WO2015133629A1 - 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 - Google Patents

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 Download PDF

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Publication number
WO2015133629A1
WO2015133629A1 PCT/JP2015/056731 JP2015056731W WO2015133629A1 WO 2015133629 A1 WO2015133629 A1 WO 2015133629A1 JP 2015056731 W JP2015056731 W JP 2015056731W WO 2015133629 A1 WO2015133629 A1 WO 2015133629A1
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monomer composition
acrylic resin
monomer
meth
emulsion
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PCT/JP2015/056731
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English (en)
Japanese (ja)
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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 CN201580012513.7A priority Critical patent/CN106068117A/zh
Priority to KR1020167027429A priority patent/KR102318407B1/ko
Publication of WO2015133629A1 publication Critical patent/WO2015133629A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate

Definitions

  • the present invention relates to an acrylic resin emulsion useful as a hair styling agent (hair styling agent). More specifically, the present invention is excellent in water-solubility and / or redispersibility in water. The present invention relates to an acrylic resin emulsion excellent in balance with performance.
  • hairdressing agents such as liquid, gel, foam, mist, cream and wax.
  • hairdressing agents are mainly composed of a polymer (setting polymer) for maintaining a desired shape by forming a film on the hair surface, and depending on 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 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 aesthetics at the time of use by blending a polyvinyl alcohol resin in the emulsion composition, and does not impart unnatural shine to the hair after application. It has performance.
  • the hair styling agent described in Patent Document 1 has room for improvement in terms of inadequate goodness as a hand comb (finger), comb, brush, or the like, and in terms of re-styling when hair is broken once. It remained.
  • the hair styling agent described in Patent Document 2 has a large stickiness, and further improvement in the feeling of use is required.
  • recent hair styling agents are required to have good hair styling power and re-hair styling performance, and further have a hair styling holding power capable of holding a hair style once hair styled for a long time.
  • the hair styling agent with good hair styling power as described above, is often poorly washed off because it contains many oil components such as wax, so it can be rubbed strongly with shampoo or twice. It is necessary to do so, which causes rough scalp and dry trouble. There is also concern about scalp troubles such as dandruff, itching and hair loss due to oil components remaining if washing is insufficient. Therefore, recent hair styling agents are desired to have both good styling performance (hair styling) and good washability.
  • the present invention provides styling performance (hair styling performance (setting power), re-hair styling performance (re-setting power, re-setting holding power), tactile sensation and performance to be washed with water or lukewarm water. It is an object of the present invention to provide an acrylic resin emulsion for a hair styling agent that is effectively used in a hair styling that is excellent in balance.
  • the inventors of the present invention are acrylic resin emulsions obtained by emulsion polymerization of at least two monomer compositions, at least one of which is a (meth) acrylate monomer.
  • the difference between the glass transition temperatures of the two polymers when each of the monomer compositions is polymerized is 30 ° C. or more, and the monomer composition having the higher glass transition temperature is the monomer having the lower glass transition temperature.
  • a hair styling agent containing an acrylic resin emulsion obtained by emulsion polymerization in an amount less than the composition has styling performance (hair styling performance (setting power), re-hair styling performance (re-setting power), tactile sensation) and cleaning performance.
  • the present invention has been completed by finding that it is excellent in balance.
  • the gist of the present invention is as follows.
  • An acrylic resin emulsion for hairdressing agent obtained by emulsion polymerization of the monomer composition [I] and the monomer composition [II] An acrylic resin emulsion for a hair conditioner, wherein the monomer composition [I] and the monomer composition [II] satisfy the following conditions (i) to (iii):
  • At least one of the monomer composition [I] and the monomer composition [II] contains a (meth) acrylate monomer.
  • Tg2 glass transition temperature determined by the Fox formula of the polymer polymerized using the monomer composition [II] is determined by the Fox formula of the polymer polymerized using the monomer composition [I].
  • 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.
  • a hair styling method including the following step (A) and step (B).
  • the monomer composition [I] and the monomer composition [II] satisfy the following conditions (i) to (iii).
  • At least one of the monomer composition [I] and the monomer composition [II] contains a (meth) acrylate monomer.
  • the glass transition temperature (Tg2) determined by the Fox formula of the polymer polymerized using the monomer composition [II] is determined by the Fox formula of the polymer polymerized using the monomer composition [I]. 30 ° C. or more higher than the glass transition temperature (Tg1).
  • the acrylic resin emulsion for hairdressing agent of the present invention is excellent in water solubility and / or redispersibility in water, and the hairdressing agent containing such an acrylic resin emulsion for hairdressing agent is excellent in performance to be washed, It also has an excellent effect in 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 agent of the present invention is an acrylic resin emulsion obtained by emulsion polymerization of the monomer composition [I] and the monomer composition [II], and the monomer composition [I] and the monomer composition.
  • the product [II] satisfies the following conditions (i) to (iii).
  • At least one of the monomer composition [I] and the monomer composition [II] contains a (meth) acrylate monomer.
