WO2014098052A1 - Émulsion de résine acrylique pour agents de coiffage, agent de coiffage la comprenant et procédé de coiffage - Google Patents

Émulsion de résine acrylique pour agents de coiffage, agent de coiffage la comprenant et procédé de coiffage Download PDF

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Publication number
WO2014098052A1
WO2014098052A1 PCT/JP2013/083682 JP2013083682W WO2014098052A1 WO 2014098052 A1 WO2014098052 A1 WO 2014098052A1 JP 2013083682 W JP2013083682 W JP 2013083682W WO 2014098052 A1 WO2014098052 A1 WO 2014098052A1
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Prior art keywords
acrylic resin
hairdressing
resin emulsion
emulsion
hair
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PCT/JP2013/083682
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English (en)
Japanese (ja)
Inventor
光則 上田
延能 吉村
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日本合成化学工業株式会社
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Priority to CN201380066728.8A priority Critical patent/CN104869975B/zh
Priority to KR1020157019066A priority patent/KR102146899B1/ko
Publication of WO2014098052A1 publication Critical patent/WO2014098052A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8129—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers or esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers, e.g. polyvinylmethylether
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to an acrylic resin emulsion useful for a hair styling agent (hair styling agent).
  • hairdressing agents such as liquid, gel, foam, mist, cream and wax.
  • hair styling agents are based on a polymer (set polymer) for maintaining a desired shape by forming a film on the hair surface, and depending on the additives and dosage forms applied for various purposes.
  • hair styling agents can be freely arranged at the time of hair styling, and hair creams and hair waxes, which are emulsifiers using oil and water, have become mainstream as dosage forms that can be easily modified after styling. Yes.
  • hairdressing agents are required to have performance in styling (conditioning hair) such as the ability to give the hair a desired shape and hold it for a long time, excellent appearance performance, and excellent tactile feel.
  • styling condition hair
  • the convenience of washing and removing the hairdressing agent from the hair after use is also required as a performance, and various hairdressing agents have been developed.
  • Patent Document 1 describes an aqueous hair styling agent using a polyvinyl alcohol-based resin having a specific structure as a main component of a polymer component as a main ingredient.
  • Patent Document 2 describes beeswax and an interface.
  • a hair cosmetic is described in which polyvinyl alcohol is blended as a blending agent in an emulsion composition comprising an active agent and water.
  • the hair styling agent of the above-mentioned patent document 1 has the performance that the polyvinyl alcohol-based resin having a specific structure has a good curl holding power under high humidity conditions, has less stickiness, has a moisturizing power, and has little damage to hair.
  • the hairdressing agent of Patent Document 2 described above improves the aesthetics at the time of use by blending a polyvinyl alcohol-based resin in the emulsion composition, and does not impart unnatural shine to the hair after application. It calls for performance.
  • the hair styling agent described in Patent Document 1 still has room for improvement in terms of poor hand-comb (finger), comb, brush, and the like, and the point of re-styling when hair is broken once.
  • the hair styling agent described in Patent Document 2 has a large stickiness and a poor usability, and further improvement is required.
  • hair styling agents are required to be easily washed after use, but when exposed to moisture, sweat, rain, etc., the hair styling flows down and the hair styling collapses, the forehead and cheeks are sticky, Since there should be no inconveniences such as inability to re-hair, it was also necessary to have an appropriate performance for washing.
  • the purpose is to provide a resin emulsion.
  • the present inventors have used a polyvinyl alcohol resin, which has been conventionally used as a main polymer or as a compounding agent, as a dispersion stabilizer for an acrylic resin.
  • the hair-styling agent containing the emulsion obtained by the above has excellent balance between styling performance (hair-styling performance (setting power), re-hair-styling performance (re-setting power), tactile sensation) and washable performance, and completed the present invention. .
  • the gist of the present invention relates to the following (1) to (7).
  • R 1 to R 6 each independently represents a hydrogen atom or an organic group, and X represents a single bond or a bond chain.
  • the content of the side chain 1,2-diol structural unit in the polyvinyl alcohol resin [I] containing the side chain 1,2-diol structural unit represented by the formula (1) is 1 to 15 mol. %
  • the acrylic resin (A) is obtained by polymerizing a monomer component containing 40% by weight or more of an aliphatic (meth) acrylate monomer having an alkyl group having 4 to 12 carbon atoms.
  • the acrylic resin emulsion for hairdressing agent according to any one of (1) to (3).
  • the acrylic resin emulsion for hairdressing agents according to any one of (1) to (4), wherein the glass transition temperature of the acrylic resin (A) is 70 ° C. or lower.
  • a hair styling comprising the acrylic resin emulsion for hair styling according to any one of (1) to (5).
  • a step of applying to the hair an acrylic resin emulsion for hairdressing that contains an acrylic resin (A) dispersed and stabilized with polyvinyl alcohol resin [I], and the acrylic for hairdressing agent A step of adjusting the hair into a desired shape during or before or after the application of the system resin emulsion.
  • the acrylic resin emulsion for hairdressing agents of the present invention is excellent in water-solubility and / or redispersibility in water, the hairdressing agent using such an acrylic resin emulsion for hairdressing agents is excellent in cleaning performance. And has an excellent balance with styling performance.
  • (meth) acryl means acryl or methacryl
  • (meth) acryloyl means acryloyl or methacryloyl
  • (meth) acrylate means acrylate or methacrylate. It is a resin obtained by polymerizing a monomer component containing at least one (meth) acrylic monomer.
  • the acrylic resin emulsion for hairdressing agents of the present invention contains an acrylic resin (A) dispersed and stabilized by a polyvinyl alcohol resin (hereinafter sometimes referred to as “PVA resin”) [I]. It is.
