KR20150096498A - Acrylic resin emulsion for hairdressing agents, hairdressing agent comprising same, and hairdressing method - Google Patents

Abstract

It is an object of the present invention to provide an acrylic resin emulsion which is preferable for obtaining a stable substance having a good balance between a styling performance (a repelling performance, a rewriting performance, a tactile property) and a cleaning performance. The acrylic resin emulsion for regularizers of the present invention contains an acrylic resin (A) which is dispersed and stabilized by a polyvinyl alcohol-based resin [I].

Description

[0001] The present invention relates to an acrylic resin emulsion for regular purifying agent, a purifying agent containing the same, and a method for purifying the same,

The present invention relates to an acrylic resin emulsion useful for a hair styling agent.

Examples of the positive active agent include liquid, gel, foam, spray, cream, wax, and the like. Normally, a correcting agent forms a film on the surface of a hair, and it is composed of a polymer (a polymer for a set) for maintaining a desired shape as a main component, an additive imparted for various purposes, a solvent compounded according to the formulation, . In the case of the regular purifying agent, in recent years, the hair can be freely arranged at the time of regular rectification, and a hair cream or hair wax, which is an emulsifier type using an emulsion and water, becomes mainstream as a formulation which can be easily modified even after the regular treatment.

In addition, the performance of the hair styling (hair trim) such as excellent appearance performance and excellent tactile performance is demanded for the performance of maintaining the hair for a long time by adding a desired shape to the hair, · The ease of removal is also required as performance, and various stabilizers have been developed.

For example, Patent Document 1 discloses a stabilizing agent of an aqueous solution type using a polyvinyl alcohol-based resin having a specific structure as a main component of a polymer component as a main agent. In Patent Document 2, A hair cosmetic composition containing polyvinyl alcohol as a blending agent in an emulsifying composition composed of an active agent and water is described.

(Patent Document 1) JP 2009-286724 A (Patent Document 2) JP 2011-148721 A

The cleaning agent of Patent Document 1 is intended to assure the performance that a polyvinyl alcohol resin having a specific structure has a good curl retention under high humidity conditions, less stickiness, and has low moisture damage due to moisture, Further, the cleaning agent of Patent Document 2 is claimed to improve the aesthetics at the time of use by blending a polyvinyl alcohol-based resin into the emulsion composition, and does not impart unnatural gloss to the hair after application. However, the corrective agent described in Patent Document 1 is insufficient in that a finger comb (finger), a comb, a brush or the like is satisfactory, but there is still room for improvement in terms of retaliation in the event of collapsing the normal leg, and , And the corrective agent described in Patent Document 2 is in need of further improvement because it has a large stickiness and a poor feeling of use.

In addition, while the corrective agent is required to be easily cleaned after use, when it is exposed to sweat, rain, or the like, it becomes damp at the time of use, and the inconvenience that the regular hair falls and clings to the forehead or cheeks, It is necessary to have a proper washing performance.

Therefore, the present invention provides an acrylic resin emulsion which is effectively used as a correcting agent with excellent balance in styling performance (settling performance, settling performance, re-set performance, tactile property) .

The inventors of the present invention have conducted intensive studies in view of such circumstances, and as a result, they have found that a polyvinyl alcohol-based resin which has conventionally been used as a polymer of a subject or as a compounding agent can be obtained by using it as a dispersion stabilizer for an acrylic resin (A settling performance, a settling performance, a re-set performance, and a tactile property) and a cleaning performance, and has completed the present invention.

That is, the gist of the present invention relates to the following (1) to (7).

(1) An acrylic resin emulsion for regularizers containing an acrylic resin (A) dispersed and stabilized by a polyvinyl alcohol-based resin [I].

(2) The acrylic resin emulsion for regularizing agent as described in (1) above, wherein the polyvinyl alcohol resin [I] contains a side chain 1,2-diol structural unit represented by the following general formula (1).

[Formula 1]

(In the formula (1), R ¹ to R ⁶ each independently represent a hydrogen atom or an organic group, and X represents a single bond or a bonding chain.)

(3) In the above (2), the content of the side chain 1,2-diol structural unit in the polyvinyl alcohol-based resin [I] containing the side chain 1,2-diol structural unit represented by the formula (1) 15% by mole of an acrylic resin emulsion for regular-purifying preparations.