  • the acrylic resin emulsion for hairdressing agent may be an acrylic resin emulsion obtained by emulsion polymerization of only the monomer composition [I] and the monomer composition [II] in two stages, or other monomer compositions. It may be an acrylic resin emulsion obtained by emulsion polymerization in three or more stages. When emulsion polymerization is performed in three or more stages, the polymerization may be performed before, after or during the emulsion polymerization of the monomer composition [I] and the monomer composition [II].
  • an acrylic resin emulsion obtained by emulsion polymerization of only the monomer composition [I] and the monomer composition [II] as monomer components in two stages is preferable because the operation procedure is simple. Further, an acrylic resin emulsion obtained by emulsion polymerization of only the monomer composition [I] and the monomer composition [II] in two steps in this order is particularly preferable because it can be stably produced.
  • ⁇ other components> described later can be used as appropriate.
  • the monomer composition [I] and the monomer composition [II] includes a (meth) acrylate monomer, and preferably the monomer composition [I] and the monomer composition. It is preferable that both of [II] contain a (meth) acrylate-based monomer because unreacted products tend to decrease and the amount of residual monomer is reduced, that is, the safety is increased and the odor is low.
  • the glass transition temperature (Tg2) determined by the Fox formula of the polymer polymerized using the monomer composition [II] is determined by the Fox formula of the polymer polymerized using the monomer composition [I]. It is necessary that the monomer composition [I] and the monomer composition [II] are adjusted to be higher by 30 ° C. or more than the glass transition temperature (Tg1), and the glass transition temperature (Tg1) and the glass transition temperature (The difference from Tg2) is preferably 40 ° C. or higher, particularly preferably 50 ° C. or higher, more preferably 60 ° C. or higher, particularly preferably 90 ° C. or higher. If the difference between Tg2 and Tg1 is too small, the washability tends to decrease, which is not preferable.
  • the upper limit of the difference between Tg2 and Tg1 is usually 300 ° C., preferably 200 ° C.
  • Tg1 and Tg2 are calculated based on the glass transition temperature of each homopolymer by the following Fox equation.
  • the glass transition temperature of the homopolymer in the following Fox formula is determined by the monomer type of the homopolymer. That is, the glass transition temperatures (Tga, Tgb,... Tgn) of the homopolymers can use values described in “Polymer Handbook 3rd Edition, John Wiley & Sons, Inc, 1989”, respectively.
  • a homopolymer having an average molecular weight of 10,000 or more and less than 1,000,000 can be polymerized and confirmed by differential scanning calorimetry (DSC) or the like.
  • the said average molecular weight is a weight average molecular weight in polystyrene conversion by gel permeation chromatography (GPC).
  • the glass transition temperature (Tg1 and Tg2) of the polymer can be determined from the monomer species and the weight fraction.
  • the glass transition temperature (Tg) of the homopolymer may not be measured for some monomers.
  • the monomer content is about 5% by weight or less, there is little influence on the polymer physical properties. Therefore, the monomer is not considered as a constituent in the Fox formula.
  • the Tg1 is preferably 0 ° C. or less, particularly preferably ⁇ 20 ° C. or less, and further preferably ⁇ 30 ° C. or less. If Tg1 is too high, the acrylic resin particles in the acrylic resin emulsion become too hard and sufficient tackiness cannot be obtained, and the re-styling property tends to decrease.
  • the lower limit of Tg1 is usually ⁇ 80 ° C., preferably ⁇ 75 ° C.
  • the Tg2 is preferably 30 ° C. or higher, particularly preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and particularly preferably 60 ° C. or higher.
  • Tg2 is too low, the acrylic resin particles in the resulting acrylic resin emulsion are too soft, and there is a tendency that continuous hair styling performance cannot be obtained.
  • Tg2 is high, the cohesive strength of the acrylic resin obtained increases locally, and thus there is a tendency for stickiness to appear and good re-hairing properties.
  • the upper limit of Tg2 is usually 230 ° C, preferably 150 ° C.
  • the monomer composition [I] will be specifically described.
  • the monomer composition [I] include (meth) acrylic monomers (I-1) and functional group-containing monomers (I-2).
  • the monomer composition [I] may be composed of only one or two or more (meth) acrylic monomers (I-1) or only one or two or more functional group-containing monomers (I-2).
  • one or more kinds of (meth) acrylic monomers (I-1) and one or more kinds of functional group-containing monomers (I-2) may be contained.
  • the (meth) acrylic monomer (I-1) is preferably the main component.
  • Examples of the (meth) acrylic monomer (I-1) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and t-butyl (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, stearyl (meth) acrylate, and other aliphatic (meth) acrylate monomers; phenoxy (meth) Aromatic (meth) acrylate monomers such as acrylate; trifluoroethyl (meth) acrylate and the like.
  • an aliphatic (meth) acrylate monomer having an alkyl group having 1 to 18 carbon atoms is preferable, and particularly preferably an alkyl group having 1 to 12 carbon atoms 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.