  • PVA resin polyvinyl alcohol resin
  • the above-mentioned dispersion-stabilized state is a dispersion state in which the emulsion does not settle and separate even after being allowed to stand at 23 ° C. for 1 month, and maintains a uniform state.
  • the PVA resin [I] is preferably a PVA resin having the following specific average saponification degree and average polymerization degree.
  • the average saponification degree of the PVA resin [I] is preferably 70 to 99.9 mol%, particularly preferably 80 to 99.5 mol%, and further preferably 85 to 99.0 mol%. .
  • the average degree of saponification is too low, it is difficult for the polymerization to proceed stably, and even when the polymerization is completed, there is a tendency that the storage stability of the emulsion is lowered, the emulsion stability is too high, and the production is There is a tendency to become difficult.
  • the average saponification degree can be determined according to the saponification degree calculation method described in JIS K 6726 (1994).
  • the average degree of polymerization of the PVA resin [I] is preferably 50 to 3,000, particularly preferably 100 to 2,000, more preferably 200 to 1,000. Preferably it is 200-500. If the average degree of polymerization is too low, the protective colloid ability at the time of emulsion polymerization will be insufficient and the polymerization will tend not to proceed stably. If it is too high, the reaction system will become unstable due to thickening during the polymerization. Dispersion stability tends to decrease.
  • the average degree of polymerization can be determined according to the method for calculating the average degree of polymerization described in JIS K 6726 (1994).
  • PVA-based resin [I] means PVA itself or, for example, one modified by various modified species, and the degree of modification is usually 20 mol% or less, preferably 15 mol% or less, More preferably, it is 10 mol% or less.
  • modified PVA resin examples include an anion modified PVA resin modified with an anionic group including a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group, and modified with a cationic group such as a quaternary ammonium group.
  • Cationic modified PVA resin, modified PVA resin modified with various functional groups such as acetoacetyl group, diacetone acrylamide group, mercapto group, silanol group, and 1,2-diol structural unit in side chain PVA-based resin to be used.
  • the PVA-based resin [I] in the present invention is a PVA-based resin containing a 1,2-diol structural unit in the side chain, since it has excellent dispersion stability when an acrylate monomer is polymerized.
  • a PVA resin containing a 1,2-diol structural unit represented by the following formula (1) is particularly preferable.
  • R 1 to R 6 each independently represents a hydrogen atom or an organic group, and X represents a single bond or a bond chain.
  • R 1 to R 6 each independently represents a hydrogen atom or an organic group.
  • R 1 to R 6 are preferably all hydrogen atoms, but may be organic groups as long as the resin properties are not significantly impaired.
  • the organic group is not particularly limited, but is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a tert-butyl group. You may have substituents, such as a halogeno group, a hydroxyl group, an ester group, a carboxylic acid group, and a sulfonic acid group, as needed.
  • X is a single bond or a bonded chain, and is preferably a single bond from the viewpoints of set retention, non-stickiness, familiarity with hair, and the like.
  • the bonding chain is not particularly limited, but other hydrocarbons such as alkylene, alkenylene, alkynylene, phenylene, naphthylene (these hydrocarbons may be substituted with halogen such as fluorine, chlorine, bromine, etc.) , —O—, — (CH 2 O) m —, — (OCH 2 ) m —, — (CH 2 O) m CH 2 —, —CO—, —COCO—, —CO (CH 2 ) m CO— , —CO (C 6 H 4 ) CO—, —S—, —CS—, —SO—, —SO 2 —, —NR—, —CONR—, —NRCO—, —CSNR—, —NRCS—, —
  • Such a PVA resin containing a 1,2-diol structural unit represented by the formula (1) is, for example, (I) a method for saponifying a copolymer of vinyl acetate and 3,4-diacetoxy-1-butene , (II) a method for saponifying and decarboxylating a copolymer of vinyl acetate and vinyl ethylene carbonate, and (III) a copolymer of vinyl acetate and 2,2-dialkyl-4-vinyl-1,3-dioxolane Can be obtained by a method of saponifying and deketalizing, and (IV) a method of saponifying a copolymer of vinyl acetate and glyceryl monoallyl ether.
  • the content of the 1,2-diol structural unit in the PVA resin containing the 1,2-diol structural unit represented by the formula (1) is preferably 1 to 15 mol%, particularly preferably 1 to It is 12 mol%, more preferably 2 to 10 mol%, particularly preferably 2 to 9 mol%. If the content of the 1,2-diol structural unit is too low, the mechanical stability of the emulsion tends to be lowered. If it is too high, the stability during polymerization is lowered, and a stable emulsion having a high nonvolatile content can be obtained. There is a tendency to become difficult.
  • the content of the side chain 1,2-diol unit in the PVA resin is obtained from a 1 H-NMR spectrum (solvent: DMSO-d6, internal standard: tetramethylsilane) of completely saponified PVA. Specifically, it can be calculated from the peak area derived from the hydroxyl proton, methine proton, and methylene proton in the 1,2-diol unit, the methylene proton in the main chain, the hydroxyl proton linked to the main chain, etc. Good.
  • the average saponification degree of the PVA-based resin containing the 1,2-diol structural unit represented by the formula (1) is preferably 85 mol% or more, more preferably 86.5 to 99.8 mol. %, Particularly preferably 95 to 99 mol%. If the degree of saponification is too small, the stability of the emulsion during polymerization tends to decrease, making it difficult to obtain the desired emulsion.
  • the average degree of polymerization of the PVA resin containing the 1,2-diol structural unit represented by the formula (1) is preferably 50 to 3,000, more preferably 100 to 2,500, and still more preferably 200 to 2,000, particularly preferably 200 to 500. If the average degree of polymerization is too small, it tends to be difficult to produce a PVA resin industrially, and if it is too large, the viscosity of the emulsion tends to be too high, or the polymerization stability of the emulsion tends to decrease.
