WO2017170961A1 - 共重合体、該共重合体を含有する増粘剤および該共重合体を配合した化粧料 - Google Patents
共重合体、該共重合体を含有する増粘剤および該共重合体を配合した化粧料 Download PDFInfo
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- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- 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
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- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/48—Thickener, Thickening system
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- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
Definitions
- the present invention relates to a copolymer having a thickening property, a thickener containing the copolymer, and a cosmetic compounded with the copolymer.
- thickeners such as polymers and surfactants are added to cosmetics to maintain active ingredients on the skin, hair, etc., and to improve the feeling of use and luxury, the cosmetics are thickened or gelled.
- organic thickeners natural polymers such as polysaccharides, casein and xanthan gum, semi-natural polymers such as hydroxyethyl cellulose, synthetic polymers such as acrylic polymers, carboxyvinyl polymers, and polyethylene oxide are used.
- inorganic thickeners clay minerals such as montmorillonite, silica, and the like are used.
- a carboxyvinyl polymer is frequently used because of its high thickening effect and gelation in a small amount (for example, Patent Document 1).
- the polymer aggregates when an electrolyte is added, and when the added amount of electrolyte exceeds 2% by weight, the viscosity rapidly decreases. Therefore, when a high concentration of electrolyte coexists, the viscosity can be maintained. There is no problem.
- the carboxy vinyl polymer mentioned above suppresses the viscosity fall by addition of electrolyte, there exists a problem that the effect cannot be said to be enough.
- the present invention relates to a copolymer capable of forming a viscous aqueous solution having a desired viscosity in the presence of an electrolyte, particularly a polyelectrolyte, a thickener containing the copolymer, and a cosmetic comprising the copolymer.
- an electrolyte particularly a polyelectrolyte, a thickener containing the copolymer, and a cosmetic comprising the copolymer.
- the present inventors have found that a fluorinated acrylate ester having a specific structure and, if necessary, a polymerizable unsaturated group and a specific acidity as a component of the copolymer. It has been found that by using a compound having a group in a specific ratio, a copolymer capable of forming a viscous aqueous solution having a desired viscosity can be provided, and the present invention has been completed.
- the present invention has the following configuration.
- (1) (A) the acrylic acid ester represented by the general formula [1], and (B) a polymerizable unsaturated group, and any functional group selected from the group consisting of a carboxyl group, a sulfo group, and a phosphoric acid group As a constituent component,
- the copolymer of the present invention has an effect that a viscous aqueous solution having a desired viscosity can be formed in the presence of an electrolyte, particularly a polyelectrolyte. Moreover, even when the concentration of the electrolyte is high, the desired viscosity can be maintained.
- the copolymer of the present invention has good coatability, is difficult to drip, and has the effect of having a pleasing tactile feeling (elastic tactile feeling), so if the copolymer of the present invention is used, It is possible to provide a cosmetic material that is excellent in use feeling and applicability and has a unique tactile sensation.
- the copolymer of the present invention has an effect of being excellent in transparency
- the copolymer of the present invention can be suitably used for cosmetics characterized by non-coloring such as skin lotions and cosmetic liquids. Can do.
- the “acrylic ester (A) / compound (B) copolymer” is derived from the acrylic ester (A) containing at least the acrylic ester (A) and the compound (B) as constituent components. It means a copolymer having a structural unit and a structural unit derived from the compound (B).
- the alkyl group having 1 to 6 carbon atoms represented by R 1 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably an alkyl group having 1 carbon atom.
- the alkyl group may be linear, branched or cyclic. Specific examples of such an alkyl group include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl.
- n-pentyl group isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, Isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, cyclohexyl group, etc.
- straight, branched or cyclic having 1 to 3 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group and cyclopropyl group
- Alkyl groups are preferred, among them, more preferably a methyl group which is an alkyl group having one carbon atom.
- R 1 in the general formula [1] is more preferably a hydrogen atom.
- M in the general formula [1] is an integer of 2 to 4, preferably an integer of 2 to 3, and more preferably 2 among them.
- acrylic ester represented by (A) the general formula [1] examples include 2-perfluorohexylethyl (meth) acrylate, 3-perfluorohexylpropyl (meth) acrylate, and 4-perfluorohexyl. Examples include butyl (meth) acrylate.
- (meth) acrylate means acrylate and / or methacrylate.
- 2-perfluorohexylethyl (meth) acrylate is preferable, and 2-perfluorohexylethyl acrylate is particularly preferable.
- acrylic ester represented by the above-described (A) general formula [1] a commercially available one may be used, or one appropriately synthesized by a method known per se may be used.
- the compound having in the molecule thereof a polymerizable unsaturated group and any functional group selected from the group consisting of a carboxyl group, a sulfo group and a phosphate group includes, for example, a carbon-carbon double bond, carbon A compound having in the molecule thereof a polymerizable unsaturated group such as a carbon triple bond and any functional group selected from the group consisting of a carboxyl group, a sulfo group and a phosphate group, wherein the polymerizable unsaturated group (A) is a compound that reacts with the acrylic ester represented by the general formula [1] to form an acrylic ester (A) / compound (B) copolymer.
- Such a compound (B) include those represented by the general formulas [2] to [5].
- an alkyl group having 1 to 6 carbon atoms represented by R 2 to R 5 in the general formulas [2] to [5] an alkyl group having 1 to 3 carbon atoms is preferable, and among them, an alkyl group having 1 carbon atom is preferable. More preferred.
- the alkyl group may be linear, branched or cyclic. Specific examples of such an alkyl group include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl.
- n-pentyl group isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, Isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, cyclohexyl group, etc.
- straight, branched or cyclic having 1 to 3 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group and cyclopropyl group
- Alkyl groups are preferred, among them, more preferably a methyl group which is an alkyl group having one carbon atom.
- an oxygen atom is more preferable.
- the alkylene group having 1 to 6 carbon atoms which may have a hydroxyl group and represented by T 1 in the general formula [3] is an alkylene group having 1 to 4 carbon atoms which may have a hydroxyl group. Among them, an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group is more preferable.
- the alkylene group may be linear or branched, and when it has a hydroxyl group, the number of hydroxyl groups may be one or more.
- alkylene group examples include, for example, a methylene group, a hydroxymethylene group, a dimethylene group (ethylene group), a hydroxydimethylene group (hydroxyethylene group), a trimethylene group, a 1-hydroxytrimethylene group, and a 2-hydroxy group. Trimethylene, isopropylene, hydroxyisopropylene, tetramethylene, hydroxytetramethylene, 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethyldimethylene, pentamethylene, hexa Examples include a methylene group, and among them, a dimethylene group (ethylene group), a trimethylene group, a 2-hydroxytrimethylene group, and a 1,1-dimethyldimethylene group are preferable.
- T 2 in the general formula [4], there is no atom in T 2, and "sulfur atom” are bonded to T 2, the "R 4 bonded to T 2
- the “bonded carbon atom” means that they are directly bonded without passing through T 2 .
- the alkylene group having 1 to 6 carbon atoms represented by T 2 in the general formula [4] is preferably an alkylene group having 1 carbon atom.
- the alkylene group may be linear or branched.
- Specific examples of such an alkylene group include, for example, methylene group, dimethylene group (ethylene group), trimethylene group, isopropylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1, Examples thereof include a 1-dimethyldimethylene group, a pentamethylene group, a hexamethylene group, and the like.
- a methylene group that is an alkylene group having 1 carbon atom is preferable.
- the alkylene group having 1 to 6 carbon atoms represented by T 3 in the general formula [5] is preferably an alkylene group having 2 carbon atoms.
- the alkylene group may be linear or branched.
- Specific examples of such an alkylene group include, for example, methylene group, dimethylene group (ethylene group), trimethylene group, isopropylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1, Examples thereof include a 1-dimethyldimethylene group, a pentamethylene group, a hexamethylene group, and among them, a dimethylene group (ethylene group) which is an alkylene group having 2 carbon atoms is preferable.
- Specific examples of the compound represented by the general formula [2] include acrylic acid and methacrylic acid.
- Specific examples of the compound represented by the general formula [3] include 2- (acryloyloxy) ethanesulfonic acid, 2- (methacryloyloxy) ethanesulfonic acid, 3- (acryloyloxy) propanesulfonic acid, 3- ( Methacryloyloxy) propanesulfonic acid, 2-acryloyloxy-2-methylpropanesulfonic acid, 2-methacryloyloxy-2-methylpropanesulfonic acid, 3-acryloyloxy-2-hydroxypropanesulfonic acid, 3-methacryloyloxy-2- Examples thereof include hydroxypropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid and the like.
- Specific examples of the compound represented by the general formula [4] include vinyl sulfonic acid and allyl sulfonic acid.
- Specific examples of the compound represented by the general formula [5] include 2- (acryloyloxy) ethyl phosphate and 2- (methacryloyloxy) ethyl phosphate.
- a compound represented by the above general formula [2] is more preferable, among which acrylic acid and methacrylic acid are more preferable, and among them, acrylic acid is particularly preferable.
- the ratio (weight ratio) between the acrylic ester (A) and the compound (B) is smaller than 9.0 / 91.0, a sufficient viscosity can be obtained in the presence of an electrolyte when a viscous aqueous solution is prepared.
- the ratio of the acrylic acid ester (A) and the compound (B) is as described above.
- the copolymer of the present invention in the range of (weight ratio) can be suitably used for cosmetics in which a high concentration of electrolyte coexists.
- the acrylic acid ester (A) and the compound (B) are described above, because when the viscous aqueous solution is prepared, a higher viscosity is easily maintained in the presence of a high concentration of electrolyte.
- the copolymer of the present invention in the range of the ratio (weight ratio) can be suitably used for cosmetics characterized by high viscosity.
- the ratio (molar ratio) between the acrylic ester (A) and the compound (B) is less than 1.5 / 98.5, when the viscous aqueous solution is prepared, sufficient viscosity is present in the presence of the electrolyte. It becomes difficult to use without being obtained. Further, when the ratio (molar ratio) between the acrylic ester (A) and the compound (B) exceeds 6.5 / 93.5, when the viscous aqueous solution is prepared, the presence of a low concentration electrolyte is present. Not only does the viscosity increase remarkably, but as the electrolyte concentration increases, the viscosity decreases rapidly, and the change in viscosity due to the electrolyte concentration is large, making it difficult to use.