  • Examples of the functional group-containing monomer (I-2) include monomers having two or more vinyl groups in the molecular structure, glycidyl group-containing monomers, allyl group-containing monomers, hydrolyzable silyl group-containing monomers, and acetoacetyl group-containing monomers. , Hydroxyl group-containing monomers, carboxyl group-containing monomers, and the like. Among these, it is preferable to use a monomer having two or more vinyl groups in the molecular structure or a hydrolyzable silyl group-containing monomer in terms of improving the washability without degrading the hairstyling property.
  • 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, trimethylolpropane tri (meth) acrylate are included in the (meth) acrylic monomer (I-1) and the monomer composition [II]. It is preferable at the point which is excellent in the copolymerizability with a (meth) acrylate type 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.
  • the (meth) acryloxy-based silyl group-containing monomer is excellent in copolymerization with the (meth) acrylic monomer (I-1) and the (meth) acrylate-based monomer contained in the monomer composition [II]. Is preferable.
  • 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 colloid action and 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 during emulsion polymerization and washability.
  • the content ratio of the (meth) acrylic monomer (I-1) is preferably 80 to 100% by weight, particularly preferably 85 to 99.99% by weight, based on the entire monomer composition [I]. More preferably, it is 90 to 99.9% by weight. If the content ratio of the (meth) acrylic monomer (I-1) is too small, sufficient hair styling performance tends not to be exhibited. When two or more monomers are included as the (meth) acrylic monomer (I-1), the total content of these monomers is preferably in the above range.
  • the content of the functional group-containing monomer (I-2) is preferably 0 to 20% by weight, particularly preferably 0.01 to 15% by weight, and more preferably, based on the whole monomer composition [I]. Preferably, the content is 0.1 to 10% by weight. If the content is too high, the acrylic resin becomes too hard, and sufficient hair strength does not appear and hair styling properties tend to decrease. If the content is too low, the effect of washability tends to be difficult to be exhibited. When two or more types of monomers are included as the functional group-containing monomer (I-2), the total content of these monomers is preferably in the above range.
  • the content ratio of the monomer having two or more vinyl groups in the molecular structure is the monomer composition.
  • the content is preferably 0.01 to 10% by weight, particularly preferably 0.05 to 5% by weight, more preferably 0.1 to 3% by weight, based on the total amount of [I].
  • the functional group-containing monomer (I-2) includes a hydrolyzed silyl group-containing monomer
  • the content of the hydrolyzed silyl group-containing monomer is from 0.01 to the entire monomer composition [I]. It is preferably 5% by weight, particularly preferably 0.02 to 3% by weight, more preferably 0.05 to 2% by weight.
  • styrene monomer such as styrene and ⁇ -methylstyrene, vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, and pivalic acid, as long as the effects of the present invention are not impaired.
  • Vinyl ester monomers such as vinyl, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl versatate and vinyl 2-ethylhexanoate may be used.
  • the monomer composition [II] will be specifically described.
  • Examples of the monomer composition [II] include (meth) acrylic monomer (II-1) and functional group-containing monomer (II-2).
  • the monomer composition [II] may consist of only one or two or more (meth) acrylic monomers (II-1) or only one or two or more functional group-containing monomers (II-2). In addition, it may contain one or more (meth) acrylic monomers (II-1) and one or more functional group-containing monomers (II-2). Of these, the (meth) acrylic monomer (II-1) is preferably the main component.
  • Examples of the (meth) acrylic monomer (II-1) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, and n-butyl (meth) acrylate, similar to the (meth) acrylic monomer (I-1).
  • an aliphatic (meth) acrylate monomer having an alkyl group having 1 to 18 carbon atoms is preferable, and particularly preferably an alkyl group having 1 to 12 carbon atoms from the viewpoint of hair bundle feeling and re-styling.
  • Aliphatic (meth) acrylate monomers more preferably aliphatic (meth) acrylate monomers having an alkyl group of 1 to 4 carbon atoms, particularly preferably methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate.
  • Examples of the functional group-containing monomer (II-2) include, for example, a monomer having two or more vinyl groups in the molecular structure, a glycidyl group-containing monomer, and an allyl group-containing monomer, similar to the functional group-containing monomer (I-2). , Hydrolyzable silyl group-containing monomers, acetoacetyl group-containing monomers, hydroxyl group-containing monomers, carboxyl group-containing monomers, and the like. Among these, it is preferable to copolymerize a monomer having two or more vinyl groups or a hydrolyzable silyl group-containing monomer in the molecular structure from the viewpoint of improving the washability without degrading the hairstyling property.
  • 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, trimethylolpropane tri (meth) acrylate are included in the (meth) acrylic monomer (II-1) and the monomer composition [I]. It is preferable at the point which is excellent in the copolymerizability with a (meth) acrylate type 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.
  • the (meth) acryloxy-based silyl group-containing monomer has excellent copolymerizability with the (meth) acrylic monomer (II-1) and the (meth) acrylate-based monomer contained in the monomer composition [I]. Is preferable.
  • 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 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 during emulsion polymerization and washability.
  • the content ratio of the (meth) acrylic monomer (II-1) is preferably 80 to 100% by weight, particularly preferably 85 to 99.99% by weight, based on the entire monomer composition [II]. More preferably, it is 90 to 99.9% by weight.