(4) The acrylic resin composition according to any one of (1) to (3) above, wherein the acrylic resin (A) is a monomer component containing 40% by weight or more of an aliphatic (meth) acrylate monomer having 4 to 12 carbon atoms in the alkyl group Acrylic resin emulsion for a normalizing agent.

(5) The acrylic resin emulsion for regular use as defined in any one of (1) to (4) above, wherein the acrylic resin (A) has a glass transition temperature of 70 ° C or lower.

(6) A regular-purifying agent containing the acrylic resin emulsion for regular-purifying agent according to any one of (1) to (5).

(7) a step of applying an effective amount of an acrylic resin emulsion for stabilizing agent containing an acrylic resin (A) dispersed and stabilized by a polyvinyl alcohol-based resin [I] to hair; Or before or after the hair is trimmed to a desired shape.

Since the acrylic resin emulsion for regular purifying agent of the present invention is excellent in water solubility and / or redispersibility into water, the regular purifying agent prepared using such an acrylic resin emulsion for regular purifying agent has excellent cleaning performance and is excellent in balance with styling performance It has an excellent effect.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail, but these are only examples of preferred embodiments. Also, in the present invention, (meth) acryl means acryl or methacryl, (meth) acryloyl means acryloyl or methacryloyl, and (meth) acrylate means acrylate or methacrylate , And the acrylic resin is a resin obtained by polymerizing a monomer component containing at least one (meth) acrylic monomer.

The acrylic resin emulsion for regular use of the present invention contains an acrylic resin (A) dispersed and stabilized by a polyvinyl alcohol resin (hereinafter referred to as "PVA resin") [I].

In the present invention, the dispersion stabilized state refers to a dispersed state in which the emulsion remains in a uniform state without sedimentation separation even at 23 DEG C for one month.

≪ Polyvinyl alcohol-based resin [I]

As the PVA resin [I], a PVA resin having a specific average degree of saponification and an average degree of polymerization shown below is preferable.

The PVA resin [I] preferably has an average degree of saponification of 70 to 99.9 mol%, particularly preferably 80 to 99.5 mol%, and more preferably 85 to 99.0 mol%. If the average degree of saponification is too low, the polymerization tends not to proceed stably, and even if the polymerization is completed, the storage stability of the emulsion tends to be lowered, and the emulsion stability tends to be too low and the preparation tends to become difficult.

Further, in the present invention, the average degree of saponification can be obtained by the method of calculating the degree of saponification 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, and particularly preferably 200 to 500. When the average degree of polymerization is too low, the protective colloid capacity during emulsion polymerization tends to be insufficient and the polymerization tends to be difficult to proceed stably. When the degree of polymerization is too high, the polymerization system becomes thicker at the time of polymerization so that the reaction system becomes unstable, There is a tendency to decrease.

In the present invention, the average degree of polymerization can be obtained by a method of calculating the average degree of polymerization described in JIS K 6726 (1994).

In the present invention, the PVA resin [I] means PVA itself or, for example, modified by various modified species, and the degree of modification thereof is usually 20 mol% or less, preferably 15 mol% or less , And more preferably 10 mol% or less.

Examples of modified PVA resins include cation-modified PVA resins modified with cationic groups such as anionic-modified PVA resins modified with anionic groups such as carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups; cationic modified PVA resins modified with cationic groups such as quaternary ammonium groups; , A diacetone acrylamide group, a mercapto group, a silanol group and the like, or a PVA-based resin containing a 1,2-diol structural unit in the side chain.

The PVA-based resin [I] in the present invention is preferably a PVA-based resin containing a 1,2-diol structural unit in its side chain from the viewpoint of excellent dispersion stability when polymerizing an acrylic acid ester monomer, Is a PVA-based resin containing a 1,2-diol structural unit represented by the following general formula (1).

(Formula 1)

(In the formula (1), R ¹ to R ⁶ each independently represent a hydrogen atom or an organic group, and X represents a single bond or a bonding chain.)

In the general formula (1), R ¹ to R ⁶ independently represent a hydrogen atom or an organic group. It is preferable that all of R ¹ to R ⁶ are hydrogen atoms, but it may be an organic group if the amount is such that the resin properties are not significantly impaired. The organic group is not particularly limited and is preferably an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, And may have a substituent such as a halogeno group, a hydroxyl group, an ester group, a carboxylic acid group or a sulfonic acid group, if necessary.

