部とすることが好ましい。 The amount of the solvent used is 100 parts by weight of component (a) from the viewpoint of adjusting the salt-resistant viscosity of the alkyl-modified carboxyl group-containing copolymer to the above range, from the viewpoint of improving the stirring operability, and from the viewpoint of economy. On the other hand, it is preferably 300 to 5,000 parts by mass.
　重合開始剤としては、例えば、ラジカル重合開始剤が好ましい。重合開始剤の具体例としては、α、α’－アゾ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、ジメチル－２，２’－アゾビスイソブチレート、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などがある。重合開始剤は、１種類で使用してもよいし、２種類以上を組み合わせて使用してもよい。 As the polymerization initiator, for example, a radical polymerization initiator is preferable. Specific examples of the polymerization initiator include α, α′-azoisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, dimethyl-2,2′-azobisisobutyrate, peroxide Examples include benzoyl, lauroyl peroxide, cumene hydroperoxide, and tertiary butyl hydroperoxide. A polymerization initiator may be used by 1 type and may be used in combination of 2 or more types.
　重合開始剤の使用量としては、反応速度を適度に保つ観点から成分（ａ）１００質量部に対して、好ましくは０．０１質量部～０．４５質量部、より好ましくは０．０１質量部～０．３５質量部である。 The amount of the polymerization initiator used is preferably 0.01 parts by mass to 0.45 parts by mass, more preferably 0.01 parts by mass with respect to 100 parts by mass of the component (a) from the viewpoint of keeping the reaction rate moderately. Is 0.35 parts by mass.
　重合温度としては、重合速度を適度に保つ観点から好ましくは５０℃～９０℃程度、より好ましくは５５℃～８５℃程度である。 The polymerization temperature is preferably about 50 ° C. to 90 ° C., more preferably about 55 ° C. to 85 ° C. from the viewpoint of keeping the polymerization rate moderate.
　重合時間は、重合温度などによって異なるが、通常、０．５時間～１０時間程度である。 The polymerization time varies depending on the polymerization temperature and the like, but is usually about 0.5 to 10 hours.
　重合後のスラリー液を、乾燥時間を短くし共重合体の塊状化を抑制する観点から例えば８０℃～１３０℃に加熱して溶媒を除去することにより、本発明のアルキル変性カルボキシル基含有共重合体を得ることができる。 From the viewpoint of shortening the drying time and suppressing the agglomeration of the copolymer, the slurry liquid after polymerization is heated to, for example, 80 ° C. to 130 ° C. to remove the solvent, whereby the alkyl-modified carboxyl group-containing copolymer of the present invention is removed. Coalescence can be obtained.
　本発明のアルキル変性カルボキシル基含有共重合体を使用することにより、安定性の高いエマルジョン（特に、Ｏ／Ｗ型エマルジョン）を得ることができる。したがって、本発明のアルキル変性カルボキシル基含有共重合体を必須成分として含むエマルジョン安定化剤は、エマルジョン（特に、Ｏ／Ｗ型エマルジョン）の安定化剤として有用である。 By using the alkyl-modified carboxyl group-containing copolymer of the present invention, a highly stable emulsion (in particular, an O / W emulsion) can be obtained. Therefore, the emulsion stabilizer containing the alkyl-modified carboxyl group-containing copolymer of the present invention as an essential component is useful as a stabilizer for emulsions (particularly, O / W emulsions).
　本発明のエマルジョン安定化剤は、前述の本発明のアルキル変性カルボキシル基含有共重合体を含むことを特徴としている。本発明のエマルジョン安定化剤は、本発明のアルキル変性カルボキシル基含有共重合体のみより形成されていてもよい。 The emulsion stabilizer of the present invention is characterized by containing the above-mentioned alkyl-modified carboxyl group-containing copolymer of the present invention. The emulsion stabilizer of the present invention may be formed only from the alkyl-modified carboxyl group-containing copolymer of the present invention.
　また、本発明のエマルジョンは、本発明のアルキル変性カルボキシル基含有共重合体を含むことを特徴としている。すなわち、本発明のエマルジョンは、エマルジョン安定化剤として、本発明のアルキル変性カルボキシル基含有共重合体を含んでいる。 The emulsion of the present invention is characterized by including the alkyl-modified carboxyl group-containing copolymer of the present invention. That is, the emulsion of the present invention contains the alkyl-modified carboxyl group-containing copolymer of the present invention as an emulsion stabilizer.