  • the content ratio of the (meth) acrylic monomer (II-1) is the above lower limit, sufficient hair styling performance tends to be exhibited.
  • the total content of these monomers is preferably within the above range.
  • the content ratio of the functional group-containing monomer (II-2) is preferably 0 to 20% by weight, particularly preferably 0.01 to 15% by weight, more preferably, based on the whole monomer composition [II]. Preferably, the content is 0.1 to 10% by weight. When the content is too large, the polymerization stability tends to be lowered, and when the content is too small, the effect of the washability tends to be difficult to understand. When two or more types of monomers are included as the functional group-containing monomer (II-2), the total content of these monomers is preferably within the above range.
  • the content ratio of the monomer having two or more vinyl groups in the molecular structure is the monomer composition.
  • the content is preferably from 0.01 to 10% by weight, particularly preferably from 0.05 to 5% by weight, and still more preferably from 0.1 to 3% by weight, based on the whole.
  • the content ratio of the hydrolyzed silyl group-containing monomer is from 0.01 to the entire monomer composition [II]. It is preferably 5% by weight, particularly preferably 0.02 to 3% by weight, more preferably 0.05 to 2% by weight.
  • styrenic monomer such as styrene and ⁇ -methylstyrene, vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, pivalin as long as the effects of the present invention are not impaired.
  • 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.
  • the acrylic resin emulsion according to the present invention in addition to the monomer composition [I] and the monomer composition [II], other components can be appropriately used as necessary.
  • other components include an emulsifier, a polymerization initiator, a polymerization regulator, and a plasticizer.
  • an emulsifier is preferably a water-soluble polymer, particularly preferably a polyvinyl alcohol resin (hereinafter sometimes referred to as “PVA resin”).
  • PVA resin polyvinyl alcohol resin
  • the acrylic resin particles in the acrylic resin emulsion are dispersed and stabilized with a polyvinyl alcohol resin from the viewpoint of good washability.
  • the dispersion-stabilized state refers to a dispersion state in which the emulsion does not settle and separate even when left at 23 ° C. for 1 month, and maintains a uniform state.
  • the PVA resin is preferably a PVA resin having the following specific average saponification degree and average polymerization degree.
  • the average degree of saponification of the PVA resin is preferably 70 to 99.9 mol%, particularly preferably 80 to 99.5 mol%, and further preferably 85 to 99 mol%. If the average saponification degree is too low, it is difficult for the polymerization to proceed stably, and even when the polymerization is completed, there is a tendency for the storage stability of the emulsion to decrease, and if it is too high, the emulsion stability decreases. There is a tendency that the production of emulsion becomes difficult.
  • the average saponification degree can be obtained according to the saponification degree calculation method described in JIS K 6726 (1994).
  • the average degree of polymerization of the PVA resin is preferably 50 to 3,000, particularly preferably 100 to 2,000, more preferably 200 to 1,000, and particularly preferably 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).
  • the PVA-based resin means PVA itself or one modified by, for example, 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 such as a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group; 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, etc .; contains 1,2-diol structural unit in side chain Examples thereof include PVA-based resins.
  • the PVA resin is preferably a PVA resin containing a 1,2-diol structural unit in the side chain from the viewpoint of excellent dispersion stability when polymerizing a (meth) acrylic monomer, particularly preferably. It is a PVA resin containing a 1,2-diol structural unit represented by the following formula (1).
  • 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 bond chain, and is preferably a single bond from the viewpoint of set holding power, non-stickiness, familiarity with hair, and the like.
  • the bonding chain is not particularly limited, but hydrocarbons such as alkylene, alkenylene, alkynylene, phenylene and naphthylene (these hydrocarbons may be substituted with halogen such as fluorine, chlorine and bromine).
  • each R is independently an arbitrary substituent, preferably a hydrogen atom or an alkyl group.
  • M is a natural number.
  • an alkylene group having 6 or less carbon atoms or —CH 2 OCH 2 — is preferable, and a methylene group and —CH 2 OCH 2 — are more preferable in terms of viscosity stability at the time of production, heat resistance, and the like.
  • the PVA resin containing the 1,2-diol structural unit represented by the formula (1) is, for example, (a) a method for saponifying a copolymer of vinyl acetate and 3,4-diacetoxy-1-butene (B) a method of saponifying and decarboxylating a copolymer of vinyl acetate and vinyl ethylene carbonate, and (c) 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 (d) 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 determined from 1 H-NMR spectrum (solvent: DMSO-d 6 , internal standard: tetramethylsilane) of PVA completely saponified. Specifically, it can be calculated from a peak area derived from a hydroxyl proton in the 1,2-diol unit, a methine proton, a methylene proton, a methylene proton in the main chain, or a proton in a hydroxyl group linked to the main chain. That's fine.
  • 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 average degree of saponification is too small, the stability of the emulsion during polymerization tends to be lowered, making it difficult to obtain the intended 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 industrially produce a PVA resin, 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 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 in the aqueous solution is not particularly limited, but is preferably 5 to 30% by weight from the viewpoint of easy handling.