  • the PVA resin [I] is usually made into an aqueous solution using an aqueous medium, and this is used in the process of emulsion polymerization.
  • the aqueous medium refers to water or an alcoholic solvent mainly composed of water, preferably water.
  • the amount (nonvolatile content) of the PVA resin [I] in this aqueous solution is not particularly limited, but is preferably 5 to 30% by weight from the viewpoint of ease of handling.
  • the acrylic resin (A) in the present invention is obtained by polymerizing a monomer component containing the (meth) acrylic monomer (a1) as a main component.
  • the main component is preferably 40% by weight or more, more preferably 50% by weight or more, particularly preferably 60% by weight or more, and further preferably 70% by weight or more based on the whole monomer component.
  • Examples of the (meth) acrylic monomer (a1) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and t-butyl (meth) acrylate.
  • Aliphatic (meth) acrylate monomers such as 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, stearyl (meth) acrylate, and phenoxy (meth) acrylate
  • aromatic (meth) acrylate monomers such as trifluoroethyl (meth) acrylate.
  • these can be used individually or in combination of 2 or more types.
  • an aliphatic (meth) acrylate monomer having an alkyl group having 1 to 18 carbon atoms is preferable, and an aliphatic group having an alkyl group having 1 to 12 carbon atoms is particularly preferable from the viewpoint of hair bundle feeling and re-styling.
  • a combination of 2-ethylhexyl acrylate and methyl methacrylate, or a combination of n-butyl acrylate and methyl methacrylate can be preferably used.
  • the functional group-containing monomer (a2) may be copolymerized with the (meth) acrylic monomer (a1).
  • the functional group-containing monomer (a2) for example, two or more vinyl groups are included in the molecular structure. And the like, a glycidyl group-containing monomer, an allyl group-containing monomer, a hydrolyzable silyl group-containing monomer, an acetoacetyl group-containing monomer, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and the like.
  • Examples of the monomer having two or more vinyl groups in the molecular structure include divinylbenzene, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, ethylene glycol di (meth) acrylate, 1,2-propylene glycol di ( (Meth) acrylate, 1,3-propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tri Examples include methylolpropane tri (meth) acrylate and allyl (meth) acrylate.
  • ethylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, 1,3-propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, 6-Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate are preferable in terms of good copolymerizability with the (meth) acrylate monomer.
  • glycidyl group-containing monomer examples include glycidyl (meth) acrylate, glycidyl (meth) allyl ether, 3,4-epoxycyclohexyl (meth) acrylate, and the like.
  • allyl group-containing monomer examples include monomers having two or more allyl groups such as triallyloxyethylene, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, tetraallyloxyethane, allyl glycidyl ether, and allyl acetate. Etc.
  • hydrolyzable silyl group-containing monomer examples include vinyl silyl group-containing monomers such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris ( ⁇ -methoxyethoxy) silane, and vinylmethyldimethoxysilane; ⁇ - (meth) (Meth) acryloxy systems such as acryloxypropyltrimethoxysilane, ⁇ - (meth) acryloxypropylmethyldimethoxysilane, ⁇ - (meth) acryloxypropyltriethoxysilane, ⁇ - (meth) acryloxypropylmethyldiethoxysilane Examples thereof include silyl group-containing monomers. Among these, a (meth) acryloxy-based silyl group-containing monomer is preferable in terms of excellent copolymerizability with the (meth) acrylate-based monomer (a1).
  • acetoacetyl group-containing monomer examples include acetoacetate vinyl ester, acetoacetate allyl ester, diacetoacetate allyl ester, acetoacetoxyethyl (meth) acrylate, acetoacetoxyethyl crotonate, acetoacetoxypropyl (meth) acrylate, acetoacetoxy Examples thereof include propyl crotonate and 2-cyanoacetoacetoxyethyl (meth) acrylate.
  • hydroxyl group-containing monomer examples include (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like, and protection during emulsion polymerization From the viewpoint of colloidal action and water washability, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferred.
  • carboxyl group-containing monomer examples include (meth) acrylic acid, acrylic acid dimer, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, acrylamide N-glycolic acid, and cinnamon.
  • acrylic acid and methacrylic acid are preferable from the viewpoint of protective colloidal action and water washability during emulsion polymerization.
  • the content ratio of the functional group-containing monomer (a2) is preferably from 0.01 to 10% by weight, particularly preferably from 0.05 to 5% by weight, more preferably based on the whole monomer component. 0.1 to 3% by weight. If the content is too high, the acrylic resin becomes too hard and sufficient adhesive force does not appear and hair styling tends to be reduced. If the content is too low, the effect of washing properties tends to be difficult to understand.
  • the functional group-containing monomer (a2) is a monomer having two or more vinyl groups in the molecular structure, it is preferably 0.01 to 5% by weight with respect to the whole monomer component, Particularly preferred is 0.05 to 3% by weight, and further preferred is 0.1 to 1% by weight.
  • styrene monomer such as styrene and ⁇ -methylstyrene, vinyl oxalate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, pivalin within the range not impairing the effects of the present invention.
  • Vinyl ester monomers such as vinyl acid, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl versatate, vinyl 2-ethylhexanoate and the like may be used.
  • acrylic resin emulsion according to the present invention other components can be further used as necessary in addition to the above-mentioned monomer components.
  • Such other components can be appropriately selected depending on the purpose, and examples thereof include a polymerization initiator, a polymerization regulator, an auxiliary emulsifier, and a plasticizer.