　本発明のエマルジョン中における、本発明のアルキル変性カルボキシル基含有共重合体の含有量は、エマルジョンの安定性を高める観点からは、好ましくは０．１質量％以上、より好ましくは０．２質量％～１質量％である。 The content of the alkyl-modified carboxyl group-containing copolymer of the present invention in the emulsion of the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass from the viewpoint of improving the stability of the emulsion. To 1% by mass.
　本発明のエマルジョンは、水溶成分と油溶成分とのエマルジョンであり、特にＯ／Ｗ型エマルジョンであることが好ましい。水溶成分としては、水に溶ける成分であればよい。例えば、低級アルコール、多価アルコール、水溶性高分子、水溶性界面活性剤、保湿剤、薬用成分、ｐＨ調整剤、酸化防止剤、色材などの化粧品に配合される公知の成分を水に添加することができる。また、油溶成分としては、水と分離してエマルジョンを形成できる成分であればよい。例えば、炭化水素、エステル、高級脂肪酸、などの化粧品に配合される公知の成分を油溶成分に用いることができる。本発明のエマルジョンは、美容成分などを配合した化粧品とすることもできる。 The emulsion of the present invention is an emulsion of a water-soluble component and an oil-soluble component, and particularly preferably an O / W type emulsion. The water-soluble component may be any component that is soluble in water. For example, known ingredients blended in cosmetics such as lower alcohols, polyhydric alcohols, water-soluble polymers, water-soluble surfactants, humectants, medicinal ingredients, pH adjusters, antioxidants, and coloring materials are added to water. can do. The oil-soluble component may be any component that can be separated from water to form an emulsion. For example, known components blended in cosmetics such as hydrocarbons, esters and higher fatty acids can be used as oil-soluble components. The emulsion of the present invention can be a cosmetic containing a cosmetic ingredient.
　以下に実施例及び比較例を示して本発明を詳細に説明する。但し本発明は実施例に限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.
（実施例１）
　攪拌機、温度計、窒素吹込み管及び冷却管を備えた容量５００ｍＬの四つ口フラスコに、アクリル酸４５ｇ、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が１質量部以下の混合物）０．９９ｇ、ペンタエリスリトールポリアリルエーテル（ペンタエリスリトールトリアリルエーテルとペンタエリスリトールテトラアリルエーテルの混合物）０．２０３ｇ、ノルマルヘプタン１６３．２ｇ、酢酸エチル５４ｇ及び２，２’－アゾビスメチルイソブチレート０．０２５ｇを仕込んだ。その後、フラスコの内容物を撹拌しながら、フラスコ内の酸素を除去するために、溶液中に窒素ガスを吹き込んだ。その後、攪拌と窒素ガスの吹き込みを続けた状態でオイルバスの設定温度を７５～７９℃に設定し、フラスコの内容物を４時間加熱した。その後、オイルバスの設定温度を１１０℃に設定して加熱し、フラスコ内からノルマルヘプタンと酢酸エチルを除去した。その後フラスコの内容物を減圧乾燥機（Ｙａｍａｔｈｏ社製、バキュームドライオーブンＤＰ３３）に移し、オーブンの設定温度を１１５℃に設定して、設定圧力を１０ｍｍＨｇに設定して８時間乾燥し、白色粉末状のアルキル変性カルボキシル基含有共重合体４４ｇを得た。 Example 1
In a 500 mL four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube and cooling tube, 45 g of acrylic acid, Blemmer VMA70 (manufactured by NOF Corporation: 10-20 parts by mass of stearyl methacrylate, eicosanyl methacrylate) 0.99 g of a mixture of 10 to 20 parts by mass, 59 to 80 parts by mass of behenyl methacrylate and 1 part by mass or less of tetracosanyl methacrylate), pentaerythritol polyallyl ether (pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) Mixture) 0.203 g, normal heptane 163.2 g, ethyl acetate 54 g and 2,2′-azobismethylisobutyrate 0.025 g were charged. Thereafter, nitrogen gas was blown into the solution to remove oxygen in the flask while stirring the contents of the flask. Thereafter, the temperature of the oil bath was set to 75 to 79 ° C. while stirring and nitrogen gas blowing were continued, and the contents of the flask were heated for 4 hours. Thereafter, the set temperature of the oil bath was set to 110 ° C. and heated, and normal heptane and ethyl acetate were removed from the flask. Thereafter, the contents of the flask were transferred to a vacuum dryer (Yamato, vacuum dry oven DP33), the oven set temperature was set to 115 ° C., the set pressure was set to 10 mmHg, and dried for 8 hours. 44 g of an alkyl-modified carboxyl group-containing copolymer was obtained.