  • the amount of the PVA resin used is preferably 0.01 to 40 parts by weight, particularly preferably 0.1 to 100 parts by weight in total of the monomer composition [I] and the monomer composition [II]. -30 parts by weight, more preferably 0.5-20 parts by weight. If the amount of the PVA resin used is too small, the amount of protective colloid at the time of emulsion polymerization is insufficient, and the polymerization stability tends to decrease. If the amount used is too large, the acrylic resin emulsion is used. The viscosity tends to increase and the stability decreases.
  • emulsifier other than the PVA resin examples include anionic, cationic, and nonionic surfactants, water-soluble polymers having protective colloid ability other than the PVA resin, and water-soluble oligomers.
  • the surfactant examples include anionic surfactants such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate, and nonionic surfactants such as those having a pluronic type structure and those having a polyoxyethylene type 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.
  • the amount used is an auxiliary amount with respect to the PVA resin, that is, as small as possible.
  • water-soluble polymer having protective colloid ability other than the PVA-based resin examples include 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 polymer having a hydrophilic group such as a sulfonic acid group, a carboxyl group, a hydroxyl group or an alkylene glycol group is preferable, and a polymer or copolymer having a polymerization degree of about 10 to 500 is preferable. It is mentioned in.
  • 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, and a water-soluble oligomer obtained by previously copolymerizing a radical polymerizable reactive emulsifier alone or with another monomer. It is done. These may be used alone or in combination of two or more.
  • 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.
  • an adipate plasticizer As the plasticizer, an adipate plasticizer, a phthalic acid plasticizer, a phosphoric acid plasticizer, or the like can be used.
  • a monomer composition [I] is first emulsion-polymerized using a PVA resin as a dispersion stabilizer to obtain a first emulsion, and then the monomer composition [II]. And emulsion polymerization in the first emulsion.
  • the emulsion polymerization is carried out using the above-mentioned other components such as a polymerization initiator, a polymerization regulator, an auxiliary emulsifier, etc., if necessary, in addition to the PVA resin 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, a monomer dropping type emulsion polymerization method in which water and a PVA-based resin are charged in a reaction can and heated to drop a monomer component and a polymerization initiator; An emulsion monomer dropping type emulsion polymerization method in which a mixed monomer is previously dispersed and emulsified with water-soluble polymer having protective colloid ability other than PVA resin and / or PVA resin and water, and then the dispersed / emulsified monomer is dropped.
  • the emulsion monomer dropping polymerization method is advantageous in terms of reactivity when using a hydrophobic monomer, management of the polymerization process, controllability, and the like.
  • a water-soluble polymer having a protective colloid ability other than PVA resin and / or PVA resin at the end of the polymerization reaction for the purpose of imparting stability to the emulsion and imparting water solubility and / or redispersibility to water. It can also be added later.
  • the monomer dropping emulsion polymerization for example, first, water, a PVA resin, and an auxiliary emulsifier as necessary are charged into a reaction vessel, and this is heated (usually 40 to 90 ° C.), and then the monomer composition [I] Part of the monomer (generally 0.1 to 50% by weight, preferably 1 to 30% by weight, based on the total amount of the monomer composition [I]) and a polymerization initiator are added to the reaction vessel, and initial polymerization is carried out. . Next, the remaining monomer composition of the monomer composition [I] is added to the reaction can in a lump or dropwise, and polymerization is allowed to proceed while further adding a polymerization initiator as necessary.
  • the monomer composition [II] is added to the reaction can all at once or dropwise, 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.
  • emulsion monomer dropping type emulsion polymerization method for example, first, water, if necessary, a PVA resin and an auxiliary emulsifier are charged in a reaction vessel, and this is heated (usually 40 to 90 ° C.) and then PVA type.
  • the remaining monomer composition of the monomer composition [I] is added to the reaction can in a lump or dropwise, and polymerization is allowed to proceed while further adding a polymerization initiator as necessary.
  • the reactor can be used while the PVA resin and / or the water-soluble polymer having protective colloid ability other than the PVA resin, and the monomer composition [II] emulsified / dispersed with an auxiliary emulsifier and water as necessary are added all at once or dropwise. Polymerization is allowed to proceed while 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.
  • the initial amount of the monomer composition [I] and the polymerization initiator are added dropwise to the reaction can without performing the initial polymerization, and then the reaction is performed while dropping the total amount of the monomer composition [II] and the polymerization initiator. It can also be carried out by adding to the can.
  • 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 emulsion polymerization of the monomer composition [I] is usually continued for 5 minutes to 1 hour (preferably 10 minutes to 30 minutes) after the addition of the entire amount of the monomer composition [I] is completed.
  • the polymerization is completed when the polymerization rate of I] exceeds 90% (preferably 95%), and it can be considered that the first emulsion is obtained. If the emulsion composition of the monomer composition [II] is subsequently carried out, Good.
  • the acrylic resin emulsion obtained by emulsion polymerization is typically uniform milky white, and the average particle size of the acrylic resin in the acrylic resin emulsion is 0.2 to 2 ⁇ m. And more 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 present invention it is determined that at least a part of the PVA-based resin is grafted to the acrylic resin, and the measured value in the storage stability and adhesive strength measurement of the resulting acrylic resin emulsion before drying itself. This is preferable from the viewpoint of less variation.