In the general formula (1), X is a single bond or a bond chain, and is preferably a single bond in terms of set holding power, no stickiness, familiarity with hair, and the like. Examples of the bonding chain include, but are not limited to, hydrocarbons such as alkylene, alkenylene, alkynylene, phenylene and naphthylene (these hydrocarbons may be substituted with halogens such as fluorine, chlorine and bromine) _{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 -, - NRNR- _{, -HPO 4 -, - Si (} OR) 2 -, - OSi (OR) 2 -, - OSi (OR) 2 O -, - Ti (OR) 2 -, - OTi (OR) 2 -, - OTi ( _{OR) 2 O -, - Al} (OR) -, - OAl (OR) -, - OAl (OR) O- may be mentioned such as (R is an optional substituent for each independently, a hydrogen atom, and the alkyl group is preferably , And m is a natural number). Among them, an alkylene group having 6 or less carbon atoms, particularly a methylene group or -CH ₂ OCH ₂ - is preferable in view of viscosity stability and heat resistance at the time of production.

The PVA resin containing the 1,2-diol structural unit represented by the above formula (1) can be obtained, for example, by saponifying (I) a copolymer of vinyl acetate and 3,4-diacetoxy- (II) a method of saponifying and decarboxylating a copolymer of vinyl acetate and vinylethylene carbonate, (III) a method of saponifying and decarboxylating a copolymer of vinyl acetate and vinyl ethylene carbonate with 2,2-dialkyl-4-vinyl-1,3-dioxolane A method of saponifying and decarboxylating the copolymer, (IV) a method of saponifying a copolymer of vinyl acetate and glycerin monoaryl ether, and the like.

The content of the 1,2-diol structural unit in the PVA-based resin containing the 1,2-diol structural unit represented by the formula (1) is preferably from 1 to 15 mol%, particularly preferably from 1 to 12 mol% , More preferably 2 to 10 mol%, and particularly preferably 2 to 9 mol%. When the content of the 1,2-diol structural unit is too low, the mechanical stability of the emulsion tends to decrease. When the content is too high, the stability at the time of polymerization tends to be lowered, and it tends to be difficult to obtain a stable emulsion having a high non- .

The content of the side chain 1,2-diol unit in the PVA resin can be determined from the ¹ H-NMR spectrum (solvent: DMSO-d 6, internal standard: tetramethylsilane) of the PVA completely saponified, May be calculated from the peak area derived from the hydroxyl group in the 1,2-diol unit, the methine proton, and the methylene proton, the methylene proton in the main chain, the proton in the hydroxyl group connected to the main chain, and the like.

The average saponification degree of the PVA 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 deteriorate, and it tends to be 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 from 50 to 3,000, more preferably from 100 to 2,500, still more preferably from 200 to 2,000, Preferably 200 to 500. If the average degree of polymerization is too low, it tends to be difficult to industrially produce a PVA resin. When the average degree of polymerization is too large, the viscosity of the emulsion becomes too high or the polymerization stability of the emulsion tends to decrease.

In the present invention, the PVA resin [I] is usually used as an aqueous solution using an aqueous medium, and this is used for the emulsion polymerization process. Here, the aqueous medium means water or an alcoholic solvent mainly composed of water, and preferably water.

The amount (non-volatile component) of the PVA resin [I] in the aqueous solution is not particularly limited, but is preferably 5 to 30% by weight from the viewpoint of ease of handling.

≪ Acrylic resin (A) >

The acrylic resin (A) in the present invention is obtained by polymerizing a monomer component containing a (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 even more preferably 70% by weight or more, based on the entire monomer component.

Examples of the (meth) acrylic monomer (a1) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, (Meth) acrylate such as 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, octyl (Meth) acrylate-based monomers, aromatic (meth) acrylate-based monomers such as phenoxy (meth) acrylate, and trifluoroethyl (meth) acrylate. These may be used alone or in combination of two or more. Of these, aliphatic (meth) acrylate-based monomers having 1 to 18 carbon atoms in the alkyl group are preferable from the viewpoint of hair feel and financial restraint, and particularly preferred are aliphatic (Meth) acrylate monomer, more preferably an aliphatic (meth) acrylate monomer having 4 to 12 carbon atoms in the alkyl group, and particularly preferably n-butyl acrylate and 2-ethylhexyl acrylate. Also, a combination of 2-ethylhexyl acrylate and methyl methacrylate or a combination of n-butyl acrylate and methyl methacrylate can be suitably used.