- the ratio of the acrylic acid ester (A) and the compound (B) is as described above.
- the copolymer of the present invention within the range of (molar ratio) can be suitably used for cosmetics in which a high concentration of electrolyte coexists.
- the acrylic acid ester (A) and the compound (B) are described above, because when the viscous aqueous solution is prepared, a higher viscosity is easily maintained in the presence of a high concentration of electrolyte.
- the copolymer of the present invention within the range of the ratio (molar ratio) can be suitably used for cosmetics characterized by high viscosity.
- the acrylic ester (A) / compound (B) copolymer of the present invention may further contain (C) a compound having two or more ethylenically unsaturated groups as a constituent component. That is, the copolymer of the present invention further including the compound (C) is derived from the acrylate ester (A) containing at least the acrylate ester (A), the compound (B), and the compound (C) as constituent components. It is a copolymer having a structural unit, a structural unit derived from the compound (B), and a structural unit derived from the compound (C).
- the copolymer of the present invention is preferably an acrylic acid ester (A) / compound (B) / compound (C) copolymer further comprising (C) a compound having two or more ethylenically unsaturated groups as a constituent component. .
- the compound having two or more ethylenically unsaturated groups is a compound having in the molecule two or more ethylenically unsaturated groups capable of reacting with the acrylic ester (A) and the compound (B), It is a compound that plays the role of a so-called crosslinking agent.
- Such a compound (C) include those represented by the general formulas [6] to [16].
- k in the general formula [6] an integer of 1 to 4 is more preferable, and 1 is more preferable.
- the alkylene group having 1 to 20 carbon atoms represented by T 4 in the general formula [7] is preferably an alkylene group having 1 to 10 carbon atoms.
- the alkylene group may be linear, branched or cyclic, and is preferably linear.
- alkylene group examples include, for example, methylene group, dimethylene group (ethylene group), trimethylene group, isopropylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1, 1-dimethyldimethylene group, pentamethylene group, cyclopentylene group, hexamethylene group, cyclohexylene group, heptamethylene group, cycloheptylene group, octamethylene group, cyclooctylene group, nonamethylene group, cyclononylene group, decamethylene group, cyclodecylene Group, undecamethylene group, cycloundecylene group, dodecamethylene group, cyclododecylene group, tridecamethylene group, cyclotridecylene group, tetradecamemethylene group, cyclotetradecylene group, pentadecamemethylene group, cyclopentadecylene group, Hexadeca
- methylene group dimethylene group (ethylene group), trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, Straight chain having 1 to 20 carbon atoms such as dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group, hexadecamethylene group, heptacamethylene group, octadecamethylene group, nonadecamethylene group, icosylene group, etc.
- a chain-like alkylene group is preferable, and among them, Straight chain having 1 to 10 carbon atoms such as tylene group, dimethylene group (ethylene group), trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, etc.
- An alkylene group is more preferred.
- An alkylene group is preferred.
- the alkylene group may be linear, branched or cyclic, and is preferably linear.
- alkylene group examples include, for example, methylene group, dimethylene group (ethylene group), trimethylene group, isopropylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1, Examples include 1-dimethyldimethylene group, pentamethylene group, cyclopentylene group, hexamethylene group, cyclohexylene group, etc. Among them, carbon atoms of 1 to 3 such as methylene group, dimethylene group (ethylene group), trimethylene group, etc. These linear alkylene groups are preferred.
- an integer of 2 to 6 is more preferable, and an integer of 4 to 6 is more preferable.
- an integer of 1 to 7 is more preferable, an integer of 1 to 5 is more preferable, and an integer of 1 to 3 is particularly preferable.
- An alkylene group is preferred.
- the alkylene group may be linear or branched. Specific examples of such an alkylene group include, for example, a methylene group, a dimethylene group (ethylene group), a trimethylene group, an isopropylene group, and the like. Among these, a methylene group that is an alkylene group having 1 carbon atom is preferable.
- the alkylene group having 1 to 6 carbon atoms represented by T 8 , T 8 ′, T 9 and T 9 ′ in the general formula [9] is preferably an alkylene group having 1 to 3 carbon atoms.
- the alkylene group is more preferable.
- the alkylene group may be linear, branched or cyclic, and is preferably linear. Specific examples of such an alkylene group include, for example, methylene group, dimethylene group (ethylene group), trimethylene group, isopropylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1, Examples include 1-dimethyldimethylene group, pentamethylene group, cyclopentylene group, hexamethylene group, cyclohexylene group and the like.
- T 8 and T 8 ′ are alkylene groups having 1 carbon atom.
- a methylene group is preferable.
- a linear alkylene group having 1 to 3 carbon atoms such as a methylene group, a dimethylene group (ethylene group), and a trimethylene group is preferable.
- r is more preferably an integer of 1 to 2.
- r ′ in the general formula [9] an integer of 0 to 2 is more preferable.
- R 7 to R 14 may be a vinyl group or a vinylcarbonyl group, and among them, 5 to 8 are preferably a vinyl group or a vinylcarbonyl group, and among them, More preferably, 5 to 7 are vinyl groups or vinylcarbonyl groups.
- the alkylene group having 1 to 6 carbon atoms represented by T 10 , T 11 and T 11 ′ in the general formula [11] may be linear, branched or cyclic.
- Specific examples of such an alkylene group include, for example, methylene group, dimethylene group (ethylene group), trimethylene group, isopropylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1, 1-dimethyldimethylene group, pentamethylene group, cyclopentylene group, hexamethylene group, cyclohexylene group, etc. are mentioned.
- cyclopentylene group and cyclohexylene group are preferred, Of these, a cyclohexylene group is more preferable, and in T 11 and T 11 ′, a methylene group and a dimethylene group (ethylene group) are preferable, and among these, a methylene group is more preferable.
- Examples of the divalent to tetravalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R 15 in the general formula [12] include, for example, a divalent aromatic having 6 to 10 carbon atoms such as a phenylene group and a naphthylene group.
- Examples include hydrocarbon groups (arylene groups), for example, trivalent aromatic hydrocarbon groups derived from benzene and naphthalene, for example, tetravalent aromatic hydrocarbon groups derived from benzene and naphthalene.
- a trivalent to tetravalent aromatic hydrocarbon group of formula 6 is preferred.
- the alkylene group having 1 to 6 carbon atoms represented by T 12 in the general formula [12] is preferably an alkylene group having 1 to 3 carbon atoms.
- the alkylene group may be linear, branched or cyclic, and is preferably linear. Specific examples of such an alkylene group include, for example, methylene group, dimethylene group (ethylene group), trimethylene group, isopropylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1, Examples include 1-dimethyldimethylene group, pentamethylene group, cyclopentylene group, hexamethylene group, cyclohexylene group, etc. Among them, carbon atoms of 1 to 3 such as methylene group, dimethylene group (ethylene group), trimethylene group, etc. These linear alkylene groups are preferred.
- T in the general formula [12] is more preferably an integer of 3 to 4.
- the alkylene group having 1 to 6 carbon atoms represented by T 13 in the general formula [13] is preferably an alkylene group having 1 to 3 carbon atoms.
- the alkylene group may be linear, branched or cyclic, and is preferably linear. Specific examples of such an alkylene group include, for example, methylene group, dimethylene group (ethylene group), trimethylene group, isopropylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1, Examples include 1-dimethyldimethylene group, pentamethylene group, cyclopentylene group, hexamethylene group, cyclohexylene group, etc. Among them, carbon atoms of 1 to 3 such as methylene group, dimethylene group (ethylene group), trimethylene group, etc. These linear alkylene groups are preferred.
- Examples of the arylene group having 6 to 10 carbon atoms represented by T 14 and T 14 ′ in the general formula [13] include an arylene group having 6 carbon atoms such as a phenylene group, and an arylene group having 10 carbon atoms such as a naphthylene group.
- a phenylene group which is an arylene group having 6 carbon atoms is preferable.
- Examples of the arylene group having 6 to 10 carbon atoms represented by T 15 in the general formula [14] include an arylene group having 6 carbon atoms such as a phenylene group, an arylene group having 10 carbon atoms such as a naphthylene group, and the like. Among them, a phenylene group which is an arylene group having 6 carbon atoms is preferable.
- v in the general formula [15] an integer of 0 to 2 is more preferable, and 0 is more preferable.
- the alkylene group having 1 to 6 carbon atoms represented by T 16 in the general formula [16] is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 1 carbon atom.
- the alkylene group may be linear, branched or cyclic, and is preferably linear. Specific examples of such an alkylene group include, for example, methylene group, dimethylene group (ethylene group), trimethylene group, isopropylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1, Examples include 1-dimethyldimethylene group, pentamethylene group, cyclopentylene group, hexamethylene group, cyclohexylene group, etc. Among them, carbon atoms of 1 to 3 such as methylene group, dimethylene group (ethylene group), trimethylene group, etc. Are preferred, and among these, a methylene group is more preferred.
- Examples of the compound (C) include the compound represented by the general formula [7], the compound represented by the general formula [8], the compound represented by the general formula [9], and the general formula [16]. Are preferred.
- Specific examples of the compound represented by the general formula [7] include 1,10-decanediol diacrylate and the like.
- Specific examples of the compound represented by the general formula [8] include, for example, pentaerythritol triallyl ether.
- dialkylene glycol diallyl ethers such as diethylene glycol diallyl ether, dipropylene glycol diallyl ether, and dibutylene glycol diallyl ether, such as polyethylene glycol diallyl ether and polypropylene glycol diallyl.
- examples thereof include polyalkylene glycol diallyl ethers such as ether and polybutylene glycol diallyl ether.
- Specific examples of the compound represented by the general formula [16] include N, N′-methylenebisacrylamide and the like.
- 1,10-decane Diol diacrylate, pentaerythritol triallyl ether, diethylene glycol diallyl ether and N, N′-methylenebisacrylamide are preferred, and among them, diethylene glycol diallyl ether is more preferred.
- the proportion of compound (C) in the copolymer of the present invention is usually 0.0001 to 1.5 parts by weight, preferably 100 parts by weight in total of acrylic ester (A) and compound (B), preferably It is 0.02 to 1.5 parts by weight, more preferably 0.04 to 1.25 parts by weight, still more preferably 0.05 to 1.01 parts by weight, and particularly preferably 0.20 to 0 parts by weight. .35 parts by weight.
- the amount of the compound (C) used is more than 1.5 parts by weight with respect to 100 parts by weight.