  • polymerization initiator those that can be used for usual emulsion polymerization can be used, for example, inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate; organic peroxides, azo-based initiators, peroxides Examples thereof include peroxides such as hydrogen and butyl peroxide; and redox polymerization initiators obtained by combining these with reducing agents such as acidic sodium sulfite and L-ascorbic acid. These may be used alone or in combination of two or more. Among these, ammonium persulfate and potassium persulfate are preferable in terms of easy polymerization.
  • inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate
  • organic peroxides such as hydrogen and butyl peroxide
  • redox polymerization initiators obtained by combining these with reducing agents such as acidic sodium sulfite
  • the polymerization regulator can be appropriately selected from known ones.
  • Examples of such a polymerization regulator include a chain transfer agent and a buffer.
  • chain transfer agent examples include alcohols such as methanol, ethanol, propanol and butanol; aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, furfural and benzaldehyde; and dodecyl mercaptan, lauryl mercaptan, normal mercaptan, thiol And mercaptans such as glycolic acid, octyl thioglycolate, and thioglycerol. These may be used alone or in combination of two or more.
  • the use of a chain transfer agent is effective in that the polymerization is performed stably, and it is desirable to use it to adjust the degree of polymerization of the acrylic resin.
  • buffer examples include sodium acetate, ammonium acetate, dibasic sodium phosphate, and sodium citrate. These may be used alone or in combination of two or more.
  • auxiliary emulsifier may be used as long as it is known to those skilled in the art as being usable for emulsion polymerization. Therefore, auxiliary emulsifiers are, for example, known anionic, cationic and nonionic surfactants, water-soluble polymers having protective colloid ability other than PVA resin [I], and water-soluble oligomers. Can be selected as appropriate.
  • the surfactant examples include anionic surfactants such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate, and nonionic surfactants such as those having a pluronic structure and those having a polyoxyethylene structure. Agents.
  • the reactive surfactant which has a radically polymerizable unsaturated bond in a structure can also be used as a surfactant. These may be used alone or in combination of two or more.
  • the use of the above-mentioned surfactant has the effect of making the emulsion polymerization proceed smoothly, making it easy to control (effect as an emulsifier), and suppressing the generation of coarse particles and block-like substances generated during the polymerization.
  • these surfactants are used as emulsifiers, the graft rate tends to decrease.
  • it is desirable that the amount used is auxiliary to the PVA resin [I], that is, as small as possible.
  • water-soluble polymer having protective colloid ability other than the PVA-based resin [I] examples include PVA-based resins other than the PVA-based resin [I], hydroxyethyl cellulose, polyvinyl pyrrolidone, methyl cellulose, and the like. These may be used alone or in combination of two or more. These are effective in that the viscosity is changed by increasing the viscosity of the emulsion or changing the particle size of the emulsion.
  • the water-soluble oligomer for example, a degree of polymerization having a hydrophilic group such as a sulfonic acid group, a carboxyl group, a hydroxyl group, and an alkylene glycol group is preferable, and a polymer or copolymer of about 10 to 500 is preferable.
  • Specific examples of the water-soluble oligomer include amide copolymers such as 2-methacrylamide-2-methylpropanesulfonic acid copolymer, sodium methacrylate-4-styrenesulfonate copolymer, styrene / maleic acid copolymer, and the like.
  • Examples include polymers, melamine sulfonic acid formaldehyde condensates, poly (meth) acrylates, and the like. Furthermore, specific examples include a monomer having a sulfonic acid group, a carboxyl group, a hydroxyl group, an alkylene glycol group or the like, a water-soluble oligomer obtained by copolymerizing a radical polymerizable reactive emulsifier in advance alone or with another monomer, and the like. It is done. These may be used alone or in combination of two or more.
  • an adipate plasticizer As the plasticizer, an adipate plasticizer, a phthalic acid plasticizer, a phosphoric acid plasticizer, or the like can be used.
  • the acrylic resin emulsion of the present invention can be produced, for example, by emulsion polymerization of the above monomer components using PVA resin [I] as a dispersion stabilizer.
  • PVA resin [I] a dispersion stabilizer
  • an acrylic resin emulsion using the dispersion stabilized acrylic resin (A) as a dispersoid is produced using PVA resin [I] as a dispersion stabilizer.
  • the amount of the PVA resin [I] used is preferably 0.01 to 40 parts by weight with respect to 100 parts by weight as a whole of the monomer components constituting the acrylic resin (A).
  • the amount is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight. If the amount of the PVA resin [I] used is too small, the amount of protective colloid at the time of emulsion polymerization will be insufficient, and the polymerization stability tends to decrease. The viscosity of the resin emulsion tends to increase and the stability tends to decrease.
  • the PVA resin [I] used is generally present in the acrylic resin emulsion formed by polymerization.
  • the emulsion polymerization is carried out using the above-described other components such as a polymerization initiator, a polymerization regulator, and an auxiliary emulsifier as necessary in addition to the PVA resin [I] and the monomer component.
  • the polymerization reaction conditions can be appropriately selected according to the type and purpose of the monomer.
  • a method of emulsion polymerization for example, water and PVA-based resin [I] are charged into a reaction can, and a monomer dropping type emulsion polymerization method in which a monomer component and a polymerization initiator are dropped by raising the temperature;
  • the mixed monomer of the monomer component is dispersed and emulsified in advance with water-soluble polymer having protective colloid ability other than PVA resin [I] and / or PVA resin [I] and water, and then dispersed and emulsified.
  • An emulsified monomer dropping type emulsion polymerization method in which a monomer is dropped, and the like.
  • the emulsified monomer dropping type polymerization method is advantageous in terms of reactivity when using a hydrophobic monomer, management and controllability of the polymerization process, and the like.
  • it has protective colloid ability other than PVA-based resin [I] and / or PVA-based resin [I] at the end of the polymerization reaction in order to impart stability of the emulsion and water-dispersibility and / or re-dispersibility in water. It is also possible to add a water-soluble polymer later.