The functional group-containing monomer (a2) may be copolymerized with the (meth) acrylic monomer (a1). Examples of the functional group-containing monomer (a2) include monomers having two or more vinyl groups in the molecular structure, glycidyl- Containing monomers, hydrolyzable silyl group-containing monomers, acetoacetyl group-containing monomers, hydroxyl group-containing monomers, and carboxyl group-containing monomers. Of 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 in view of improving the water repellency without deteriorating the regularity.

Examples of the monomer having two or more vinyl groups in the molecular structure include divinylbenzene, diarylphthalate, triarylisocyanurate, triarylisocyanurate, ethylene glycol di (meth) acrylate, 1,2 Propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl Glycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, and aryl (meth) acrylate. Among these, ethylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, 1,3-propylene glycol di (meth) acrylate, 1,4- (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate and trimethylolpropane tri desirable.

Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate, glycidyl (meth) arylether and 3,4-epoxycyclohexyl (meth) acrylate.

Examples of the aryl group-containing monomer include monomers having two or more aryl groups such as triaryloxyethylene, diaryl maleate, triarylcyanurate, triarylisocyanurate and tetraaryloxyethane, Dicyclohexylcarbodiimide, diallyl ether, and acetic acid aryl.

Examples of the hydrolyzable silyl group-containing monomer include vinyl-based silyl group-containing monomers such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (? -Methoxyethoxy) silane and vinylmethyldimethoxysilane (Meth) acryloxypropyltrimethoxysilane,? - (meth) acryloxypropyltrimethoxysilane,? - (meth) acryloxypropylmethyldimethoxysilane,? - (Meth) acryloxycyclosilyl group-containing monomers such as diethoxy silane. Among them, the (meth) acryloylcyclotrisilyl group-containing monomer is preferable in view of excellent copolymerization with the (meth) acrylate-based monomer (a1).

Examples of the above-mentioned acetacetyl group-containing monomer include vinyl acetate esters, acyl acetate aryl esters, diacetyl acylaryl esters, acetacetoxyethyl (meth) acrylate, acetoacetoxyethelactonat, acetacetoxypropyl (Meth) acrylate, acetacetoxypropyl crotonate, and 2-cyanoacetoxyethyl (meth) acrylate.

Examples of the hydroxyl group-containing monomer include (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and 4-hydroxybutyl From the viewpoint of protective colloidal action and water washability in emulsion polymerization, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferable.

Examples of the carboxyl group-containing monomer include (meth) acrylic acid, acrylic acid dimer, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, acrylamide N- And cinnamic acid. Of these, acrylic acid and methacrylic acid are preferable from the viewpoint of protecting colloid action and water washability in emulsion polymerization.

The content 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 from 0.1 to 3% by weight, based on the whole monomer component. If the content ratio is too large, the acrylic resin becomes too hard and does not exhibit sufficient adhesive strength, and regularity tends to deteriorate, while when it is too small, the effect of washing with water tends to be difficult to be understood.

When the functional group-containing monomer (a2) is a monomer having two or more vinyl groups in the molecular structure, it is preferably from 0.01 to 5% by weight, particularly preferably from 0.05 to 3% by weight, More preferably 0.1 to 1% by weight.

A small amount of a styrene-based monomer such as styrene or? -Methylstyrene, a vinyl monomer such as vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyl, A vinyl ester monomer such as vinyl sebacate, vinyl sebacate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl butyric acid and vinyl 2-ethylhexanoate may be used.

With respect to the acrylic resin emulsion according to the present invention, in addition to the above-mentioned monomer components, other components may be further used if necessary. These other components may be appropriately selected depending on the purpose, and examples thereof include polymerization initiators, polymerization regulators, auxiliary emulsifiers, and plasticizers.