- an aqueous solution is prepared, a sufficient viscosity cannot be obtained in the presence of an electrolyte, making it difficult to use.
- the proportion of the compound (C) in the copolymer of the present invention is in the range of 0.05 to 1.01 parts by weight, it is high in the presence of a high concentration of electrolyte when preparing a viscous aqueous solution. Since the viscosity is easily maintained, the copolymer of the present invention in which the proportion of the compound (C) is within the above-mentioned range of parts by weight can be suitably used for cosmetics in which a high concentration of electrolyte coexists.
- the proportion of the compound (C) in the copolymer of the present invention is in the range of 0.20 to 0.35 parts by weight, when the viscous aqueous solution is prepared, it is more in the presence of a high concentration of electrolyte. Since the high viscosity is easily maintained, the copolymer of the present invention in which the proportion of the compound (C) is within the above-mentioned range of parts by weight can be suitably used for cosmetics characterized by high viscosity.
- the ratio of the compound (C) in the copolymer of the present invention is usually from 0.00005 to 1.0 mol, preferably from 0.0005 to 1.0 mol, based on a total of 100 mol of the acrylic ester (A) and the compound (B). 0005 to 0.70 mol, more preferably 0.0005 to 0.60 mol, still more preferably 0.0005 to 0.50 mol, and particularly preferably 0.07 to 0.14 mol. .
- a viscous aqueous solution is prepared if the amount of compound (C) used exceeds 1.0 mole relative to 100 moles. In this case, a sufficient viscosity cannot be obtained in the presence of the electrolyte, making it difficult to use.
- the proportion of compound (C) is that of acrylic ester (A) and compound (B).
- the total amount is preferably from 0.01 to 1.0 mol, more preferably from 0.03 to 0.70 mol, still more preferably from 0.05 to 0.60 mol, particularly preferably from 100 to 1.0 mol. Is from 0.07 to 0.50 mol, most preferably from 0.07 to 0.14 mol.
- the total amount is preferably from 0.0005 to 0.70 mol, more preferably from 0.0005 to 0.70 mol, still more preferably from 0.0005 to 0.50 mol, particularly preferably from 0.0005 to 0.70 mol. Is from 0.0005 to 0.40 mol, most preferably from 0.0005 to 0.14 mol.
- the copolymer of the present invention may contain a compound (D) as a constituent component other than the above-described acrylic ester (A), compound (B) and compound (C).
- Examples of such a compound (D) include (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate.
- the compound (D) mentioned above may use a commercially available thing, and may use what was synthesize
- the copolymer of the present invention is preferably composed of an acrylic ester (A), a compound (B) and a compound (C) that does not contain the above-mentioned compound (D).
- the method for producing the above-described copolymer of the present invention is not particularly limited, and examples thereof include the following methods.
- the copolymer of the present invention can be produced.
- inert gas for obtaining an inert gas atmosphere examples include nitrogen gas and argon gas.
- the solvent is not particularly limited as long as it does not react with the acrylic ester (A), the compound (B), the compound (C) and, if necessary, the compound (D) and does not inhibit these polymerization reactions.
- a solvent include, for example, purified water such as distilled water and deionized water, and water such as ultrapure water; for example, n-hexane, cyclohexane, n-heptane, n-octane, and isooctane.
- Aliphatic hydrocarbon solvents such as, for example, halogenated aliphatic hydrocarbon solvents such as dichloromethane, trichloromethane (chloroform), tetrachloromethane (carbon tetrachloride); for example, aromatic carbonization such as benzene, toluene, xylene, etc.
- halogenated aliphatic hydrocarbon solvents such as dichloromethane, trichloromethane (chloroform), tetrachloromethane (carbon tetrachloride); for example, aromatic carbonization such as benzene, toluene, xylene, etc.
- Hydrogen solvents for example, ether solvents such as diethyl ether, diisopropyl ether, methyl-tert-butyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane; for example, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, Ethylene Glycol ether solvents such as coal diethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether; for example, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene Glycol ether acetate solvents such as glycol monomethyl ether acetate, propylene glycol monoethyl ether
- the use amount of the above-mentioned solvent is usually 100 to 5000 parts by weight, preferably 300 to 3000 parts by weight with respect to 100 parts by weight of the compound (B) from the viewpoints of practicality and economy.
- the polymerization initiator is not particularly limited as long as it is a polymerization initiator used in this field.
- Specific examples of such a polymerization initiator include persulfates such as persulfuric acid, sodium persulfate, potassium persulfate, and ammonium persulfate; hydroperoxides such as hydrogen peroxide and tert-butyl hydroperoxide.
- Peroxydicarbonates such as di (4-tert-butylcyclohexyl) peroxydicarbonate; for example, 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2 Radical polymerization of azo compounds such as 2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (N-butyl-2-methylpropionamide) Agents.
- the polymerization initiator mentioned above may use a commercially available thing, and may use what was synthesize
- the amount of the polymerization initiator used is usually 0.0001 to 0.002 mol, preferably 0.0002 to 0.001 mol, relative to 1 mol of the compound (B). If the amount of the polymerization initiator used is too small, there is a possibility that the reaction rate becomes slow, so that it is not economical or the polymerization reaction does not proceed. Moreover, when there is too much usage-amount of a polymerization initiator, there exists a possibility that a polymerization reaction may advance rapidly and control of reaction may become difficult.
- the polymerization for producing the copolymer of the present invention is preferably carried out under heating conditions and / or light (active energy ray) irradiation conditions.
- the reaction temperature when the polymerization is carried out under heating is, for example, usually 40 to 120 ° C., preferably 45 to 100 ° C., more preferably 50 to 90 ° C.
- the reaction temperature is less than 40 ° C.
- the viscosity of the reaction solution increases and it may be difficult to stir uniformly.
- reaction temperature exceeds 120 degreeC, reaction may advance rapidly and there exists a possibility that control of reaction may become difficult.
- the reaction time varies depending on the reaction temperature, it cannot be generally stated, but it is usually 0.5 to 6 hours.
- the wavelength of light (active energy ray) when polymerization is performed under light (active energy ray) irradiation conditions is not particularly limited as long as the polymerization reaction proceeds well.
- Specific examples of the wavelength of such light (active energy ray) are usually 1 to 1000 nm, for example, and examples of the light having such a wavelength include X-rays, ultraviolet rays, visible rays, and infrared rays. .
- the irradiation amount (integrated exposure amount) of light (active energy rays) is not particularly limited as long as the polymerization reaction proceeds well.
- the irradiation amount (integrated exposure amount) of light (active energy rays) are, for example, usually 0.1 J or more, preferably 0.5 J or more, more preferably 1.0 J or more.
- the reaction temperature in the case of superposing
- the reaction time varies depending on the wavelength of light (active energy rays) and the irradiation amount (integrated exposure amount), and cannot be generally specified, but is usually 0.5 to 6 hours.
- the post-treatment method and purification method for producing the copolymer of the present invention may be general methods usually performed in this field. For example, after the polymerization is completed, the reaction solution is cooled as necessary, the copolymer precipitated in the solution is filtered, and the filtered copolymer is dried. The inventive copolymer can be obtained. If necessary, the copolymer collected by filtration may be put into a suitable precipitating agent to purify the copolymer.
- acrylic ester (A) / compound (B) copolymer of the present invention those having the following property (1) are useful.
- the viscosity at 20 ° C. of an aqueous solution containing 1% by weight of an acrylic ester (A) / compound (B) copolymer and 3% by weight of ascorbyl magnesium phosphate and having a pH of 8 is 5000 mPa ⁇ s. That's it.
- a compound having in the molecule, if necessary, (C) a compound having two or more ethylenically unsaturated groups is used as a monomer, and each monomer is converted into an acrylate ester (A) and a compound (B).
- (A) / (B) 9.0 / 91.0 to 28.5 / 71.5, and if necessary, the ratio of the compound (C) is an acrylate ester.
- the viscosity is the B type rotational viscometer and rotor No. 4 and measured at a temperature of 20 ° C. and a rotation speed of 3 rpm.
- the viscosity at 20 ° C. of a pH 8 aqueous solution containing 1% by weight of the acrylic ester (A) / compound (B) copolymer of the present invention and 3% by weight of ascorbyl magnesium phosphate is preferably 5000 mPa ⁇ s or more. 7000 mPa ⁇ s or more, more preferably 12000 mPa ⁇ s or more, particularly preferably 15000 mPa ⁇ s or more, and most preferably 20000 mPa ⁇ s or more.
- an upper limit of a viscosity although it may change with uses of cosmetics, it is 100000 mPa * s or less, for example. Since it has such characteristics, when the copolymer of the present invention is used in cosmetics, it can be thickened with a small amount of addition, and a cosmetic having excellent feeling in use and applicability and a unique feel can be obtained.
- the viscosity at 20 ° C. of a pH 8 aqueous solution containing 1% by weight of the acrylic ester (A) / compound (B) copolymer of the present invention and 3% by weight of ascorbyl magnesium phosphate is 15000 mPa ⁇ s or more
- the acrylic ester (A) / compound (B) copolymer of the present invention can be used for various cosmetics containing a high concentration of electrolyte because high viscosity is easily maintained in the presence of a high concentration of electrolyte. Can do.
- the acrylic ester (A) / compound (B) copolymer of the present invention is preferably used for cosmetics characterized by high viscosity, because a higher viscosity is easily maintained in the presence of a high concentration of electrolyte. Can do.
- the acrylic acid ester (A) / compound (B) copolymer of the present invention is dissolved in pure water such as deionized water, and the pH of the copolymer is about 1% by weight using an alkali.
- a weakly acidic to alkaline viscous aqueous solution having a pH of 5 to 11 it can be used as a thickener for cosmetics and the like. That is, the thickener containing the acrylic ester (A) / compound (B) copolymer of the present invention is also included in the present invention.
- the alkali for neutralization is not particularly limited, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, for example, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, Examples thereof include amines such as triethanolamine and diisopropanolamine, and sodium hydroxide is particularly preferable.
- the blending amount of the copolymer of the present invention into the cosmetic is not particularly limited as long as the desired effect is exhibited. For example, 0.01 to 5.0% by weight of the copolymer of the present invention in the cosmetic. %, Preferably 0.05 to 3.0% by weight, more preferably 0.1 to 1.5% by weight.