  • the emulsion polymerization process will be described more specifically as follows.
  • the monomer dropping type emulsion polymerization for example, first, water, PVA resin [I], and an auxiliary emulsifier as necessary are charged into a reaction vessel, and this is heated (usually 40 to 90 ° C.), then the monomer A part of the components and a polymerization initiator are added to the reaction vessel to carry out initial polymerization. Next, the remaining monomer components are added to the reaction can while dropping all at once, and the polymerization is allowed to proceed while further adding a polymerization initiator as necessary. When it is determined that the polymerization reaction is completed, the reaction can is cooled, and the target acrylic resin emulsion can be taken out.
  • emulsion monomer dropping type emulsion polymerization method for example, first, water, if necessary, PVA resin [I] and an auxiliary emulsifier are charged into a reaction vessel, and this is heated (usually 40 to 90 ° C.). , A water-soluble polymer having protective colloid ability other than PVA-based resin [I] and / or PVA-based resin [I], a part of a monomer component emulsified and dispersed with an auxiliary emulsifier and water as necessary A polymerization initiator is added to the reaction vessel to carry out initial polymerization.
  • the remaining monomer components are added to the reaction can while dropping all at once, and the polymerization is allowed to proceed while further adding a polymerization initiator as necessary.
  • the reaction can is cooled, and the target acrylic resin emulsion can be taken out.
  • the above initial polymerization can be carried out without adding the total amount of monomer components and the polymerization initiator to the reaction can while dropping.
  • the reaction temperature is less than 70 ° C., it is preferable that a redox polymerization reaction system using a reducing agent is used because the reaction proceeds smoothly.
  • the acrylic resin emulsion obtained by emulsion polymerization is typically uniform milky white, and the average particle size of the acrylic resin (A) in the acrylic resin emulsion is 0.2 to 2 ⁇ m.
  • the thickness is preferably 0.3 to 1.5 ⁇ m.
  • the average particle diameter can be measured by a conventional method, for example, a laser analysis / scattering particle size distribution measuring apparatus “LA-950S2” (manufactured by Horiba, Ltd.).
  • the acrylic resin (A) in the acrylic resin emulsion preferably has a glass transition temperature of 70 ° C. or less, particularly preferably 40 ° C. or less, more preferably 20 ° C. or less, particularly preferably 0 ° C. or less. is there.
  • the glass transition temperature is too high, the acrylic resin becomes hard and becomes brittle when it dries, so that the re-hairing performance tends to be lowered.
  • the lower the glass transition temperature the better the hair styling property tends to be because the polymer becomes sticky, but the lower limit is usually ⁇ 80 ° C., preferably ⁇ 70 ° C.
  • the one where the content ratio of PVA-type resin [I] is large, the one where the glass transition temperature of acrylic resin (A) is low is preferable at the point of re-styling.
  • the glass transition temperature of the acrylic resin (A) in the present invention is a value obtained by calculating the glass transition temperature of a homopolymer composed of each polymerization component constituting the acrylic resin by the Fox equation. It can adjust by adjusting suitably the weight ratio of each polymerization component which comprises A). In addition, when using together a functional group containing monomer, it may be calculated by the formula of Fox based on the main monomer component except this functional group containing monomer.
  • the PVA-based resin [I] is grafted to the acrylic resin (A). This is preferable from the viewpoint of reducing variations in measured values in intensity measurement.
  • the value (W) represented by the following formula (2) is preferably 90% by weight or less, more preferably 85% by weight. Or less, more preferably 80% by weight or less. In addition, as a minimum, it is 1 weight% normally, Preferably it is 5 weight%, More preferably, it is 10 weight%. This value is a measure of the degree of grafting, and if this value is too low, the degree of grafting is low, the protective colloid action during emulsion polymerization is reduced, and the polymerization stability tends to decrease. If it is too high, it tends to be difficult to form a stable emulsion at a high concentration.
  • the value (W) of equation (2) is calculated as follows. That is, a target emulsion or the like is dried at room temperature to prepare a film, and the film is extracted in boiling water and acetone for 8 hours, respectively, to remove ungrafted resin and the like.
  • the absolute dry weight of the film before extraction is w 1 (g)
  • the absolute dry weight of the film after extraction is w 2 (g), which is obtained from the following formula (2).
  • the emulsion polymerization temperature may be changed (higher (W) is higher, lower (W) is lower), or excessively used as a polymerization catalyst.
  • a very small amount of reducing agent for example, acidic sodium sulfite
  • sulfate or the like ((W) increases).
  • additives may be further added to the acrylic resin emulsion after emulsion polymerization, if necessary.
  • additives include organic pigments, inorganic pigments, water-soluble additives, pH adjusters, preservatives, and antioxidants.
  • the acrylic resin emulsion of the present invention can be obtained, and when used, it is preferable to adjust the nonvolatile content to usually 0.1 to 65% by weight. Further, when such an acrylic resin emulsion is used as a hair styling agent, when it is used in combination with other compounding components (resin or additive described later), the non-volatile content is usually 30 to 60% by weight. This is preferable in that the use of the resin and additives is not easily restricted. When such an acrylic resin emulsion is used alone as a hair styling agent, it is preferable that the non-volatile content is usually 1 to 10% by weight because it can be uniformly applied to hair.
  • the acrylic resin emulsion of the present invention can be obtained.
  • Such an acrylic resin emulsion is used for hairdressing agents, and hairdressing agents using the emulsion exhibit desired performance.
  • the hair styling agent of the present invention may be one using an acrylic resin emulsion alone, or may be a combination of an acrylic resin emulsion and various compounding agents.