（実施例２）
　実施例１において、ペンタエリスリトールポリアリルエーテル（ペンタエリスリトールトリアリルエーテルとペンタエリスリトールテトラアリルエーテルの混合物）の使用量を０．２２５ｇに変更したこと以外は、実施例１と同様にして、白色粉末状のアルキル変性カルボキシル基含有共重合体４４ｇを得た。 (Example 2)
In Example 1, except that the amount of pentaerythritol polyallyl ether (a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) was changed to 0.225 g, a white powder form was obtained. 44 g of an alkyl-modified carboxyl group-containing copolymer was obtained.
（実施例３）
　実施例１において、ペンタエリスリトールポリアリルエーテル（ペンタエリスリトールトリアリルエーテルとペンタエリスリトールテトラアリルエーテルの混合物）の使用量を０．２４８ｇに変更したこと以外は、実施例１と同様にして、白色粉末状のアルキル変性カルボキシル基含有共重合体４３ｇを得た。 (Example 3)
In Example 1, a white powder form was obtained in the same manner as in Example 1 except that the amount of pentaerythritol polyallyl ether (a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) was changed to 0.248 g. 43 g of an alkyl-modified carboxyl group-containing copolymer was obtained.
（実施例４）
　実施例１において、ペンタエリスリトールポリアリルエーテル（ペンタエリスリトールトリアリルエーテルとペンタエリスリトールテトラアリルエーテルの混合物）の使用量を０．２７０ｇに変更したこと以外は、実施例１と同様にして、白色粉末状のアルキル変性カルボキシル基含有共重合体４３ｇを得た。 (Example 4)
In Example 1, except that the amount of pentaerythritol polyallyl ether (a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) was changed to 0.270 g, a white powder form was obtained. 43 g of an alkyl-modified carboxyl group-containing copolymer was obtained.
（実施例５）
　実施例１において、ペンタエリスリトールポリアリルエーテル（ペンタエリスリトールトリアリルエーテルとペンタエリスリトールテトラアリルエーテルの混合物）の使用量を０．２２５ｇ、ブレンマーＶＭＡ７０の使用量を０．４５ｇに変更したこと以外は、実施例１と同様にして、白色粉末状のアルキル変性カルボキシル基含有共重合体４４ｇを得た。 (Example 5)
In Example 1, except that the usage amount of pentaerythritol polyallyl ether (a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) was changed to 0.225 g and the usage amount of Blemmer VMA70 was changed to 0.45 g. In the same manner as in Example 1, 44 g of a white powdery alkyl-modified carboxyl group-containing copolymer was obtained.
（実施例６）
　実施例１において、ペンタエリスリトールポリアリルエーテル（ペンタエリスリトールトリアリルエーテルとペンタエリスリトールテトラアリルエーテルの混合物）の使用量を０．２２５ｇ、ブレンマーＶＭＡ７０の使用量を２．２５ｇに変更したこと以外は、実施例１と同様にして、白色粉末状のアルキル変性カルボキシル基含有共重合体４５ｇを得た。 (Example 6)
In Example 1, except that the usage amount of pentaerythritol polyallyl ether (a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) was changed to 0.225 g and the usage amount of Blemmer VMA70 was changed to 2.25 g. In the same manner as in Example 1, 45 g of a white powdery alkyl-modified carboxyl group-containing copolymer was obtained.