  • the value (W) represented by the following formula (2) is preferably 90% by weight or less, more preferably 85% by weight or less, and still more preferably Is 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).
  • Examples of the method of adjusting the value (W) of the above formula (2) include a method of changing the emulsion polymerization temperature or using a trace amount of reducing agent in combination with a persulfate used as a polymerization catalyst. It is done. For example, the value (W) can be increased by increasing the emulsion polymerization temperature, and the value (W) can be decreased by decreasing the emulsion polymerization temperature. When acidic sodium sulfite or the like is used as the reducing agent, the value (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 according to 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 hairdressing agent, when other compounding components such as resins and additives described later are used in combination, the nonvolatile content is usually 30 to 60% by weight. This is preferable in that the use of the resin or additive 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 according to the present invention is obtained.
  • Such acrylic resin emulsions are used for hairdressing agents, and hairdressing agents using the emulsions exhibit desired performances such as styling properties, re-styling performance, tactile sensation, and performance to be cleaned.
  • the hair styling agent according to the present invention only needs to contain the above-mentioned acrylic resin emulsion, and may be an acrylic resin emulsion used alone, or an acrylic resin emulsion and various compounding agents are used in combination. It may be what you did.
  • 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). More preferably, it is 5% by weight or more (in terms of solid content). In addition, as an upper limit, Preferably it is 70 weight% (solid content conversion), More 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. Moreover, from the viewpoint of reducing the oiliness and stickiness of the hairdressing material, it is preferable to make the content as small as possible, but by using the acrylic resin emulsion of the present invention, the amount of oil used is reduced or not used. can do.
  • 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.
  • Examples of the hair styling method using the hair styling agent containing the acrylic resin emulsion for hair styling according to the present invention include a hair styling method including the following steps (A) and (B).
  • the monomer composition [I] and the monomer composition [II] satisfy the following conditions (i) to (iii).
  • At least one of the monomer composition [I] and the monomer composition [II] contains a (meth) acrylate monomer.
  • the glass transition temperature (Tg2) determined by the Fox formula of the polymer polymerized using the monomer composition [II] is determined by the Fox formula of the polymer polymerized using the monomer composition [I]. 30 ° C. or more higher than the glass transition temperature (Tg1).
  • the effective hair styling amount of the acrylic resin emulsion for hair styling agent is preferably from 0.01 to 1 g per hair bundle having a length of 20 cm and a weight of 1.2 g from the viewpoint of efficient hair styling.
  • 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.
  • Monomer composition [I]: 75 parts of 2-ethylhexyl acrylate, 16 parts of methyl methacrylate, 0.9 part of ethylene glycol dimethacrylate (trade name “Acryester ED”), Tg1 ⁇ 52 ° C.
  • Emulsion X 64 parts of deionized water, 4.5 parts of unmodified PVA resin (average saponification degree 88 mol%, average polymerization degree 500 / manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), monomer composition [I] Emulsified at 1200 rpm for 20 minutes using a turbine blade.
  • Emulsified liquid Y 7 parts of deionized water, 0.5 part of unmodified PVA resin (average saponification degree 88 mol%, average polymerization degree 500 / manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), monomer composition [II] Emulsified at 1200 rpm for 20 minutes using a turbine blade.
  • Solution Z 2.7 parts of 10% APS (ammonium persulfate) aqueous solution
  • a stainless steel (SUS) reaction can equipped with a cooling pipe and a stirring blade, PVA containing 1,2-diol structural unit in the side chain in deionized water (72 parts) (average saponification degree 99 mol%, average The polymerization degree is 300, the content of the 1,2-diol structural unit in the side chain is 8 mol% / manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), 10 parts, sodium bisulfite 0.2 parts, sodium carbonate trihydrate 0.4 was completely dissolved and the temperature was raised to 75 ° C.
  • Emulsion X and 30% of Solution Z were added all at once to the reaction can and stirred for 45 minutes, then the remaining 89% of Emulsion X and 53% of Solution Z were consumed over 3.1 hours.
  • the first emulsion was obtained by continuing stirring for 10 minutes after completion of the dropping.
  • the total amount of the emulsion Y and 7% of the solution Z are added dropwise over 0.4 hours, 10 minutes after the completion of the addition, 5% of the solution Z is added all at once, and further 35% after 5 minutes of the solution Z is added all at once. Added and stirred for 45 minutes.
  • the polymerization was carried out so that the internal temperature of the polymerization solution was maintained at 75 to 80 ° C.
  • the internal temperature was then brought to 55 ° C., and 1.7 parts of a 10% aqueous solution of perbutyl H-69 (manufactured by NOF Corporation) was added all at once, and 3.4 parts of a 5% aqueous solution of vitamin C was divided into two portions for 30 minutes. Every other portion was added and stirred while maintaining the internal temperature of 50 to 55 ° C. for a total of 1 hour to obtain a second emulsion.