As the polymerization initiator, those which can be used for ordinary emulsion polymerization can be used, and examples thereof include inorganic peroxides such as potassium persulfate, sodium persulfate and ammonium persulfate; organic peroxides, azo type initiators, hydrogen peroxide, butyl peroxide , And a redox polymerization initiator in combination with a reducing agent such as acidic sodium sulfite or L-ascorbic acid. These may be used alone or in combination of two or more. Of these, ammonium persulfate and potassium persulfate are preferable in view of easy polymerization.

As the polymerization regulator, any of the known polymerization regulators can be appropriately selected. Examples of such polymerization regulators include chain transfer agents and buffers.

Examples of the chain transfer agent include alcohols such as methanol, ethanol, propanol and butanol; aldehydes such as acetaldehyde, propionaldehyde, n-butylaldehyde, furfural and benzaldehyde; and aldehydes such as dodecyl mercaptan, Mercaptans such as thioglycolic acid, octyl thioglycolate, thioglycerol and the like. These may be used alone or in combination of two or more. The use of a chain transfer agent is effective in terms of stably carrying out polymerization, and is preferably used for adjusting the degree of polymerization of an acrylic resin.

Examples of the buffer include sodium acetate, ammonium acetate, sodium phosphate dibasic, sodium citrate and the like. These may be used alone or in combination of two or more.

As the auxiliary emulsifier, any of those which can be used for emulsion polymerization and are known to those skilled in the art can be used. Therefore, the auxiliary emulsifier can be appropriately selected from known surfactants such as anionic, cationic, and nonionic surfactants, water-soluble polymers having protective colloid functions other than the PVA resin [I], and water-soluble oligomers You can choose.

Examples of the surfactant include anionic surfactants such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate and nonionic surfactants such as those having a pluronic structure or a polyoxyethylene structure . As the surfactant, a reactive surfactant having a radical polymerizable unsaturated bond in its structure may also be used. These may be used alone or in combination of two or more.

The use of the surfactant has the effect of facilitating the emulsion polymerization to proceed smoothly (as an emulsifier) or inhibiting the generation of defective particles or block form during polymerization. However, when these surfactants are widely used as an emulsifier, the graft ratio tends to decrease. For this reason, when a surfactant is used, it is preferable that the amount of the surfactant used is an amount that is auxiliary to the PVA resin [I], that is, it is reduced as much as possible.

Examples of the water-soluble polymer having a protective colloid function other than the PVA resin [I] include PVA resins other than the PVA resin [I], hydroxyethyl cellulose, polyvinyl pyrrolidone, methyl cellulose, . These may be used alone or in combination of two or more. These are effective in changing the viscosity of the emulsion by changing the particle size of the emulsion or the particle size of the emulsion.

As the water-soluble oligomer, for example, a polymer having a hydrophilic group such as a sulfonic acid group, a carboxyl group, a hydroxyl group, an alkylene glycol group and the like is preferable, and a polymer or copolymer having a degree of polymerization of about 10 to 500 is particularly preferable . Specific examples of the water-soluble oligomer include amide-based copolymers such as 2-methacrylamide-2-methylpropane sulfonic acid copolymer and the like, sodium methacrylate-4-styrene sulfonate copolymer, styrene / maleic acid copolymer, Melamine sulfonic acid formaldehyde condensates, and poly (meth) acrylate salts. Specific examples thereof include a water-soluble oligomer obtained by copolymerizing a monomer having a sulfonic acid group, a carboxyl group, a hydroxyl group, an alkylene glycol group or the like, or a reactive polymerizable reactive emulsifier in advance, alone or in combination with other monomers. These may be used alone or in combination of two or more.

As the plasticizer, an adipate plasticizer, a phthalic acid plasticizer, a phosphoric acid plasticizer and the like can be used.

The amount of these other components to be used can be appropriately selected depending on the purpose within a range not to impair the effect of the present invention.

≪ Process for producing acrylic resin emulsion >

Next, a method for producing the acrylic resin emulsion of the present invention will be described.

The acrylic resin emulsion of the present invention can be produced by, for example, emulsion-polymerizing the above-mentioned monomer components using a PVA resin [I] as a dispersion stabilizer. In this polymerization process, an acrylic resin emulsion in which the PVA resin [I] is used as a dispersion stabilizer and the dispersion stabilized acrylic resin (A) is used as a dispersion medium is produced.