（実施例７）
　攪拌機、温度計、窒素吹込み管、添加装置及び冷却管を備えた容量５００ｍＬの５つ口フラスコを用意した。フラスコにブレンマー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が１質量部以下の混合物）１．１ｇ、ノルマルヘプタン１０４ｇ、酢酸エチル３５ｇ及び２，２’－アゾビスメチルイソブチレート０．０３０ｇを仕込み、また、添加装置にアクリル酸５０ｇとペンタエリスリトールポリアリルエーテル（ペンタエリスリトールトリアリルエーテルとペンタエリスリトールテトラアリルエーテルの混合物）０．２２５ｇ、ノルマルヘプタン４０ｇ、および酢酸エチル１４ｇを仕込んだ。その後、フラスコの内容物を攪拌しながら、フラスコ内の酸素を除去する為に、溶液中に窒素ガスを吹き込んだ。その後、攪拌と窒素ガスの吹き込みを続けた状態で、フラスコを加熱し、フラスコの内容物の温度が６０℃に到達したときから、添加装置に仕込んだ混合物を１１０分かけてフラスコの内容物に滴下した。滴下を開始した後にフラスコ内の内容物の温度が７０～７３℃になるようにオイルバスを設定した。添加装置に仕込んだ混合物の滴下が終了した後、フラスコの内容物の温度が７０～７３℃になるようにオイルバスを設定した状態で１時間フラスコの内容物を攪拌した。その後、オイルバスの設定温度を１１０℃に設定してフラスコを加熱し、フラスコ内からノルマルヘプタンと酢酸エチルを除去した。その後フラスコの内容物を減圧乾燥機（Ｙａｍａｔｈｏ社製、バキュームドライオーブンＤＰ３３）に移し、オーブンの設定温度を１１５℃に設定し、設定圧力を１０ｍｍＨｇに設定して８時間乾燥して、白色粉末状のアルキル変性カルボキシル基含有共重合体４９ｇを得た。 (Example 7)
A 500 mL five-necked flask equipped with a stirrer, a thermometer, a nitrogen blowing tube, an addition device, and a cooling tube was prepared. In a flask, Bremer VMA70 (manufactured by NOF Corporation: 10-20 parts by mass of stearyl methacrylate, 10-20 parts by mass of eicosanyl methacrylate, 59-80 parts by mass of behenyl methacrylate, and 1 part by mass or less of tetracosanyl methacrylate 1.1 g of mixture, 104 g of normal heptane, 35 g of ethyl acetate, and 0.030 g of 2,2′-azobismethylisobutyrate, and 50 g of acrylic acid and pentaerythritol polyallyl ether (pentaerythritol triallyl) were added to the addition apparatus. 0.225 g of a mixture of ether and pentaerythritol tetraallyl ether), 40 g of normal heptane, and 14 g of ethyl acetate were charged. Thereafter, nitrogen gas was blown into the solution to remove oxygen in the flask while stirring the contents of the flask. Thereafter, the flask is heated while stirring and blowing of nitrogen gas are continued, and when the temperature of the contents of the flask reaches 60 ° C., the mixture charged in the addition apparatus is changed to the contents of the flask over 110 minutes. It was dripped. After starting the dropping, the oil bath was set so that the temperature of the contents in the flask would be 70-73 ° C. After the dropping of the mixture charged in the addition apparatus was completed, the contents of the flask were stirred for 1 hour in an oil bath set so that the temperature of the contents of the flask was 70 to 73 ° C. Thereafter, the set temperature of the oil bath was set to 110 ° C., the flask was heated, and normal heptane and ethyl acetate were removed from the flask. Thereafter, the contents of the flask were transferred to a vacuum dryer (Yamato, vacuum dry oven DP33), the oven set temperature was set to 115 ° C., the set pressure was set to 10 mmHg and dried for 8 hours, 49 g of an alkyl-modified carboxyl group-containing copolymer was obtained.
（実施例８）
　実施例７において、添加装置に仕込んだペンタエリスリトールポリアリルエーテル（ペンタエリスリトールトリアリルエーテルとペンタエリスリトールテトラアリルエーテルの混合物）の使用量を０．２６３ｇに変更したこと以外は、実施例７と同様にして、白色粉末状のアルキル変性カルボキシル基含有共重合体４７ｇを得た。 (Example 8)
In Example 7, except that the amount of pentaerythritol polyallyl ether (a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) charged in the addition apparatus was changed to 0.263 g, the same as in Example 7. As a result, 47 g of a white powdery alkyl-modified carboxyl group-containing copolymer was obtained.
（実施例９）
　実施例７において、添加装置に仕込んだペンタエリスリトールポリアリルエーテル（ペンタエリスリトールトリアリルエーテルとペンタエリスリトールテトラアリルエーテルの混合物）の使用量を０．２５ｇ、１．１ｇのブレンマーＶＭＡ７０の代わりに１．５ｇのステアリルメタクリレートを使用したこと以外は、実施例７と同様にして、白色粉末状のアルキル変性カルボキシル基含有共重合体４９ｇを得た。 Example 9
In Example 7, the amount of pentaerythritol polyallyl ether (a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) charged in the addition apparatus was changed to 0.25 g, and 1.5 g instead of 1.1 g of Bremer VMA70. 49 g of a white powdery alkyl-modified carboxyl group-containing copolymer was obtained in the same manner as in Example 7 except that the stearyl methacrylate was used.