- the blending amount of the copolymer of the present invention is preferably 0.01% by weight or more, and from the viewpoint of usability and applicability, the blending amount of the copolymer of the present invention is 5. It is preferably 0% by weight or less.
- the degree of neutralization of the copolymer in the weakly acidic to alkaline viscous aqueous solution having a pH of 5 to 11 containing the acrylic ester (A) / compound (B) copolymer of the present invention is, for example, 30 to 100 mol%.
- the viscous aqueous solution obtained by using the acrylic ester (A) / compound (B) copolymer of the present invention can be thickened with a small addition amount in the presence of a high concentration electrolyte, and the feeling of use and applicability. Excellent and has a unique feel.
- the fluorine atom in the acrylate ester (A) in the copolymer of the present invention forms an aggregate between polymer chains by an electrostatic interaction with the electrolyte in an aqueous solution, thereby increasing the viscosity and increasing the viscosity. It is presumed that the effect of thinning is reduced.
- the compound (C) according to the present invention is presumed to affect the viscosity by acting as a crosslinking agent.
- the viscosity can be increased with a small addition amount in the presence of a high concentration of electrolyte, and the use feeling and coating property are excellent and unique.
- a cosmetic material having a tactile feel can be produced.
- the electrolyte used in the present invention refers to a compound that dissociates ions in water.
- the type of electrolyte is not particularly limited, but for example, lactic acid, gluconic acid, succinic acid, glutaric acid, adipic acid, malic acid, tartaric acid, maleic acid, fumaric acid, itaconic acid, citric acid, phthalic acid, acetic acid, benzoic acid, Carboxylic acids such as salicylic acid, gallic acid, diethyl barbituric acid and hyaluronic acid; for example, amino acids such as glycine, alanine, valine, leucine, serine, glutamic acid and aspartic acid; for example, ethanesulfonic acid, phenolsulfonic acid, p- Organic sulfonic acids such as toluenesulfonic acid and m-xylenesulfonic acid; aminosulfonic acids such as taurine; acid agents such as
- carboxylic acids such as lactic acid, malic acid, maleic acid, citric acid, benzoic acid, salicylic acid, and hyaluronic acid from the viewpoint of stable blending in cosmetics and water retention and moisture retention during skin application.
- Amino acids such as glycine, alanine, valine, leucine, serine, glutamic acid, aspartic acid; alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, cocamidomethylmonoethanolamine; sodium hydroxide, sodium hydroxide, Inorganic bases such as potassium hydroxide, magnesium hydroxide and calcium hydroxide; acid agents and alkalis such as sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium citrate, potassium citrate, magnesium citrate and calcium citrate Neutralization with agents Salt-forming; ascorbic acid; phosphoric acid L- ascorbyl sodium, ascorbic acid derivatives such as phosphoric acid L- ascorbyl magnesium; dipotassium glycyrrhizinate are preferred.
- the amount of these electrolytes is usually 1 to 3000 parts by weight, preferably 5 to 2000 parts by weight, per 100 parts by weight of the acrylate (A) / compound (B) copolymer.
- a polyelectrolyte such as magnesium phosphate or L-ascorbyl magnesium phosphate may be preferred.
- the copolymer of the present invention can form a viscous aqueous solution having a desired viscosity in the presence of such a polyelectrolyte.
- the cosmetics of the present invention include, for example, lotion, milky lotion, beauty essence, cream, cream pack, massage cream, cleansing cream, cleansing gel, facial cleansing foam, body shampoo, body lotion, styling gel, hair restorer, hair growth agent. , Anti-dandruff agents, eyeliner, mascara, foundation, sunscreen, moisturizer, antiperspirant, whitening agent, anti-aging agent, anti-wrinkle agent and the like.
- the cosmetics of the present invention may contain additives that are usually used in the cosmetics field in addition to the electrolytes described above.
- additives include hair dyes, hair styling agents, UV inhibitors, whitening agents, anti-aging agents, moisturizers, softeners, antioxidants, antiseptics, antibacterial agents, and pH adjusters.
- Quasi-drug raw material standards 2006 such as buffers, surfactants, antacids, foam enhancers, foam improvers, oils, emulsifiers, dispersants, viscosity modifiers, antistatic agents, colorants, fragrances, etc. The various components currently recorded are mentioned.
- the thickener of the present invention has a relatively low viscosity in the absence of an electrolyte, it can be said that it is a very useful thickener in terms of production efficiency of cosmetics and the like. That is, in various manufacturing processes of the product, the viscosity of the solution before the addition of the (polyvalent) electrolyte is low, and the process of adding the electrolyte is a subsequent process, so that the reaction process, the transfer process, the heating process before the electrolyte addition The work efficiency of the process, the blending process, etc. can be significantly improved.
- the thickener of the present invention can be used for various purposes besides cosmetics.
- cosmetics antibacterial agents, antifungal agents, caries preventive agents, anticalculus agents, antiplaque agents, haptic agents, ointments, etc.
- soil water retention agents for pharmaceuticals (antibacterial agents, antifungal agents, caries preventive agents, anticalculus agents, antiplaque agents, haptic agents, ointments, etc.), soil water retention agents, antistatic agents, medical waste solidifying agents, etc.
- the thickener of the present invention can be provided.
- the thickener of the present invention may contain additives ordinarily used in the pharmaceutical field, agricultural and horticultural field, etc. in addition to the electrolyte described above. Any of these additives may be used as long as they are known in this field.
- Example 1 Synthesis of Acrylic Ester (A) / Compound (B) Copolymer (1) of the Present Invention
- Acrylic acid 35 g (0.49 mol; manufactured by Wako Pure Chemical Industries, Ltd.), 2-perfluorohexyl ethyl acrylate 10 .69 g (0.0256 mol; manufactured by Unimatec Co., Ltd.), diethylene glycol diallyl ether 0.1333 g (0.72 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) and di (4-tert-butylcyclohexyl) peroxydicarbonate 0.0734 g ( 0.18 mmol; product name: Perkadox 16; manufactured by Kayaku Akzo Co., Ltd.) was introduced into a mixed solvent of 411 mL of cyclohexane and 45.7 mL of ethyl acetate, and the solution was uniformly mixed.
- the mixed solution was bubbled under a nitrogen gas atmosphere for 30 minutes to degas oxygen contained in the solution. Thereafter, the solution was heated to 55 ° C. over 30 minutes while stirring, and the solution was further stirred for 1 hour while maintaining the same temperature. The solution was then heated to 75 ° C. over 1 hour 30 minutes and the solution was stirred for an additional 2 hours while maintaining the same temperature. After stirring, the solution is cooled to room temperature, and the copolymer (polymer) precipitated by cooling is collected by filtration, and then the collected copolymer is dried under reduced pressure at 90 to 110 ° C. for 8 hours. Of acrylic acid ester (A) / compound (B) copolymer (1) (42.43 g) was obtained (yield: 93%). Table 1 shows the names of the components and the proportions (weight ratio, parts by weight, molar ratio, and molar amount) of each component in Example 1.
- Examples 2 to 20 Synthesis of Acrylic Ester (A) / Compound (B) Copolymers (2) to (20) of the Present Invention
- the components listed in Table 1 Acrylic ester (A) / compound (B) of the present invention according to the same method as in Example 1 except that (weight ratio, parts by weight, molar ratio and molar amount) are used as shown in Table 1.
- Copolymers (2) to (20) were obtained.
- Table 1 shows the names of the components and the ratios (weight ratio, parts by weight, molar ratio, and molar amount) of each component in Examples 2 to 20.
- Comparative Examples 1 to 7 Synthesis of Comparative Acrylate Esters / Compound (B) Copolymers (1) to (7)
- the ratio of each component (weight ratio, parts by weight, molar ratio and mole) Acrylic ester / compound (B) copolymers (1) to (7) for comparison were obtained in the same manner as in Example 1 except that the amount was used as shown in Table 1.
- Table 1 shows the names of the components and the proportions (weight ratio, parts by weight, molar ratio, and molar amount) of each component in Comparative Examples 1 to 7.
- the aqueous solution containing the copolymer of the present invention contains a high concentration (3 wt%) of a polyelectrolyte such as L-ascorbyl magnesium phosphate. It was found to have a viscosity of 5000 mPa ⁇ s or more. Therefore, the copolymer of the present invention can form a viscous aqueous solution having a desired viscosity in the presence of an electrolyte, particularly a polyelectrolyte, and the desired viscosity can be obtained even when the concentration is high. I found that I could hold it.
- the copolymer of the present invention contains a predetermined amount of a fluorine-containing acrylate ester having a specific structure and, if necessary, a predetermined amount of a cross-linking agent component as components of the copolymer, and therefore increases in the presence of an electrolyte. It was found to have a sticky effect and a salt resistance effect.
- the acrylic ester (A) / compound (B) copolymer of the present invention can form a viscous aqueous solution having a desired viscosity in the presence of an electrolyte, particularly a polyelectrolyte, a good thickening can be achieved.
- it can be used as a thickener having a salt-resistant property, and can be expected, for example, as a thickener used in cosmetics and the like.
- the aqueous solution containing the comparative copolymer (8) was not sufficiently liquid or coated, and had no elastic touch.
- the aqueous solution containing the copolymer of the present invention has a good degree of liquid breakage, has a plunging tactile sensation (elastic tactile sensation), is difficult to drip, and has good coating properties. For this reason, it can be expected as a thickener used in cosmetics having excellent usability and a unique feel.
- the aqueous solution containing the copolymer (1) or (3) of the present invention is excellent in transparency of appearance, and thus is suitably used for cosmetics characterized by non-coloring such as skin lotions and cosmetic liquids. can do.
- Example 21 Preparation of lotion using acrylic ester (A) / compound (B) copolymer (3) of the present invention After component 1 was added to a part of component 11 and swollen, the component was stirred. 2 was added to adjust the pH to 8.0. Next, ingredients 3 to 9 were added and stirred and mixed uniformly. Finally, ingredients 10 and 11 were added to prepare a lotion. Table 4 shows the names of the components and the proportions (% by weight) of the components in Example 21.
- the lotion obtained in Example 21 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 22 Preparation of Emulsion Using Acrylic Ester (A) / Compound (B) Copolymer (3) of the Present Invention
- Components 1 to 7 and a part of components 8, 13, 14 and 16 were mixed in respective proportions. The mixture was stirred and mixed at 80 ° C. After the latter was added dropwise to the former, the mixture was stirred and emulsified. Next, the viscosity was adjusted to pH 8.0 with component 9, and further components 10 to 12 were added and cooled. Finally, components 15 and 16 were added to prepare an emulsion.