  • the acrylic resin emulsion for hair styling agent of the present invention preferably contains 1% by weight or more (in terms of solid content) in the hair styling agent, more preferably 3% by weight or more (in terms of solid content). Yes, more preferably 5% by weight or more (in terms of solid content).
  • it is 70 weight% (solid content conversion) normally, Preferably it is 60 weight% (solid content conversion), More preferably, it is 50 weight% (solid content conversion). If the amount of the acrylic resin emulsion for hairdressing agent of the present invention is too small, the hairstyling power tends to decrease, and if it is too large, the cleaning property tends to decrease.
  • various blending components used in known general hair styling agents such as oils, polyhydric alcohols, lower alcohols, surfactants, ultraviolet absorbers, fragrances, antioxidants are added to the acrylic resin emulsion.
  • An agent, a moisturizer, a refreshing agent, vitamins, a plant extract and the like can be appropriately blended according to the purpose.
  • oils examples include sunflower oil, cottonseed oil, soybean oil, olive oil, coconut oil, castor oil, jojoba oil, camellia oil, mink oil and the like; beeswax, carnauba wax, candelilla wax, rice bran wax, shellac wax, whale wax, lanolin Waxes such as ceresin, paraffin wax, liquid paraffin, liquid isoparaffin, microcrystalline wax, polyethylene powder, polyethylene wax, Fischer-Tropsch wax, petrolatum, squalane, etc .; lauric acid, myristic acid, palmitic acid, stearin Higher fatty acids such as acid, oleic acid, behenic acid, 2-ethylbutanoic acid, isopentanoic acid, 2-methylpentanoic acid, 2-ethylpentanoic acid, isostearic acid, 12-hydroxystearic acid; lauryl alcohol, Higher alcohols such as stil alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol
  • the content of such an oil is usually preferably 0.5 to 50% by weight, particularly preferably 1 to 40% by weight, based on the total amount of the hair styling agent, from the viewpoint of emulsification.
  • polyhydric alcohol examples include ethylene glycol, dipropylene glycol, propylene glycol, isoprene glycol, glycerin, diglycerin, 1,3-butylene glycol, 1,2-pentanediol, 1,2-hexanediol, 1, Examples include 2-octanediol and 1,2-decanediol. These may be used alone or in combination of two or more.
  • the content of such a polyhydric alcohol is preferably 0.1 to 20% by weight, particularly preferably 0.5 to 15% by weight, based on the feeling of use, in the total amount of the hairdressing agent.
  • the acrylic resin emulsion for hairdressing agent of the present invention is used, for example, by diluting the acrylic resin emulsion with water, polyhydric alcohol, lower alcohol or the like as a liquid type hairdressing agent, or in the acrylic resin emulsion, Can be used as a viscous liquid type or cream type hair styling agent.
  • hair styling containing the acrylic resin emulsion for hair styling of the present invention can be performed as follows.
  • the acrylic resin emulsion for hairdressing agent of the present invention containing the acrylic resin (A) dispersed and stabilized by the polyvinyl alcohol resin [I] is applied to the hair for an effective amount of hairstyling, and the acrylic resin for hairstyling agent is applied.
  • the hair is trimmed to the desired shape. By styling in this way, a desired hairstyle can be easily formed.
  • various acrylic resin emulsions were prepared as follows.
  • the nonvolatile content and viscosity of the acrylic resin emulsion were measured according to the following method, and the glass transition temperature was measured according to the method described above.
  • ⁇ Nonvolatile content> 1 g of a sample is spread on a container of an aluminum foil dish formed to have the same bottom area as a flat weighing bottle 50 mm ⁇ 30 mm defined in JIS R 3503 (1994), and accurately weighed. Place the container in the center of the thermostatic bath, dry at 105 ° C. ⁇ 2 ° C. for 60 ⁇ 5 minutes, then allow to cool in a desiccator and weigh it. And it computed by the following formula. N (Wd / Ws) ⁇ 100 (Here, N is the nonvolatile content (%), Wd is the weight (g) of the sample after drying, and Ws is the weight (g) of the sample before drying.)
  • Example 1 Production of acrylic resin emulsion (1)> A SUS reaction vessel equipped with a cooling tube and a stirring blade was added to a PVA resin containing an 1,2-diol structural unit in the side chain in deionized water (92 parts) (average saponification degree 99 mol%, average polymerization degree). 300, content of 1,2-diol structural unit in the side chain: 8 mol% / manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), 10 parts, sodium hydrogen sulfite 0.2 part, sodium carbonate / water trihydrate 0.4 part And heated to 75 ° C.
  • Example 2 Production of acrylic resin emulsion (2)>
  • 100 parts of 2-ethylhexyl acrylate was changed to 90 parts of 2-ethylhexyl acrylate and 10 parts of methyl methacrylate, and “GOHSENOL GL05” (trade name, Nippon Synthetic Chemical Industry Co., Ltd.) was used as an unmodified PVA resin.
  • Synthetic Chemical Industry Co., Ltd . Acrylic resin emulsion (2) (non-volatile content: 43%; viscosity: 160 mPa ⁇ s (type B), except that the product name is “GOHSENOL EG05”.
  • the acrylic resin emulsion (2) was dispersed and stabilized.
  • Example 3 Production of acrylic resin emulsion (3)>
  • an acrylic resin emulsion was used in the same manner as in Example 2 except that 0.3 part of ethylene glycol dimethacrylate (manufactured by Mitsubishi Rayon Co., Ltd .; trade name “Acryester ED”) was added as an acrylic monomer.
  • the acrylic resin emulsion (3) was dispersed and stabilized.
  • Example 4 Production of acrylic resin emulsion (4)>
  • 100 parts of 2-ethylhexyl acrylate was changed to 75 parts of 2-ethylhexyl acrylate and 25 parts of methyl methacrylate, and “GOHSENOL GL05” (trade name, Nippon Synthetic Chemical Industry Co., Ltd.) was used as an unmodified PVA resin.