（比較例１）
　実施例７において、反応容器に仕込んだノルマルヘプタンの使用量を８２ｇ、酢酸エチルの使用量を２７ｇ、添加装置に仕込んだペンタエリスリトールポリアリルエーテル（ペンタエリスリトールトリアリルエーテルとペンタエリスリトールテトラアリルエーテルの混合物）の使用量を０．２５ｇに変更したこと以外は、実施例７と同様にして、白色粉末状のアルキル変性カルボキシル基含有共重合体４７ｇを得た。 (Comparative Example 1)
In Example 7, the amount of normal heptane charged in the reaction vessel was 82 g, the amount of ethyl acetate used was 27 g, and the pentaerythritol polyallyl ether (mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) charged in the addition device was used. ) Was changed to 0.25 g in the same manner as in Example 7 to obtain 47 g of a white powdery alkyl-modified carboxyl group-containing copolymer.
（比較例２）
　実施例７において、滴下を開始した後はフラスコ内の内容物の温度が７６～７９℃となるようオイルバスの設定を変更し、添加装置に仕込んだ混合物の滴下が終了した後はフラスコ内の内容物の温度が７６～７９℃となるようオイルバスの設定を変更したこと以外は実施例７と同様にして、白色粉末状のアルキル変性カルボキシル基含有共重合体４６ｇを得た。 (Comparative Example 2)
In Example 7, after the start of dropping, the setting of the oil bath was changed so that the temperature of the contents in the flask would be 76 to 79 ° C., and after the dropping of the mixture charged in the addition apparatus was completed, 46 g of a white powdery alkyl-modified carboxyl group-containing copolymer was obtained in the same manner as in Example 7 except that the setting of the oil bath was changed so that the temperature of the contents was 76 to 79 ° C.
（比較例３）
　実施例７において、反応容器に仕込んだノルマルヘプタンの使用量を８２ｇ、酢酸エチルの使用量を２７ｇに変更し、滴下を開始した後はフラスコ内の内容物の温度が６７～７０℃となるようオイルバスの設定を変更し、添加装置に仕込んだ混合物の滴下が終了した後はフラスコ内の内容物の温度が６７～７０℃となるようオイルバスの設定を変更し攪拌時間を２時間半に変更したこと以外は実施例７と同様にして、白色粉末状のアルキル変性カルボキシル基含有共重合体４７ｇを得た。 (Comparative Example 3)
In Example 7, the amount of normal heptane charged in the reaction vessel was changed to 82 g, the amount of ethyl acetate used was changed to 27 g, and after the addition was started, the temperature of the contents in the flask was 67-70 ° C. After changing the setting of the oil bath and dropping of the mixture charged in the adding device is completed, the setting of the oil bath is changed so that the temperature of the contents in the flask becomes 67 to 70 ° C., and the stirring time is set to 2.5 hours A white powdery alkyl-modified carboxyl group-containing copolymer 47 g was obtained in the same manner as in Example 7 except for the change.
（比較例４）
　実施例１において、ペンタエリスリトールポリアリルエーテル（ペンタエリスリトールトリアリルエーテルとペンタエリスリトールテトラアリルエーテルの混合物）の使用量を０．２７ｇに変更し、滴下を開始した後は内容物の温度が７９～８４℃になるようにオイルバスを設定し、添加装置に仕込んだ混合物の滴下が終了した後はフラスコの内容物の温度が７９～８４℃になるようにオイルバスを設定して１時間フラスコの内容物を攪拌したこと以外は、実施例１と同様にして、白色粉末状のアルキル変性カルボキシル基含有共重合体４２ｇを得た。 (Comparative Example 4)
In Example 1, the amount of pentaerythritol polyallyl ether (a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) was changed to 0.27 g, and the temperature of the contents was 79 to 84 after the dropping was started. Set the oil bath to ℃ and after the addition of the mixture charged in the addition device is completed, set the oil bath so that the temperature of the flask contents is 79 to 84 ℃ and set the contents of the flask for 1 hour. Except that the product was stirred, 42 g of a white powdery alkyl-modified carboxyl group-containing copolymer was obtained in the same manner as in Example 1.
（比較例５）
　実施例１において、ペンタエリスリトールポリアリルエーテル（ペンタエリスリトールトリアリルエーテルとペンタエリスリトールテトラアリルエーテルの混合物）の使用量を０．１８ｇに変更したこと以外は、実施例１と同様にして、白色粉末状のアルキル変性カルボキシル基含有共重合体４３ｇを得た。 (Comparative Example 5)
In Example 1, except that the amount of pentaerythritol polyallyl ether (a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) was changed to 0.18 g, a white powder form was obtained. 43 g of an alkyl-modified carboxyl group-containing copolymer was obtained.