  • the obtained second emulsion was cooled to obtain an acrylic resin emulsion (a) (non-volatile content: 43%; viscosity: 420 mPa ⁇ s (B-type viscometer: 12 rpm, 23 ° C.)).
  • the acrylic resin emulsion (a) was dispersed and stabilized.
  • Example 2 Acrylic resin emulsion (b)>
  • 68 parts of 2-ethylhexyl acrylate, 23 parts of methyl methacrylate, 0.9 parts of ethylene glycol dimethacrylate (manufactured by Mitsubishi Rayon Co., Ltd .; trade name “Acryester ED”), Tg1 ⁇
  • An acrylic resin emulsion (b) (non-volatile content: 43%; viscosity: 1000 mPa ⁇ s (B-type viscometer: 12 rpm, 23 ° C.)) was obtained in the same manner as in Example 1 except that the temperature was changed to 43 ° C.
  • the acrylic resin emulsion (b) was dispersed and stabilized.
  • Emulsion X 71 parts of deionized water, 5 parts of unmodified PVA resin (average saponification degree 88 mol%, average polymerization degree 500 / manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), and monomer composition [I] are turbine blades Emulsified for 20 minutes at 1200 rpm.
  • Solution Z 2.7 parts of 10% APS (ammonium persulfate) aqueous solution
  • a SUS reaction vessel equipped with a cooling pipe and a stirring blade was added to a PVA resin containing 1,2-diol structural units in the side chain in deionized water (72 parts) (average saponification degree 99 mol%, average polymerization degree). 300, content of side chain 1,2-diol structural unit 8 mol% / manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 10 parts, sodium hydrogen sulfite 0.2 parts, sodium carbonate trihydrate 0.4 parts was completely dissolved and heated to 75 ° C.
  • the internal temperature was then brought to 55 ° C., and 1.7 parts of a 10% aqueous solution of perbutyl H-69 (manufactured by NOF Corporation) was added all at once, and 3.4 parts of a 5% aqueous solution of vitamin C was divided into two portions for 30 minutes.
  • the solution was added in portions and stirred while maintaining the internal temperature of 50 to 55 ° C. for a total of 1 hour. Thereafter, the mixture was cooled to obtain an acrylic resin emulsion (a ′) (non-volatile content: 43%; viscosity: 490 mPa ⁇ s (B-type viscometer 12 rpm, 23 ° C.)).
  • the acrylic resin emulsion (a ′) of Comparative Example 1 was dispersed and stabilized.
  • Comparative Example 2 Acrylic resin emulsion (b ')>
  • hair styling performance (setting force), re-hair styling performance (re-setting power, re-setting holding power) and tactile sensation were evaluated as follows.
  • ⁇ Hair styling performance (setting power)> Apply 0.5g of the hair styling solution for styling performance test to the hair bundle (length 20cm x weight 1.2g; hair bundle shop) with a dropper, and apply it more evenly with fingers with 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 laid out even if shaken a little. ⁇ : Shake slightly to expand the hair tips slightly. ⁇ ... The hair ends are loose when not shaken or shake a little.
  • ⁇ 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 conditioned). [Delta] ... Matched, but the hair bundles expanded slightly. X: It is not a hair bundle and hair is not arranged. In the above evaluation, “ ⁇ ” indicates excellent performance, and “ ⁇ ” is practically acceptable. In addition, “x” is inferior in performance.
  • ⁇ Re-hair styling performance (re-set holding power)> The hair bundle state when the hair bundle after light hair styling performance (resetting power) evaluation was shaken lightly was subjected to sensory evaluation.
  • the evaluation method is as follows. (Evaluation criteria) ⁇ : The hair bundle is almost undisturbed with the hair bundles kept together (re-styling is maintained). ⁇ : Hair bundles slightly spread. X: The hair bundle is greatly separated (re-hair is not held).
  • the hair conditioner solution for cleaning performance test is applied to a 50 ⁇ m thick PET (polyethylene terephthalate) film with a 100 ⁇ m applicator and dried at 23 ° C. and 50% RH for 30 minutes to obtain a coating film having a thickness of about 25 ⁇ m (when dried). It was. Put a drop of 60 ° C deionized water on the coating film with a dropper and rub it once with a finger to draw a circle with a diameter of about 1 cm. Pulp waste cloth (Nippon Paper Crecia Co., Ltd., "Kimwipe") (Registered trademark)). Thereafter, the operation of dropping one drop of 60 ° C.
  • the evaluation method is as follows. (Evaluation criteria) ⁇ 70% to 100% wiped off. ⁇ : Wipe off from 30% to less than 70%. X: Wiped off from 0 to less than 30%.
  • ⁇ Washable performance (cold water)> The hair conditioner solution for cleaning performance test is applied to a 50 ⁇ m thick PET (polyethylene terephthalate) film with a 100 ⁇ m applicator and dried at 23 ° C. and 50% RH for 30 minutes to obtain a coating film having a thickness of about 25 ⁇ m (when dried). It was. After dropping 1 drop of deionized water at 15 ° C. onto the coating film with a dropper, after 1 minute, lightly tapping 10 times with a finger, pulp waste (Nippon Paper Crecia Co., Ltd., “Kimwipe” (registered trademark) )). The degree of cleaning of the coating-like hair styling solution was visually evaluated.