- Table 5 shows the names of the components and the proportions (% by weight) of the components in Example 22.
- Example 22 The emulsion obtained in Example 22 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 23 Preparation of Cosmetic Liquid Using Acrylic Ester (A) / Compound (B) Copolymer (3) of the Present Invention
- component 1 was added to a part of component 12 and swollen, the component was stirred. 2 was added to adjust the pH to 8.0.
- a part of components 3 to 10 and 12 were mixed and dissolved at a normal temperature in respective proportions to obtain a viscous water-soluble liquid while stirring, and finally components 11 and 12 were added to prepare a cosmetic liquid.
- Table 6 shows the names of the components and the ratio (% by weight) of each component in Example 23.
- the cosmetic liquid obtained in Example 23 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 24 Preparation of Cream Using Acrylic Ester (A) / Compound (B) Copolymer (3) of the Present Invention
- Components 1 to 6 and components 7, 9 to 11, 13 and 15 were partially mixed.
- the mixture was stirred and mixed at a rate of 80 ° C. After the latter was added dropwise to the former, the mixture was stirred and emulsified.
- the pH was adjusted to pH 8.0 with a part of ingredients 12 and 15, and a part of ingredients 8 and 15 was added and cooled.
- ingredients 14 and 15 were added to prepare a cream.
- Table 7 shows the names of the components and the ratio (% by weight) of each component in Example 24.
- Example 24 The cream obtained in Example 24 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 25 Preparation of Cream Pack Using Acrylic Ester (A) / Compound (B) Copolymer (3) of the Present Invention
- Components 1 to 3 and components 4 to 6, 9 and 11 Stir and mix at a rate and warm to 80 ° C. After the latter was added dropwise to the former, the mixture was stirred and emulsified. Next, the pH was adjusted to 8.0 with a part of components 7 and 11, and a part of components 8 and 11 were added and cooled. Finally, components 10 and 11 were added to prepare a cream pack.
- Table 8 shows the names of the components and the ratio (% by weight) of each component in Example 25.
- the cream pack obtained in Example 25 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 26 Preparation of Massage Cream Using Acrylic Ester (A) / Compound (B) Copolymer (3) of the Present Invention
- Components 1 to 7 and components 8, 10, 12, and 14 Stir and mix at a rate and warm to 80 ° C. After the latter was added dropwise to the former, the mixture was stirred and emulsified. Next, the viscosity was adjusted with a part of ingredients 9 and 14 to pH 8.0, a part of ingredients 11 and 14 was added and cooled, and finally ingredients 13 and 14 were added to prepare a massage cream.
- Table 9 shows the names of the components and the ratio (% by weight) of each component in Example 26.
- Example 26 The massage cream obtained in Example 26 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 27 Preparation of Cleansing Gel Using Acrylic Ester (A) / Compound (B) Copolymer (3) of the Invention
- Components 4 and 5 and components 1, 6, 7 and 9 Stir and mix at a rate and warm to 80 ° C. After the latter was added dropwise to the former, the mixture was stirred and emulsified. Next, the pH was adjusted to 8.0 with a part of components 2 and 9, and further, a part of components 3 and 9 was added and cooled. Finally, components 8 and 9 were added to prepare a cleansing gel.
- Table 10 shows the names of the components and the proportions (% by weight) of the components in Example 27.
- the cleansing gel obtained in Example 27 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 28 Preparation of Facial Cleansing Foam Using Acrylic Ester (A) / Compound (B) Copolymer (3) of the Present Invention
- Components 1 to 6 were stirred and mixed in respective proportions and heated to 80 ° C.
- a part of components 7 to 9, 12, 13 and 15 stirred and mixed in their respective proportions was heated to 80 ° C. and mixed.
- a part of ingredients 10 and 15 is added to adjust the viscosity.
- a part of ingredients 11 and 15 is added to adjust to pH 8.5 and cooled, and finally ingredients 14 and 15 are added.
- a facial cleansing foam was prepared.
- Table 11 shows the names of the components and the ratio (% by weight) of each component in Example 28.
- the face-washing foam obtained in Example 28 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 29 Preparation of Sunscreen Using Acrylic Ester (A) / Compound (B) Copolymer (3) of the Present Invention
- a part of component 1 and 4 to 8, and the remainder of component 1 and 9 to 13 The mixture was stirred and mixed at each ratio and heated to 80 ° C. After the latter was added dropwise to the former, the mixture was stirred and emulsified. Next, adjust the viscosity to pH 8.0 with a part of ingredients 2 and 16 and add a part of ingredients 3 and 16 to cool, and finally add a part of ingredients 14, 15 and 16 to sunscreen.
- Table 12 shows the names of the components and the ratio (% by weight) of each component in Example 29.
- Example 29 The sunscreen obtained in Example 29 was shaped without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 30 Preparation of Styling Gel Using Acrylic Ester (A) / Compound (B) Copolymer (3) of the Present Invention
- a part of components 1, 2, 4, 6 and 8 are brought to room temperature in respective proportions.
- a part of components 3 and 8 was adjusted to pH 8.0, and a part of components 5 and 8 were further added and mixed.
- ingredients 7 and 8 were added to prepare a styling gel.
- Table 13 shows the names of the components and the proportions (% by weight) of the components in Example 30.
- Example 30 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 31 Preparation of Eyeliner Using Acrylic Ester (A) / Compound (B) Copolymer (3) of the Present Invention
- a part of components 1, 2, 4, 6, 8 and 10 are each in a proportion.
- the mixture was dissolved at room temperature, then adjusted to pH 8.0 with component 5, and then a part of components 3, 7 and 10 were added and mixed.
- components 9 and 10 were added to prepare an eyeliner.
- Table 14 shows the names of the components and the ratio (% by weight) of each component in Example 31.
- Example 31 The eyeliner obtained in Example 31 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 32 Preparation of Mascara Using Acrylic Ester (A) / Compound (B) Copolymer (3) of the Present Invention
- Components 1 to 5 and components 6, 8, 11 to 14 and 16 were partially mixed The mixture was stirred and mixed at a rate of 80 ° C. After the latter was added dropwise to the former, the mixture was stirred and emulsified. Next, the viscosity was adjusted with a part of ingredients 7 and 16 to pH 8.0, and ingredients 9 and 10 were added and cooled, and finally ingredients 15 and 16 were added to prepare a mascara.
- Table 15 shows the names of the respective components in Example 32 and the ratios (% by weight) of the respective components.
- Example 32 The mascara obtained in Example 32 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 33 Preparation of Foundation Using Acrylic Ester (A) / Compound (B) Copolymer (3) of the Present Invention
- Components 1 to 5 and 11 and components 12, 13, 15 and 17 were partially mixed The mixture was stirred and mixed at a rate of 80 ° C. The latter was added to the former and mixed. Next, a part of components 14 and 17 was adjusted to pH 8.0, and further a part of components 6 to 10 and 17 was added and cooled with stirring. Finally, components 16 and 17 were added to prepare a foundation.
- Table 16 shows the names of the components and the proportions (% by weight) of the components in Example 33.
- Example 33 The foundation obtained in Example 33 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 34 Preparation of Cleansing Gel Using Acrylic Ester (A) / Compound (B) Copolymer (3) of the Present Invention
- a part of components 1, 5 to 8 and 10 were mixed in a uniform ratio and uniformly mixed Stir until.
- component 2 was added to pH 8.0 and stirred until a uniform gel was formed, and then components 3, 4 and 10 were partially added and mixed.
- ingredients 9 and 10 were added to prepare a cleansing gel.
- Table 17 shows the names of the respective components and the proportions (% by weight) of the respective components in Example 34.
- the cleansing gel obtained in Example 34 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 35 Preparation of Facial Cleansing Foam Using Acrylic Ester (A) / Compound (B) Copolymer (3) of the Present Invention
- Components 1 to 6 were mixed in respective proportions and heated to 80 ° C. A part of 7, 8, 10 and 13 mixed in advance was added and stirred. Next, adjust the viscosity to pH 8.0 with a part of ingredients 9 and 13, add a part of ingredients 11 and 13 and cool to 30 ° C. with stirring, and finally add ingredients 12 and 13 to wash the face. A foam was prepared.
- Table 18 shows the names of the respective components and the proportions (% by weight) of the respective components in Example 35.
- the face-wash foam obtained in Example 35 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 36 Preparation of Facial Cleansing Foam Using Acrylic Ester (A) / Compound (B) Copolymer (3) of the Present Invention
- Components 1 and 2 were mixed in respective proportions and heated to 80 ° C. A part of 4, 7 to 10 and 12 mixed in advance was added and stirred. Next, after adding a part of components 5 and 12 to adjust the viscosity, further adding a part of components 3, 6 and 12 and cooling to 30 ° C. while stirring, finally adding components 11 and 12 to wash the face A foam was prepared.
- Table 19 shows the names of the components and the proportions (% by weight) of the components in Example 36.
- the face-wash foam obtained in Example 36 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 37 Preparation of body shampoo using acrylic ester (A) / compound (B) copolymer (3) of the present invention
- Ingredients 1 to 3 were mixed in respective proportions and heated to 80 ° C. A portion of 5-7, 10, 11 and 13 previously mixed uniformly was gradually added and stirred until uniform. Next, adjust the viscosity to pH 8.5 with a part of components 8 and 13, add a part of components 4, 9 and 13 and cool to 30 ° C. with stirring, and finally add components 12 and 13 A body shampoo was prepared.
- Table 20 shows the names of the components and the ratio (% by weight) of each component in Example 37.
- the body shampoo obtained in Example 37 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 38 Preparation of Deodorant Gel Using Acrylic Ester (A) / Compound (B) Copolymer (3) of the Present Invention
- ingredients 5 and 6 were mixed with part of ingredient 15 and swollen, ingredients A portion of 7 and 15 was added to neutralize.
- a part of components 8 to 13 and 15 were added and mixed, and then components 1 to 4 were further added and mixed uniformly.
- ingredients 14 and 15 were added to prepare a deodorant gel.
- Table 21 shows the names of the components in Example 38 and the proportions (% by weight) of the components.