（比較例６）
　実施例１において、ペンタエリスリトールポリアリルエーテル（ペンタエリスリトールトリアリルエーテルとペンタエリスリトールテトラアリルエーテルの混合物）の使用量を０．２２５ｇ、ブレンマーＶＭＡ７０の使用量を０．２２５ｇに変更したこと以外は、実施例１と同様にして、白色粉末状のアルキル変性カルボキシル基含有共重合体４２ｇを得た。 (Comparative Example 6)
In Example 1, except that the usage amount of pentaerythritol polyallyl ether (a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) was changed to 0.225 g, and the usage amount of Blemmer VMA70 was changed to 0.225 g. In the same manner as in Example 1, 42 g of a white powdery alkyl-modified carboxyl group-containing copolymer was obtained.
（比較例７）
　実施例１において、ペンタエリスリトールポリアリルエーテル（ペンタエリスリトールトリアリルエーテルとペンタエリスリトールテトラアリルエーテルの混合物）の使用量を０．２２５ｇ、ブレンマーＶＭＡ７０の使用量を２．４７５ｇに変更したこと以外は、実施例１と同様にして、白色粉末状のアルキル変性カルボキシル基含有共重合体４２ｇを得た。 (Comparative Example 7)
In Example 1, except that the usage amount of pentaerythritol polyallyl ether (a mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether) was changed to 0.225 g, and the usage amount of Blemmer VMA70 was changed to 2.475 g. In the same manner as in Example 1, 42 g of a white powdery alkyl-modified carboxyl group-containing copolymer was obtained.
［評価方法］
　実施例、比較例により得られたアルキル変性カルボキシル基含有共重合体を以下の方法により測定、評価した。 [Evaluation methods]
The alkyl-modified carboxyl group-containing copolymers obtained in Examples and Comparative Examples were measured and evaluated by the following methods.
（１質量％中和粘稠液粘度）
　容量５００ｍＬのビーカーにイオン交換水２９７．０ｇを入れ、４枚羽根パドル（翼径５０ｍｍ）を備えた攪拌機を用いて３００ｒｐｍの回転速度で撹拌しながらアルキル変性カルボキシル基含有共重合体３．０ｇを投入した。アルキル変性カルボキシル基含有共重合体の凝集物（ママコ）が消えて均一に分散したことを目視により確認し、得られた１質量％分散液に水酸化ナトリウム水溶液を加えて、ｐＨ＝７に調整し、これを評価用中和粘稠液とした。Ｂ型回転粘度計を用い、ローターＮｏ．６、毎分２０回転、および、温度２５℃の条件下で、６０秒間ローターが回転した後の得られた評価用中和粘稠液の粘度を測定し、これを「１質量％中和粘稠液粘度」とした。 (1% by weight neutralized viscous liquid viscosity)
Put 297.0 g of ion-exchanged water in a 500 mL beaker and add 3.0 g of an alkyl-modified carboxyl group-containing copolymer while stirring at a rotational speed of 300 rpm using a stirrer equipped with a four-blade paddle (blade diameter 50 mm). I put it in. It was confirmed by visual observation that the aggregate (Mamako) of the alkyl-modified carboxyl group-containing copolymer had disappeared and was uniformly dispersed, and an aqueous sodium hydroxide solution was added to the obtained 1% by mass dispersion to adjust to pH = 7. This was used as a neutralized viscous liquid for evaluation. Using a B-type rotational viscometer, rotor No. 6. The viscosity of the neutralized viscous liquid for evaluation obtained after the rotor was rotated for 60 seconds under the conditions of 20 revolutions per minute and a temperature of 25 ° C. was measured as “1% by mass neutralized viscous liquid”. It was referred to as “consistent liquid viscosity”.