  • the evaluation method is as follows. (Evaluation criteria) ⁇ 70% to 100% wiped off. ⁇ : Wipe off from 30% to less than 70%. X: Wiped off from 0 to less than 30%.
  • Table 1 shows the results of tests using the compositions of Examples 1 and 2 and Comparative Examples 1 and 2, the glass transition temperature, and the hairdressing agent solution.
  • the styling performance (hair styling performance, re-hair styling performance, and tactile sensation) and the performance to be washed are excellent in balance. I understand.
  • the acrylic resin emulsions obtained by the non-multistage polymerization of Comparative Examples 1 and 2 have good hair styling performance, re-hair styling properties, and tactile sensation, but are inferior in washing performance, particularly washability in cold water. I know that there is.
  • 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 pour un agent de coiffage. L'émulsion de résine acrylique permet de produire un agent de coiffure qui présente des performances de lavabilité et de coiffage excellentes et équilibrées (performances de coiffure, performances réparatrices des cheveux, propriétés tactiles), elle est obtenue par polymérisation en émulsion d'une composition de monomère [I] et d'une composition de monomères [II], et se caractérise en ce qu'elle satisfait les conditions (i), (ii) et (iii). (i) Au moins l'une parmi la composition de monomère [I] et la composition de monomère [II] comprend un monomère méthacrylate. (ii) La température de transition vitreuse (Tg2) déterminée par l'équation de Fox pour un polymère qui est polymérisé en utilisant la composition de monomères [II] est d'au moins 30 °C supérieure à la température de transition vitreuse (Tg1) déterminée par l'équation de Fox pour un polymère qui est polymérisé en utilisant la composition monomère [I]. (iii) Les proportions de mélange (rapport pondéral) de la composition de monomère [I] et de la composition de monomères [II] sont [I]/[II] = 50/50 à 99/1.
PCT/JP2015/056731 2014-03-07 2015-03-06 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 WO2015133629A1 (fr)

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KR1020167027429A KR102318407B1 (ko) 2014-03-07 2015-03-06 정발제용 아크릴계 수지 에멀젼 및 이를 함유하는 정발제, 및 정발 방법

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JPH1045825A (ja) * 1996-05-02 1998-02-17 Basf Ag アルカリ可溶性（メト）アクリル酸エステルを基礎とする共重合体の製造法及びこのような共重合体からなる整髪組成物中の皮膜形成剤
JP2003507399A (ja) * 1999-08-19 2003-02-25 ビーエーエスエフ アクチェンゲゼルシャフト 水性化粧用組成物
JP2004168776A (ja) * 2002-11-18 2004-06-17 Rohm & Haas Co 持続性保持ヘアスタイリング組成物およびその使用法
JP2006124682A (ja) * 2004-09-29 2006-05-18 Nippon Synthetic Chem Ind Co Ltd:The 水性エマルジョンおよびその用途
JP2007332370A (ja) * 2006-06-13 2007-12-27 Rohm & Haas Co 多段ポリマー組成物およびその使用方法
WO2014098052A1 (fr) * 2012-12-18 2014-06-26 日本合成化学工業株式会社 Émulsion de résine acrylique pour agents de coiffage, agent de coiffage la comprenant et procédé de coiffage

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Publication number Priority date Publication date Assignee Title
CN101878231B (zh) * 2007-11-28 2013-07-24 日本合成化学工业株式会社 水性乳液及其制造方法
JP5091011B2 (ja) 2008-05-29 2012-12-05 日本合成化学工業株式会社 整髪剤
JP2011148721A (ja) 2010-01-20 2011-08-04 Mandom Corp 頭髪化粧料

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06172732A (ja) * 1992-09-10 1994-06-21 Natl Starch & Chem Investment Holding Corp 水性高凝集性感圧性接着剤
JPH1045825A (ja) * 1996-05-02 1998-02-17 Basf Ag アルカリ可溶性（メト）アクリル酸エステルを基礎とする共重合体の製造法及びこのような共重合体からなる整髪組成物中の皮膜形成剤
JP2003507399A (ja) * 1999-08-19 2003-02-25 ビーエーエスエフ アクチェンゲゼルシャフト 水性化粧用組成物
JP2004168776A (ja) * 2002-11-18 2004-06-17 Rohm & Haas Co 持続性保持ヘアスタイリング組成物およびその使用法
JP2006124682A (ja) * 2004-09-29 2006-05-18 Nippon Synthetic Chem Ind Co Ltd:The 水性エマルジョンおよびその用途
JP2007332370A (ja) * 2006-06-13 2007-12-27 Rohm & Haas Co 多段ポリマー組成物およびその使用方法
WO2014098052A1 (fr) * 2012-12-18 2014-06-26 日本合成化学工業株式会社 Émulsion de résine acrylique pour agents de coiffage, agent de coiffage la comprenant et procédé de coiffage

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JP6635248B2 (ja) 2020-01-22

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