WO2017164357A1 - Copolymère contenant un groupe carboxyle modifié par un alkyle - Google Patents

Copolymère contenant un groupe carboxyle modifié par un alkyle Download PDF

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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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English (en)
Japanese (ja)
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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/fr

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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

L'objet de la présente invention est de fournir un copolymère contenant un groupe carboxyle modifié par un alkyle permettant de stabiliser une émulsion d'un constituant hydrosoluble et d'un constituant oléosoluble. Le copolymère contenant un groupe carboxyle modifié par un alkyle comprend un monomère contenant 100 parties en masse d'un acide (méth)acrylique (a), de 1,0 à 5,0 parties en masse d'un ester alkylique d'acide (méth)acrylique (b) dont le groupe alkyle comprend de 18 à 24 atomes de carbone, et une proportion supérieure ou égale à 0,45 partie en masse d'un composé (c) comprenant au moins deux groupes éthyléniquement insaturés. Un liquide visqueux neutralisé à 1 % en masse dudit copolymère présente une viscosité de 20 000 à 40 000 mPa·s à 25 °C, et lorsque 1,0 partie en masse de chlorure de sodium est ajoutée aux 100 parties en masse du liquide visqueux neutralisé à 1 % en masse, le liquide visqueux ainsi obtenu présente une viscosité de 4 000 à 5 000 mPa.s à 25 °C.
PCT/JP2017/011952 2016-03-25 2017-03-24 Copolymère contenant un groupe carboxyle modifié par un alkyle WO2017164357A1 (fr)

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JP2016062555A JP2019094359A (ja) 2016-03-25 2016-03-25 アルキル変性カルボキシル基含有共重合体
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Citations (7)

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