（１％ＮａＣｌ耐塩粘度）
　容量３００ｍＬのビーカーに１質量％中和粘稠液粘度評価で得られた評価用中和粘稠液１５０ｇを入れ、塩化ナトリウム１．５ｇを添加し、４枚羽根パドル（翼径５０ｍｍ）を備えた攪拌機を用いて攪拌を３０分間行い、電解質添加溶液とした。Ｂ型回転粘度計を用い、ローターＮｏ．５、毎分２０回転、および、温度２５℃の条件下で、６０秒間ローターが回転した後の得られた電解質添加溶液の粘度を測定し、これを「１％ＮａＣｌ耐塩粘度」とした。 (1% NaCl salt viscosity)
In a beaker with a capacity of 300 mL, 150 g of the neutralized viscous liquid for evaluation obtained by the viscosity evaluation of 1% by weight neutralized viscous liquid is added, 1.5 g of sodium chloride is added, and a four-blade paddle (blade diameter 50 mm) is provided. Stirring was performed for 30 minutes using an agitator, to obtain an electrolyte addition solution. Using a B-type rotational viscometer, rotor No. 5. The viscosity of the electrolyte addition solution obtained after the rotor was rotated for 60 seconds under the conditions of 20 revolutions per minute and a temperature of 25 ° C. was determined as “1% NaCl salt resistant viscosity”.
（エマルジョンの安定性の評価）
　容量２００ｍＬビーカーにイオン交換水１０２．１２ｇを入れ、攪拌機（プライミクス株式会社製、型番：Ｔ．Ｋ．ロボミクス、翼直径３０ｍｍのディスパー翼）を用いて５，０００ｒｐｍで攪拌しながら、アルキル変性カルボキシル基含有共重合体０．７５ｇを投入した後、３０分間攪拌し未中和分散液を得た。その後、攪拌機の攪拌翼をホモミキサー（プライミクス株式会社製、型番：Ｔ．Ｋ．ロボミクス、ホモミキサー）に変更した。その後未中和分散液をホモミキサー１３，０００ｒｐｍで攪拌しながら、流動パラフィン４５ｇをビーカーに投入し、５分間攪拌した。その後５０質量％トリエタノールアミン水溶液２．１３ｇをビーカーに投入し、ホモミキサー１３，０００ｒｐｍで５分間攪拌し、エマルジョン安定性評価用のＯ／Ｗ型エマルジョンを得た。得られたエマルジョンを容器に密封し温度４０℃、湿度７５％ＲＨの恒温恒湿機内に静置し、Ｏ／Ｗ型エマルジョンの水溶成分と油溶成分の分離の有無を１日ごとに目視で確認した。９０日以上分離しなければ、エマルジョンの安定性が良好と判断した。Ｏ／Ｗ型エマルジョンが分離するまでの日数を表１、２に示す。 (Evaluation of emulsion stability)
While adding 102.12 g of ion-exchanged water to a 200 mL beaker and stirring at 5,000 rpm using a stirrer (manufactured by PRIMIX Corporation, model number: TK Robotics, Disper blade with blade diameter of 30 mm), alkyl-modified carboxyl group After adding 0.75 g of the containing copolymer, the mixture was stirred for 30 minutes to obtain an unneutralized dispersion. Then, the stirring blade of the stirrer was changed to a homomixer (manufactured by PRIMIX Corporation, model number: TK Robotics, homomixer). Thereafter, 45 g of liquid paraffin was charged into a beaker while stirring the unneutralized dispersion at 13,000 rpm with a homomixer, and stirred for 5 minutes. Thereafter, 2.13 g of a 50 mass% triethanolamine aqueous solution was put into a beaker and stirred at 13,000 rpm for 5 minutes to obtain an O / W emulsion for evaluating emulsion stability. The obtained emulsion is sealed in a container and left in a constant temperature and humidity chamber at a temperature of 40 ° C. and a humidity of 75% RH, and the presence or absence of separation of the water-soluble component and the oil-soluble component of the O / W emulsion is visually checked every day. confirmed. If it was not separated for 90 days or more, it was judged that the stability of the emulsion was good. Tables 1 and 2 show the number of days until the O / W emulsion is separated.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

Claims (5)

  1. 　（メタ）アクリル酸（ａ）１００質量部と、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（ｂ）１．０～５．０質量部と、エチレン性不飽和基を２個以上有する化合物（ｃ）０．４５質量部以上とを含む単量体の共重合体であり、
    　前記共重合体の１質量％中和粘稠液の粘度が、２５℃において、２０，０００ｍＰａ・ｓ～４０，０００ｍＰａ・ｓであり、
    　前記１質量％中和粘稠液１００質量部に対して１．０質量部の塩化ナトリウムを添加したときの粘度が、２５℃において、４，０００ｍＰａ・ｓ～７，５００ｍＰａ・ｓである、
    　アルキル変性カルボキシル基含有共重合体。     100 parts by weight of (meth) acrylic acid (a), 1.0 to 5.0 parts by weight of (meth) acrylic acid alkyl ester (b) having an alkyl group having 18 to 24 carbon atoms, and an ethylenically unsaturated group A copolymer of monomers containing at least 0.45 parts by mass of the compound (c) having two or more of
    The viscosity of the 1% by weight neutralized viscous liquid of the copolymer is 20,000 mPa · s to 40,000 mPa · s at 25 ° C.,
    Viscosity when 1.0 part by mass of sodium chloride is added to 100 parts by mass of the 1% by weight neutralized viscous liquid is 4,000 mPa · s to 7,500 mPa · s at 25 ° C.