- Example 38 The deodorant gel obtained in Example 38 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 39 Preparation of Color Treatment Using Acrylic Ester (A) / Compound (B) Copolymer (3) of the Present Invention Components 2 to 9 and 11, and a part of Component 1, 10 and 13 to 31
- the mixture was stirred and mixed at each ratio and heated to 90 ° C. Next, both were mixed at 90 ° C. and cooled to 60 ° C.
- Component 12 was then added, further cooled to 45 ° C., and finally components 1 and 32 were added to prepare a color treatment.
- Table 22 shows the names of the respective components in Example 39 and the ratios (% by weight) of the respective components.
- Example 39 The color treatment obtained in Example 39 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 40 Preparation of Amino Acid Shampoo Using Acrylic Ester (A) / Compound (B) Copolymer (3) of the Present Invention
- Components 3 to 10 were mixed in respective proportions and heated to 80 ° C., A part of component 1, 2, 12-17, and 19-23, which had been mixed uniformly in advance, was gradually added and stirred until uniform. Next, after cooling to 60 ° C., the viscosity was adjusted to pH 8.0 with component 18, and after cooling to 30 ° C. with stirring, component 11 was further added, and finally components 1 and 24 were added to add an amino acid shampoo.
- Table 23 shows the names of the components and the proportions (% by weight) of the components in Example 40.
- the amino acid shampoo obtained in Example 40 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 41 Preparation of sulphite shampoo using acrylic ester (A) / compound (B) copolymer (3) of the present invention
- Components 2 to 4 and 7 were mixed in respective proportions and heated to 80 ° C. A portion of component 1, 5, 8, and 10-14 previously mixed uniformly was gradually added and stirred until uniform. Next, the viscosity was adjusted to pH 8.0 with Component 9 and cooled to 30 ° C. with stirring, then Component 6 was added, and finally Components 1 and 15 were added to prepare a sulfite shampoo.
- Table 24 shows the names of the components and the ratio (% by weight) of each component in Example 41.
- the sulphite shampoo obtained in Example 41 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 42 Preparation of Paraphenylenediamine Oxidative Hair Dye Using Acrylic Ester (A) / Compound (B) Copolymer (3) of the Present Invention
- Part of Components 1 to 5, 6 and 12, 13 and 15 to 18 and components 8 to 11 were stirred and mixed in respective proportions and heated to 90 ° C. Next, both were mixed at 90 ° C. and cooled to 60 ° C. Next, component 7 was added, the mixture was further cooled to 45 ° C., and finally components 6 and 14 were added to prepare a paraphenylenediamine-based oxidative hair dye.
- Table 25 shows the names of the components and the ratio (% by weight) of each component in Example 42.
- the paraphenylenediamine oxidative hair dye obtained in Example 42 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 43 Preparation of Toluenediamine Oxidative Hair Dye Using Acrylic Ester (A) / Compound (B) Copolymer (3) of the Present Invention
- Table 26 shows the names of the components and the proportions (% by weight) of the components in Example 43.
- the toluenediamine oxidative hair dye obtained in Example 43 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 44 Preparation of thioglycolic acid-based permanent wave solution using acrylic ester (A) / compound (B) copolymer (3) of the present invention
- a part of components 1 to 3 and 5 were mixed in respective proportions.
- the mixture was mixed, the viscosity was adjusted to pH 8.5 with components 4 and 5, and the mixture was made the first liquid.
- components 6 to 9 were mixed to prepare a second liquid.
- the 1st liquid and the 2nd liquid were mixed in the ratio of the same quantity, and the liquid for thioglycolic acid type permanent waves was prepared.
- Table 27 shows the names of the components and the proportions (% by weight) of the components in Example 44.
- the thioglycolic acid permanent wave solution obtained in Example 44 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- Example 45 Preparation of Cysteamine Curling Material Using Acrylic Ester (A) / Compound (B) Copolymer (3) of the Present Invention
- Components 1 to 3 and a part of 5 are mixed in respective proportions, The viscosity was adjusted to pH 9.0 with 4 and 5 to obtain the first liquid.
- components 6 to 9 were mixed to prepare a second liquid.
- the 1st liquid and the 2nd liquid were mixed in the ratio of the same quantity, and the cysteamine type curling charge was prepared.
- Table 28 shows the names of the components and the proportions (% by weight) of the components in Example 45.
- Example 45 The cysteamine-based curling charge obtained in Example 45 had a shape without dripping. Further, the acrylic ester (A) / compound (B) copolymer of the present invention did not aggregate.
- the acrylic acid ester (A) / compound (B) copolymer of the present invention can be used as a thickener having excellent properties, it is excellent in use feeling and applicability and has a unique tactile sensation.
- Various cosmetics such as beauty essence, cream, cleansing cream, cleansing gel, styling gel, eyeliner, mascara, foundation and body shampoo can be provided.
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Abstract
Description
(1)(A)一般式[1]で示されるアクリル酸エステル、ならびに(B)重合性不飽和基と、カルボキシル基、スルホ基およびリン酸基からなる群から選ばれるいずれかの官能基とを分子内に有する化合物を構成成分とし、
上記アクリル酸エステル(A)と上記化合物(B)との割合(重量比)が、(A)/(B)=9.0/91.0~28.5/71.5である、
アクリル酸エステル(A)/化合物(B)共重合体。
一般式[1]:
(式中、R1は、水素原子または炭素数1~6のアルキル基を表し、mは、2~4の整数を表す。)
一般式[1]:
(式中、R1は、水素原子または炭素数1~6のアルキル基を表し、mは、2~4の整数を表す。)
一般式[2]:
(式中、R2は、水素原子または炭素数1~6のアルキル基を表す。)
一般式[3]:
(式中、Aは、酸素原子または-NH-基を表し、T1は、ヒドロキシル基を有していてもよい炭素数1~6のアルキレン基を表し、R3は、水素原子または炭素数1~6のアルキル基を表す。)
一般式[4]:
(式中、T2は、結合手または炭素数1~6のアルキレン基を表し、R4は、水素原子または炭素数1~6のアルキル基を表す。)
一般式[5]:
(式中、T3は、炭素数1~6のアルキレン基を表し、R5は、水素原子または炭素数1~6のアルキル基を表す。)
一般式[6]:
(式中、kは、1~6の整数を表す。)
一般式[7]:
(式中、T4は、炭素数1~20のアルキレン基、一般式[7-1]で示される基または一般式[7-2]で示される基を表し、R6およびR6'はそれぞれ独立して、水素原子またはメチル基を表す。)
一般式[7-1]:
(式中、p個のT4'はそれぞれ独立して、炭素数1~6のアルキレン基を表し、pは、1~6の整数を表す。)
一般式[7-2]:
(式中、p'個のT4''およびT4'''はそれぞれ独立して、炭素数1~6のアルキレン基を表し、p'は、1~12の整数を表す。)
一般式[8]:
(式中、T5、T5'、T5''、T6、T6'、T6''およびT7はそれぞれ独立して、炭素数1~3のアルキレン基を表す。)
一般式[9]:
(式中、q個のT8、q'個のT8'、r個のT9およびr'個のT9'はそれぞれ独立して、炭素数1~6のアルキレン基を表し、qおよびq'は、0または1を表し、rは、1~6の整数を表し、r'は、0~6の整数を表す。)
一般式[10]:
(式中、R7~R14はそれぞれ独立して、水素原子、ビニル基またはビニルカルボニル基を表す。ただし、R7~R14のうちの少なくとも2つのRは、ビニル基またはビニルカルボニル基を表す。)
一般式[11]:
(式中、T10、T11およびT11'はそれぞれ独立して、炭素数1~6のアルキレン基を表す。)
一般式[12]:
(式中、t個のT12はそれぞれ独立して、炭素数1~6のアルキレン基を表し、R15は、炭素数6~10の2~4価の芳香族炭化水素基を表し、tは、2~4の整数を表す。)
一般式[13]:
(式中、T13は、炭素数1~6のアルキレン基を表し、T14およびT14'はそれぞれ独立して、炭素数6~10のアリーレン基を表す。)
一般式[14]:
(式中、T15は、炭素数6~10のアリーレン基を表す。)
一般式[15]:
(式中、vは、0~6の整数を表す。)
一般式[16]:
(式中、T16は、炭素数1~6のアルキレン基を表す。)
(1)1重量%のアクリル酸エステル(A)/化合物(B)共重合体と、3重量%のリン酸アスコルビルマグネシウムを含み、pHが8である水溶液の20℃における粘度が、5000mPa・s以上である。
アクリル酸35g(0.49mol;和光純薬工業株式会社製)、2-パーフルオロヘキシルエチルアクリレート10.69g(0.0256mol;ユニマテック株式会社製)、ジエチレングリコールジアリルエーテル0.1333g(0.72mmol;和光純薬工業株式会社製)およびジ(4-tert-ブチルシクロヘキシル)パーオキシジカーボネート0.0734g(0.18mmol;製品名:パーカドックス16;化薬アクゾ株式会社製)をシクロヘキサン411mLおよび酢酸エチル45.7mLの混合溶媒中に投入し、溶液を均一に混合した。混合した溶液を窒素ガス雰囲気下で30分間バブリングし、溶液中に含まれる酸素を脱気した。その後、溶液を攪拌しながら、30分かけて55℃まで加熱し、同温度を維持しながら溶液をさらに1時間攪拌した。次いで、溶液を1時間30分かけて75℃まで加熱し、同温度を維持しながら溶液をさらに2時間攪拌した。攪拌後、溶液を室温まで冷却し、冷却することによって析出した共重合体(ポリマー)を濾取した後、濾取した共重合体を90~110℃で8時間減圧乾燥することにより、本発明のアクリル酸エステル(A)/化合物(B)共重合体(1)42.43gを得た(収率:93%)。実施例1における各成分の名称と各成分の割合(重量比、重量部、モル比およびモル量)を表1に示す。
実施例2~20では、表1に記載の成分を、各成分の割合(重量比、重量部、モル比およびモル量)が表1となるように使用した以外は、実施例1と同様の方法に準じて、本発明のアクリル酸エステル(A)/化合物(B)共重合体(2)~(20)を得た。実施例2~20における各成分の名称と各成分の割合(重量比、重量部、モル比およびモル量)を表1に示す。
比較例1~7では、各成分の割合(重量比、重量部、モル比およびモル量)が表1となるように使用した以外は、実施例1と同様の方法に準じて、比較用のアクリル酸エステル/化合物(B)共重合体(1)~(7)を得た。比較例1~7における各成分の名称と各成分の割合(重量比、重量部、モル比およびモル量)を表1に示す。
脱イオン水198g中に、実施例1~5、10、11、14、15、17および18で得られた本発明の共重合体(1)~(5)、(10)、(11)、(14)、(15)、(17)または(18)を2g、あるいは比較用の共重合体(1)~(7)を2g添加し、共重合体を分散させて1重量%の分散液を得た。次いで、該分散液に、攪拌下で分散液のpHを測定しながら、pHが8.0±0.5になるまで5Nの水酸化ナトリウム水溶液を添加して、本発明の共重合体を含有する水溶液(1)~(5)、(10)、(11)、(14)、(15)、(17)および(18)を含有する水溶液、ならびに比較用の共重合体を含有する水溶液(1)~(7)を得た。これらの水溶液に、リン酸L-アスコルビルマグネシウムを所定量添加して攪拌し、リン酸L-アスコルビルマグネシウムが完全に溶解した後の水溶液の粘度を測定して、電解質(リン酸L-アスコルビルマグネシウム;2価の多価電解質)の添加量が該水溶液の粘度におよぼす影響を確認した。なお、粘度測定の値は、B型回転粘度計とローターNo.4を使用し、20℃の温度で、回転数3rpmのときの粘度を測定した値である。これらの結果を表2に示す。
脱イオン水に、実施例1、3および18で得られた本発明の共重合体(1)、(3)または(18)、あるいは「アクリル酸、アクリル酸長鎖アルキルエステルおよび架橋剤からなる共重合体」(比較用の共重合体(8))(商品名:AQUPEC、住友精化株式会社製)を添加し、共重合体を分散させて1重量%の分散液を得た。次いで、該分散液に、攪拌下で分散液のpHを測定しながら、pHが7.0±0.5になるまで5Nの水酸化ナトリウム水溶液を添加した後、分散液の粘度が約5000mPa・sとなるように塩化ナトリウムを添加して、本発明の共重合体(1)、(3)および(18)を含有する水溶液、ならびに比較用の共重合体(8)を含有する水溶液を得た。
各水溶液について、男女各5名を被験者とし、以下の項目について評価した。これらの結果を表3に示す。
1)使用感
共重合体を化粧品用途に供した際の使用感を、液切れの度合い(塗布し易さ)と触感の2つの項目で評価した。
液切れの度合い(塗布し易さ)は、各水溶液をすくい取った際の液切れの良し悪しで評価した。液切れが良い場合を2点、やや良い場合を1点、やや悪い場合を0点として10名の合計点から下記の4段階で評価した。
触感は、各水溶液を指で触れた際の触感で評価した。ぷるぷるとした触感(弾力のある触感)がある場合を2点、ややぷるぷるとした触感(やや弾力のある触感)がある場合を1点、ぷるぷるとした触感(弾力のある触感)がない場合を0点として10名の合計点から下記の4段階で評価した。
合計点18点以上:◎
合計点15点以上18点未満:○
合計点10点以上15点未満:△
合計点10点未満:×
2)塗布性
塗布性は、被験者の手の甲にスポイトで各水溶液を1滴たらし、甲を縦にした際に液だれしにくいかどうかで評価した。液だれしにくい場合を2点、やや液だれしにくい場合を1点、液だれしやすい場合を0点として10名の合計点から下記の4段階で評価した。
合計点18点以上:◎
合計点15点以上18点未満:○
合計点10点以上15点未満:△
合計点10点未満:×
3)透明性
透明性は、各溶液を目視で観察し、透明性があるかどうかで評価した。透明性がある場合を2点、やや透明性がある場合を1点、透明性に乏しい場合を0点として10名の合計点から下記の4段階で評価した。
合計点18点以上:◎
合計点15点以上18点未満:○
合計点10点以上15点未満:△
合計点10点未満:×
成分1を成分11の一部に加えて膨潤させた後、攪拌しながら成分2を加え、pH8.0に調整した。次いで、成分3~9を加えて均一に攪拌・混合し、最後に成分10および11を加えて化粧水を調製した。実施例21における各成分の名称と各成分の割合(重量%)を表4に示す。
成分1~7と、成分8、13、14および16の一部をそれぞれの割合で攪拌・混合し80℃に加温した。前者に後者を滴下した後、攪拌して乳化させた。次いで、成分9でpH8.0にして粘度を調整し、さらに成分10~12を加えて冷却し、最後に成分15および16を加えて乳液を調製した。実施例22における各成分の名称と各成分の割合(重量%)を表5に示す。
成分1を成分12の一部に加えて膨潤させた後、攪拌しながら成分2を加え、pH8.0に調整した。次いで、成分3~10および12の一部をそれぞれの割合で常温にて混合・溶解させ、攪拌しながら粘稠水溶性液体とし、最後に成分11および12を加えて美容液を調製した。実施例23における各成分の名称と各成分の割合(重量%)を表6に示す。
成分1~6と、成分7、9~11、13および15の一部をそれぞれの割合で攪拌・混合し80℃に加温した。前者に後者を滴下した後、攪拌して乳化させた。次いで、成分12および15の一部でpH8.0にして粘度を調整し、さらに成分8および15の一部を加えて冷却し、最後に成分14および15を加えてクリームを調製した。実施例24における各成分の名称と各成分の割合(重量%)を表7に示す。
成分1~3と、成分4~6、9および11の一部をそれぞれの割合で攪拌・混合し80℃に加温した。前者に後者を滴下した後、攪拌して乳化させた。次いで、成分7および11の一部でpH8.0にして粘度を調整し、さらに成分8および11の一部を加えて冷却し、最後に成分10および11を加えてクリームパックを調製した。実施例25における各成分の名称と各成分の割合(重量%)を表8に示す。
成分1~7と、成分8、10、12および14の一部をそれぞれの割合で攪拌・混合し80℃に加温した。前者に後者を滴下した後、攪拌して乳化させた。次いで、成分9および14の一部でpH8.0にして粘度を調整し、さらに成分11および14の一部を加えて冷却し、最後に成分13および14を加えてマッサージクリームを調製した。実施例26における各成分の名称と各成分の割合(重量%)を表9に示す。
成分4および5と、成分1、6、7および9の一部をそれぞれの割合で攪拌・混合し80℃に加温した。前者に後者を滴下した後、攪拌して乳化させた。次いで、成分2および9の一部でpH8.0にして粘度を調整し、さらに成分3および9の一部を加えて冷却し、最後に成分8および9を加えてクレンジングジェルを調製した。実施例27における各成分の名称と各成分の割合(重量%)を表10に示す。
成分1~6をそれぞれの割合で攪拌・混合し80℃に加温した。次いで、成分7~9、12、13および15の一部をそれぞれの割合で攪拌・混合したものを80℃に加温して加え、混合した。次に、成分10および15の一部を加えて粘度を調整し、さらに攪拌しながら成分11および15の一部を加えてpH8.5に調整して冷却し、最後に成分14および15を加えて洗顔フォームを調製した。実施例28における各成分の名称と各成分の割合(重量%)を表11に示す。
成分1の一部および4~8と、成分1の残部および9~13をそれぞれの割合で攪拌・混合し80℃に加温した。前者に後者を滴下した後、攪拌して乳化させた。次いで、成分2および16の一部でpH8.0にして粘度を調整し、さらに成分3および16の一部を加えて冷却し、最後に成分14、15および16の一部を加えて日焼け止めを調製した。実施例29における各成分の名称と各成分の割合(重量%)を表12に示す。
成分1、2、4、6および8の一部をそれぞれの割合で常温にて溶解させ、次いで、成分3および8の一部でpH8.0とし、さらに成分5および8の一部を加えて混合した。最後に成分7および8を加えてスタイリングジェルを調製した。実施例30における各成分の名称と各成分の割合(重量%)を表13に示す。
成分1、2、4、6、8および10の一部をそれぞれの割合で常温にて溶解させ、次いで、成分5でpH8.0とし、さらに成分3、7および10の一部を加えて混合した。最後に成分9および10を加えてアイライナーを調製した。実施例31における各成分の名称と各成分の割合(重量%)を表14に示す。
成分1~5と、成分6、8、11~14および16の一部をそれぞれの割合で攪拌・混合し80℃に加温した。前者に後者を滴下した後、攪拌して乳化させた。次いで、成分7および16の一部でpH8.0にして粘度を調整し、さらに成分9および10を加えて冷却し、最後に成分15および16を加えてマスカラを調製した。実施例32における各成分の名称と各成分の割合(重量%)を表15に示す。
成分1~5および11と、成分12、13、15および17の一部をそれぞれの割合で攪拌・混合し80℃に加温した。前者に後者を添加して混合した。次いで、成分14および17の一部でpH8.0とし、さらに攪拌しながら成分6~10および17の一部を加えて冷却し、最後に成分16および17を加えてファンデーションを調製した。実施例33における各成分の名称と各成分の割合(重量%)を表16に示す。