  • Manufactured by Nippon Synthetic Chemical Industry Co., Ltd . Acrylic resin emulsion (4) (nonvolatile content: 46%; viscosity: 540 mPa ⁇ s (B type), except that the product name is changed to “GOHSENOL EG05”.
  • the acrylic resin emulsion (4) was dispersed and stabilized.
  • Example 5 Production of acrylic resin emulsion (5)>
  • an acrylic resin emulsion (5) (non-volatile content: 43%; viscosity; similar to Example 4) except that 0.2 part of acrylic ester ED (ethylene glycol dimethacrylate) was added as an acrylic monomer.
  • 420 mPa ⁇ s (B-type viscometer 12 rpm, 23 ° C.); glass transition temperature (Tg) ⁇ 43 ° C. of acrylic resin was obtained.
  • the acrylic resin emulsion (5) was dispersed and stabilized.
  • Example 6 Production of acrylic resin emulsion (6)>
  • 100 parts of 2-ethylhexyl acrylate was changed to 60 parts of 2-ethylhexyl acrylate and 40 parts of methyl methacrylate, and “GOHSENOL GL05” (trade name, Nippon Synthetic Chemical Industry Co., Ltd.) as an unmodified PVA resin.
  • Manufactured by Nippon Synthetic Chemical Industry Co., Ltd . acrylic resin emulsion (6) (non-volatile content: 44%; viscosity: 470 mPa ⁇ s (type B), except that the product name “GOHSENOL EG05” was changed.
  • the acrylic resin emulsion (6) was dispersed and stabilized.
  • Example 7 Production of acrylic resin emulsion (7)> In a SUS reactor equipped with a cooling tube and a stirring blade, 92 parts of deionized water, 0.2 part of sodium bisulfite, and 0.4 part of sodium carbonate / water trihydrate were completely dissolved and heated to 75 ° C. .
  • PVA resin containing 77 parts of deionized water and 1,2-diol structural units in the side chain in advance (average saponification degree 89 mol%, average polymerization degree 340, content of 1,2-diol bond in side chain 3 Mol% / manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 4 parts, 55 parts of n-butyl acrylate and 45 parts of methyl methacrylate (i) and 2.7 parts of 10% APS aqueous solution (ii) were prepared. First, 10% of (i) and 30% of (ii) were added to the reaction can and allowed to react for 45 minutes.
  • Example 8 Production of acrylic resin emulsion (8)> In a SUS reactor equipped with a cooling tube and a stirring blade, 169 parts of deionized water and a PVA resin containing 1,2-diol structural unit in the side chain (average saponification degree 99 mol%, average polymerization degree 300, 7 parts of 1,2-diol bond in the side chain / manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), 0.2 part of sodium hydrogen sulfite and 0.4 part of sodium carbonate / sansui were completely dissolved. The temperature was raised to 75 ° C.
  • Example 9 Production of acrylic resin emulsion (9)>
  • acrylic resin emulsion (9) non-volatile content: 44%; 44%; except that 0.05 part of KBM503 ( ⁇ -methacryloxypropyltrimethoxysilane) was added as a monomer component.
  • a viscosity of 550 mPa ⁇ s (B-type viscometer 12 rpm, 23 ° C.); glass transition temperature (Tg) of acrylic resin ( ⁇ 43 ° C.) was obtained.
  • the acrylic resin emulsion (9) was dispersed and stabilized.
  • an unmodified PVA resin manufactured by Nippon Synthetic Chemical Industry Co., Ltd .; trade name “GOHSENOL GL05”
  • Acrylic resin emulsion (10) non-volatile content 44%; viscosity 140 mPa ⁇ s (B-type viscometer 12 rpm, 23
  • ⁇ Comparative Example 2 Acrylic resin emulsion produced by emulsion polymerization using only an anionic surfactant (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “Cooponyl WU-6406”; nonvolatile content 56%; viscosity 1200 mPa ⁇ s; acrylic The glass transition temperature of the base resin -68 ° C.) was diluted with deionized water to produce an acrylic resin emulsion having a nonvolatile content of 45% and 3%. The state of the acrylic resin emulsion of Comparative Example 2 was dispersed and stabilized.
  • hair styling agent test solution A
  • hair styling performance setting power
  • re-hair styling performance re-setting power
  • tactile sensation was evaluated as follows.
  • ⁇ Hair styling performance (setting power)> Apply 0.5g of the above-mentioned hairdressing agent test solution (A) uniformly to the hair bundle (length 20cm x weight 1.2g; hair bundle shop) with a dropper and apply it more evenly with a finger wearing vinyl gloves. Applied. After adjusting with a finger so that the width of the bundle is about 1 cm and drying it with a blow dryer at 100 ° C. for 1 minute, turn the bundling side down with the tip of the hair at an angle of about 45 ° from directly above. And sensory evaluation was performed to determine whether the hair bundle was fixed. The evaluation method is as follows. (Evaluation criteria) ⁇ ... The hair is shaped even after being shaken a little. ⁇ ... Slightly spread the hair tip a little. ⁇ ... The hair ends are loose or slightly shaken. In the above evaluation, “ ⁇ ” indicates performance. Excellent, “ ⁇ ” is practically acceptable. In addition, “x” is inferior in performance.
  • ⁇ Re-styling performance (re-setting power)> The hair bundle after performing the hair styling evaluation was loosened with a finger, and further spread with a comb, and then the hair bundle state when the hair bundle was made again with the finger was subjected to sensory evaluation.