    An alkyl-modified carboxyl group-containing copolymer.
  2. 　前記エチレン性不飽和基を２個以上有する化合物（ｃ）が、ペンタエリスリトールポリアリルエーテル、ジエチレングリコールジアリルエーテル、ポリエチレングリコールジアリルエーテル、及びポリアリルサッカロースからなる群より選ばれた少なくとも１種である、請求項１に記載のアルキル変性カルボキシル基含有共重合体。 The compound (c) having two or more ethylenically unsaturated groups is at least one selected from the group consisting of pentaerythritol polyallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, and polyallyl saccharose. Item 11. The alkyl-modified carboxyl group-containing copolymer according to Item 1.
  3. 　前記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（ｂ）が、（メタ）アクリル酸ステアリルを含む、請求項１または２に記載のアルキル変性カルボキシル基含有共重合体。 The alkyl-modified carboxyl group-containing copolymer according to claim 1 or 2, wherein the (meth) acrylic acid alkyl ester (b) having 18 to 24 carbon atoms in the alkyl group contains stearyl (meth) acrylate.
  4. 　請求項１～３のいずれかに記載のアルキル変性カルボキシル基含有共重合体を含む、エマルジョン安定化剤。 An emulsion stabilizer comprising the alkyl-modified carboxyl group-containing copolymer according to any one of claims 1 to 3.
  5. 　請求項１～３のいずれかに記載のアルキル変性カルボキシル基含有共重合体を含む、エマルジョン。 An emulsion comprising the alkyl-modified carboxyl group-containing copolymer according to any one of claims 1 to 3.
PCT/JP2017/011952 2016-03-25 2017-03-24 Alkyl-modified carboxyl group-containing copolymer WO2017164357A1 (en)

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JPS59232107A (en) * 1983-06-13 1984-12-26 ザ・ビ−・エフ・グツドリツチ・カンパニ− Polymer and print paste composition containing same
JPH07505919A (en) * 1992-04-29 1995-06-29 ビーエーエスエフ　アクチェンゲゼルシャフト Copolymers of carboxylic acids and quaternary ammonium compounds and their use as thickeners or dispersants
WO2003016382A1 (en) * 2001-08-09 2003-02-27 Sumitomo Seika Chemicals Co., Ltd. Particle of crosslinked carboxylated polymer
JP2004512399A (en) * 2000-10-24 2004-04-22 ノベオン・アイピー・ホールディングズ・コーポレイション Rheology modifying copolymer composition
WO2011016364A1 (en) * 2009-08-04 2011-02-10 住友精化株式会社 Method for manufacturing a carboxyl-containing water-soluble polymer
JP2011088882A (en) * 2009-09-24 2011-05-06 Sumitomo Seika Chem Co Ltd Emulsion-type cosmetic
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59232107A (en) * 1983-06-13 1984-12-26 ザ・ビ−・エフ・グツドリツチ・カンパニ− Polymer and print paste composition containing same
JPH07505919A (en) * 1992-04-29 1995-06-29 ビーエーエスエフ　アクチェンゲゼルシャフト Copolymers of carboxylic acids and quaternary ammonium compounds and their use as thickeners or dispersants
JP2004512399A (en) * 2000-10-24 2004-04-22 ノベオン・アイピー・ホールディングズ・コーポレイション Rheology modifying copolymer composition
WO2003016382A1 (en) * 2001-08-09 2003-02-27 Sumitomo Seika Chemicals Co., Ltd. Particle of crosslinked carboxylated polymer
WO2011016364A1 (en) * 2009-08-04 2011-02-10 住友精化株式会社 Method for manufacturing a carboxyl-containing water-soluble polymer
JP2011088882A (en) * 2009-09-24 2011-05-06 Sumitomo Seika Chem Co Ltd Emulsion-type cosmetic
JP2015503639A (en) * 2011-12-21 2015-02-02 ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド Process for preparing acrylic polymers and products produced thereby

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