成分1、5~8および10の一部をそれぞれの割合で混合して均一になるまで撹拌した。次いで、成分2をpH8.0となるように加えて、均一なゲル状になるまで攪拌し、さらに成分3、4および10の一部を加えて混合した。最後に成分9および10を加えてクレンジングジェルを調製した。実施例34における各成分の名称と各成分の割合(重量%)を表17に示す。
成分1~6をそれぞれの割合で混合して80℃に加温し、成分7、8、10および13の一部をあらかじめ均一に混合したものを加えて撹拌した。次いで、成分9および13の一部でpH8.0にして粘度を調整し、さらに成分11および13の一部を加えて撹拌しながら30℃まで冷却し、最後に成分12および13を加えて洗顔フォームを調製した。実施例35における各成分の名称と各成分の割合(重量%)を表18に示す。
成分1および2をそれぞれの割合で混合して80℃に加温し、成分4、7~10および12の一部をあらかじめ均一に混合したものを加えて撹拌した。次いで、成分5および12の一部を加えて粘度を調整した後、さらに成分3、6および12の一部を加えて撹拌しながら30℃まで冷却し、最後に成分11および12を加えて洗顔フォームを調製した。実施例36における各成分の名称と各成分の割合(重量%)を表19に示す。
成分1~3をそれぞれの割合で混合して80℃に加温し、成分5~7、10、11および13の一部をあらかじめ均一に混合したものを徐々に加えて均一になるまで撹拌した。次いで、成分8および13の一部でpH8.5にして粘度を調整し、さらに成分4、9および13の一部を加えて撹拌しながら30℃まで冷却し、最後に成分12および13を加えてボディーシャンプーを調製した。実施例37における各成分の名称と各成分の割合(重量%)を表20に示す。
成分5および6を成分15の一部に混合して膨潤させた後、成分7および15の一部を加えて中和した。次いで、成分8~13および15の一部を加えて混合した後、さらに成分1~4を加えて均一に混合した。最後に成分14および15を加えてデオドラントジェルを調製した。実施例38における各成分の名称と各成分の割合(重量%)を表21に示す。
成分2~9および11と、成分1の一部、10および13~31をそれぞれの割合で攪拌・混合し90℃に加温した。次に、両者を90℃で混合し、60℃に冷却した。次いで、成分12を加え、さらに45℃に冷却し、最後に成分1および32を加えてカラートリートメントを調製した。実施例39における各成分の名称と各成分の割合(重量%)を表22に示す。
成分3~10をそれぞれの割合で混合して80℃に加温し、成分1の一部、2、12~17および19~23をあらかじめ均一に混合したものを徐々に加えて均一になるまで撹拌した。次いで、60℃に冷却した後、成分18でpH8.0にして粘度を調整し、撹拌しながら30℃まで冷却した後、さらに成分11を加え、最後に成分1および24を加えてアミノ酸系シャンプーを調製した。実施例40における各成分の名称と各成分の割合(重量%)を表23に示す。
成分2~4および7をそれぞれの割合で混合して80℃に加温し、成分1の一部、5、8および10~14をあらかじめ均一に混合したものを徐々に加えて均一になるまで撹拌した。次いで、成分9でpH8.0にして粘度を調整し、撹拌しながら30℃まで冷却した後、さらに成分6を加え、最後に成分1および15を加えてサルファイト系シャンプーを調製した。実施例41における各成分の名称と各成分の割合(重量%)を表24に示す。
成分1~5、6の一部、12、13および15~18と、成分8~11をそれぞれの割合で攪拌・混合し90℃に加温した。次に、両者を90℃で混合し、60℃に冷却した。次いで、成分7を加え、さらに45℃に冷却し、最後に成分6および14を加えてパラフェニレンジアミン系酸化染毛剤を調製した。実施例42における各成分の名称と各成分の割合(重量%)を表25に示す。
成分1~5、12~20および24の一部と、成分6~11をそれぞれの割合で攪拌・混合し90℃に加温した。次に、両者を90℃で混合し、60℃に冷却した。次いで、成分22および23を加え、さらに45℃に冷却し、最後に成分21および24を加えてトルエンジアミン系酸化染毛剤を調製した。実施例43における各成分の名称と各成分の割合(重量%)を表26に示す。
成分1~3および5の一部をそれぞれの割合で混合し、成分4および5でpH8.5にして粘度を調整し、第1液とした。次に、成分6~9を混合して第2液を調製した。次いで、第1液と第2液を同量の割合で混合してチオグリコール酸系パーマネントウェーブ用液を調製した。実施例44における各成分の名称と各成分の割合(重量%)を表27に示す。
成分1~3および5の一部をそれぞれの割合で混合し、成分4および5でpH9.0にして粘度を調整し、第1液とした。次に、成分6~9を混合して第2液を調製した。次いで、第1液と第2液を同量の割合で混合してシステアミン系カーリング料を調製した。実施例45における各成分の名称と各成分の割合(重量%)を表28に示す。
Claims (16)
- 前記アクリル酸エステル(A)/化合物(B)共重合体が、(1)の特性を有するものである、請求項1に記載の共重合体。
(1)1重量%の前記アクリル酸エステル(A)/化合物(B)共重合体と、3重量%のリン酸アスコルビルマグネシウムを含み、pHが8である水溶液の20℃における粘度が、5000mPa・s以上である。 - 前記アクリル酸エステル(A)と前記化合物(B)との割合(重量比)が、(A)/(B)=14.0/86.0~27.3/72.7である、請求項1または2に記載の共重合体。
- 前記アクリル酸エステル(A)と前記化合物(B)との割合(重量比)が、(A)/(B)=14.0/86.0~25.0/75.0である、請求項1または2に記載の共重合体。
- 前記アクリル酸エステル(A)/化合物(B)共重合体が、更に(C)エチレン性不飽和基を2個以上有する化合物を構成成分として含むものである、請求項1~4のいずれか1項に記載の共重合体。
- 前記化合物(C)の割合が、前記アクリル酸エステル(A)および前記化合物(B)の合計100重量部に対して、0.0001~1.5重量部である、請求項5に記載の共重合体。
- 前記アクリル酸エステル(A)が、2-パーフルオロヘキシルエチル(メタ)アクリレートである、請求項1~6のいずれか1項に記載の共重合体。
- 前記化合物(B)が、一般式[2]~[5]で示される化合物である、請求項1~7のいずれか1項に記載の共重合体。
一般式[2]:
(式中、R2は、水素原子または炭素数1~6のアルキル基を表す。)
一般式[3]:
(式中、Aは、酸素原子または-NH-基を表し、T1は、ヒドロキシル基を有していてもよい炭素数1~6のアルキレン基を表し、R3は、水素原子または炭素数1~6のアルキル基を表す。)
一般式[4]:
(式中、T2は、結合手または炭素数1~6のアルキレン基を表し、R4は、水素原子または炭素数1~6のアルキル基を表す。)
一般式[5]:
(式中、T3は、炭素数1~6のアルキレン基を表し、R5は、水素原子または炭素数1~6のアルキル基を表す。) - 前記化合物(C)が、一般式[7]で示される化合物、一般式[8]で示される化合物、一般式[9]で示される化合物または一般式[16]で示される化合物である、請求項5に記載の共重合体。
一般式[7]:
(式中、T4は、炭素数1~20のアルキレン基、一般式[7-1]で示される基または一般式[7-2]で示される基を表し、R6およびR6'はそれぞれ独立して、水素原子またはメチル基を表す。)
一般式[7-1]:
(式中、p個のT4'はそれぞれ独立して、炭素数1~6のアルキレン基を表し、pは、1~6の整数を表す。)
一般式[7-2]:
(式中、p'個のT4''およびT4'''はそれぞれ独立して、炭素数1~6のアルキレン基を表し、p'は、1~12の整数を表す。)
一般式[8]:
(式中、T5、T5'、T5''、T6、T6'、T6''およびT7はそれぞれ独立して、炭素数1~3のアルキレン基を表す。)
一般式[9]:
(式中、q個のT8、q'個のT8'、r個のT9およびr'個のT9'はそれぞれ独立して、炭素数1~6のアルキレン基を表し、qおよびq'は、0または1を表し、rは、1~6の整数を表し、r'は、0~6の整数を表す。)
一般式[16]:
(式中、T16は、炭素数1~6のアルキレン基を表す。) - 前記化合物(C)が、1,10-デカンジオールジアクリレート、ペンタエリスリトールトリアリルエーテル、ジエチレングリコールジアリルエーテルまたはN,N'-メチレンビスアクリルアミドである、請求項5に記載の共重合体。
- 前記化合物(C)が、ジエチレングリコールジアリルエーテルである、請求項5に記載の共重合体。
- 請求項1~12のいずれか1項に記載のアクリル酸エステル(A)/化合物(B)共重合体を配合した化粧料。
- 更に電解質を配合したことを特徴とする、請求項13に記載の化粧料。
- 前記電解質が多価電解質である、請求項14に記載の化粧料。
- 請求項1~12のいずれか1項に記載のアクリル酸エステル(A)/化合物(B)共重合体を含有する増粘剤。
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Cited By (4)
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JP2018173622A (ja) * | 2017-01-18 | 2018-11-08 | 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. | 光硬化性組成物及びそれから形成された光硬化膜 |
WO2019235108A1 (ja) * | 2018-06-06 | 2019-12-12 | 富士フイルム株式会社 | 改質剤、組成物、ハードコートフィルム、ハードコートフィルムを備えた物品、及び画像表示装置 |
JP6953604B1 (ja) * | 2020-12-04 | 2021-10-27 | 株式会社コスモビューティー | アスコルビン酸化合物含有組成物 |
WO2023033127A1 (ja) * | 2021-09-03 | 2023-03-09 | 富士フイルム和光純薬株式会社 | 乳化組成物、該組成物を含有する皮膚外用剤および化粧料 |
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JP2018173622A (ja) * | 2017-01-18 | 2018-11-08 | 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. | 光硬化性組成物及びそれから形成された光硬化膜 |
WO2019235108A1 (ja) * | 2018-06-06 | 2019-12-12 | 富士フイルム株式会社 | 改質剤、組成物、ハードコートフィルム、ハードコートフィルムを備えた物品、及び画像表示装置 |
CN112004838A (zh) * | 2018-06-06 | 2020-11-27 | 富士胶片株式会社 | 改性剂、组合物、硬涂膜、具备硬涂膜的物品及图像显示装置 |
JPWO2019235108A1 (ja) * | 2018-06-06 | 2021-04-22 | 富士フイルム株式会社 | 改質剤、組成物、ハードコートフィルム、ハードコートフィルムを備えた物品、及び画像表示装置 |
JP6953604B1 (ja) * | 2020-12-04 | 2021-10-27 | 株式会社コスモビューティー | アスコルビン酸化合物含有組成物 |
JP2022089582A (ja) * | 2020-12-04 | 2022-06-16 | 株式会社コスモビューティー | アスコルビン酸化合物含有組成物 |
WO2023033127A1 (ja) * | 2021-09-03 | 2023-03-09 | 富士フイルム和光純薬株式会社 | 乳化組成物、該組成物を含有する皮膚外用剤および化粧料 |
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CN108779216A (zh) | 2018-11-09 |
TW201740920A (zh) | 2017-12-01 |
CN108779216B (zh) | 2021-08-03 |
KR20180129880A (ko) | 2018-12-05 |
US10973750B2 (en) | 2021-04-13 |
JPWO2017170961A1 (ja) | 2019-02-14 |
JP6885396B2 (ja) | 2021-06-16 |
EP3438143A1 (en) | 2019-02-06 |
KR102285780B1 (ko) | 2021-08-03 |
TWI751149B (zh) | 2022-01-01 |
EP3438143A4 (en) | 2019-10-02 |
US20190110975A1 (en) | 2019-04-18 |
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