  • the evaluation method is as follows. (Evaluation criteria) ⁇ ... The hair bundles are gathered again (hairs are adjusted) ⁇ : The hair bundles are slightly spread, but the hair bundles are slightly spread. ⁇ : The hair bundles are not formed and the hair is not trimmed. In the above evaluation, “ ⁇ ” indicates excellent performance, and “ ⁇ ” is practically acceptable. In addition, “x” is inferior in performance.
  • ⁇ Tactile feel> The feeling of touch with the fingers was evaluated for the feeling of unity of the hair at the time of the above-mentioned hair styling performance evaluation.
  • the evaluation method is as follows. (Evaluation criteria) ⁇ : Moist and smooth ⁇ : Slightly crumbly X: Quite crumbly In the above evaluation, “ ⁇ ” indicates excellent performance, and “ ⁇ ” is practically acceptable. In addition, “x” is inferior in performance.
  • the hair styling agent test solution (B) was applied to a 50 ⁇ m thick PET (polyethylene terephthalate) film with a 40 ⁇ m applicator and dried at 100 ° C. for 5 minutes to obtain a coating film having a thickness of about 15 ⁇ m (when dried). Put a drop of deionized water on the coating film with a dropper and gently rub it 10 times (10 laps) with a finger to draw a circle with a diameter of about 1 cm. Pulp waste (Nippon Paper Crecia Co., Ltd., “Kimwipe” The degree of cleaning of the hairdressing agent solution on the coating film after wiping with “(registered trademark)” was visually evaluated. The evaluation method is as follows.
  • the hair styling agent using the acrylic resin emulsion dispersed and stabilized by the PVA resin of the present invention has a balance between styling performance (hair styling performance, re-hair styling performance, tactile sensation) and washing performance. It turns out that it is excellent.
  • Comparative Example 1 using PVA-based resin as an aqueous solution, it is found that the hair styling performance and the performance to be washed are good, but the hair styling property and tactile feel are poor. Moreover, in Comparative Example 2 using an acrylic resin emulsion obtained using a non-PVA surfactant, although the hair styling performance, re-hair styling performance, and touch are good, the performance to be washed is poor, It turns out that it is a practically troublesome level as a hairdressing agent.
  • the acrylic resin emulsion for hairdressing agents of the present invention has a well-balanced balance between styling performance (hairstyling performance, re-styling performance, and tactile sensation) and performance to be washed, so various compounding agents can be used in combination and applied to various dosage forms. Is a useful thing that can be.

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Abstract

La présente invention concerne une émulsion de résine acrylique appropriée pour obtenir un agent de coiffage présentant, de manière bien équilibrée, d'excellentes performances coiffantes (performances de coiffage, performances de recoiffage et texture) et une facilité d'élimination par rinçage. L'émulsion de résine acrylique pour agents de coiffage selon l'invention comprend une résine acrylique (A) qui a été dispersée de manière stable par une résine de poly(alcool vinylique) [I].
PCT/JP2013/083682 2012-12-18 2013-12-16 Émulsion de résine acrylique pour agents de coiffage, agent de coiffage la comprenant et procédé de coiffage WO2014098052A1 (fr)

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WO2015133629A1 (fr) * 2014-03-07 2015-09-11 日本合成化学工業株式会社 Émulsion de résine (méth)acrylique pour agent de coiffure, agent de coiffure contenant une émulsion de résine (méth)acrylique pour agent de coiffure, et procédé de coiffure
FR3117853A1 (fr) 2020-12-23 2022-06-24 L'oreal Composition cosmétique comprenant des particules polymériques à base de fonctions acétoacétates
FR3117855A1 (fr) 2020-12-23 2022-06-24 L'oreal : Composition cosmétique comprenant un copolymère à base de fonctions acétoacétates
FR3117856A1 (fr) 2020-12-23 2022-06-24 L'oréal Composition cosmétique comprenant un copolymère séquencé à base de fonctions acétoacétates
WO2022136104A1 (fr) 2020-12-23 2022-06-30 L'oreal Composition cosmétique comprenant un copolymère à base de fonctions acétoacétates
WO2022136110A1 (fr) 2020-12-23 2022-06-30 L'oreal Composition cosmétique comprenant des particules polymériques à base de fonctions acétoacétates

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WO2015133629A1 (fr) * 2014-03-07 2015-09-11 日本合成化学工業株式会社 Émulsion de résine (méth)acrylique pour agent de coiffure, agent de coiffure contenant une émulsion de résine (méth)acrylique pour agent de coiffure, et procédé de coiffure
JP2015180618A (ja) * 2014-03-07 2015-10-15 日本合成化学工業株式会社 整髪剤用アクリル系樹脂エマルジョン及びそれを含有する整髪剤、並びに整髪方法
FR3117853A1 (fr) 2020-12-23 2022-06-24 L'oreal Composition cosmétique comprenant des particules polymériques à base de fonctions acétoacétates
FR3117855A1 (fr) 2020-12-23 2022-06-24 L'oreal : Composition cosmétique comprenant un copolymère à base de fonctions acétoacétates
FR3117854A1 (fr) 2020-12-23 2022-06-24 L'oréal Composition cosmétique comprenant des particules polymériques à base de fonctions acétoacétates
FR3117852A1 (fr) 2020-12-23 2022-06-24 L'oréal Composition cosmétique comprenant un copolymère à base de fonctions acétoacétates
FR3117856A1 (fr) 2020-12-23 2022-06-24 L'oréal Composition cosmétique comprenant un copolymère séquencé à base de fonctions acétoacétates
WO2022136104A1 (fr) 2020-12-23 2022-06-30 L'oreal Composition cosmétique comprenant un copolymère à base de fonctions acétoacétates
WO2022136110A1 (fr) 2020-12-23 2022-06-30 L'oreal Composition cosmétique comprenant des particules polymériques à base de fonctions acétoacétates

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