In the present invention, the amount of the PVA resin [I] to be used is preferably 0.01 to 40 parts by weight, particularly preferably 0.1 to 30 parts by weight, more preferably 0.1 to 30 parts by weight based on 100 parts by weight of the total monomer components constituting the acrylic resin (A) More preferably 0.5 to 20 parts by weight. If the amount of the PVA resin [I] to be used is too small, the protective colloid amount during emulsion polymerization tends to be insufficient and the polymerization stability tends to decrease. If the amount is too large, the viscosity of the acrylic resin emulsion increases, .

Here, the total amount of the PVA resin [I] used is usually present in the acrylic resin emulsion formed by polymerization.

In general, the emulsion polymerization is carried out by using, in addition to the PVA resin [I] and the above monomer components, other components than those described above such as a polymerization initiator, a polymerization modifier, a secondary emulsifier and the like, if necessary. The reaction conditions for the polymerization may be appropriately selected depending on the kind of the monomer, the purpose, and the like.

Examples of the emulsion polymerization method include a monomer dropping emulsion polymerization method in which water and a PVA resin [I] are charged into a reaction vessel and the temperature is raised to drop the monomer component and the polymerization initiator; An emulsion monomer dropping emulsion polymerization method in which a mixed monomer is dispersed and emulsified in advance with a water-soluble polymer having a protective colloid function other than the PVA resin [I] and / or the PVA resin [I] in water and then the dispersion / emulsion monomer is dropped However, the emulsion monomer dropping polymerization method is advantageous in view of reactivity at the time of using the hydrophobic monomer, control of the polymerization process, controllability, and the like. In addition, a water-soluble polymer having a protective colloidal ability other than the PVA resin [I] and / or the PVA resin [I] is added at the completion of the polymerization reaction after the emulsion has been stabilized or given water solubility and / It is also possible to do.

The emulsion polymerization process will be more specifically described below.

In the above-mentioned monomer dropwise emulsion polymerization, for example, water, a PVA resin [I] and, if necessary, a secondary emulsifier are added to a reaction vessel, and after raising the temperature (usually 40 to 90 ° C) A part and a polymerization initiator are added to the reaction vessel to perform initial polymerization. Then, the remaining monomer components are added to the reaction vessel in a batch or dropwise manner, and the polymerization is allowed to proceed while adding a polymerization initiator, if necessary. When it is judged that the polymerization reaction has been completed, the reaction vessel can be cooled to take out the objective acrylic resin emulsion.

In the emulsion monomer dropping emulsion polymerization method, for example, water, a PVA resin (I) and an auxiliary emulsifier are added as needed to the reaction vessel, and the temperature is raised (usually 40 to 90 ° C) , A water-soluble polymer having a protective colloid function other than the PVA resin [I] and / or the PVA resin [I], and optionally a secondary emulsifier, a part of the monomer components emulsified and dispersed in water and a polymerization initiator And the initial polymerization is carried out. Then, the remaining monomer components are added to the reaction vessel in a batch or dropwise manner, and the polymerization is allowed to proceed while adding a polymerization initiator, if necessary. When it is judged that the polymerization reaction has been completed, the reaction vessel is cooled and the desired acrylic resin emulsion can be taken out.

It is also possible to carry out the above-mentioned method by adding the whole amount of the monomer components and the polymerization initiator to the reaction vessel without dropping the initial polymerization. When the reaction temperature is lower than 70 占 폚, it is preferable to use a redox polymerization reaction system in which a reducing agent is used in combination because the reaction proceeds smoothly.

In the present invention, the acrylic resin emulsion obtained by emulsion polymerization is typically a uniform milky white color. The average particle diameter of the acrylic resin (A) in the acrylic resin emulsion is preferably 0.2 to 2 占 퐉, 0.3 to 1.5 mu m.

Here, the average particle diameter can be measured by a conventional method, for example, a laser analysis / scattering type particle size distribution measuring apparatus "LA-950 S2" (manufactured by Horiba Seisakusho Co., Ltd.).

The acrylic resin (A) in the acrylic resin emulsion preferably has a glass transition temperature of 70 占 폚 or lower, particularly preferably 40 占 폚 or lower, more preferably 20 占 폚 or lower, particularly preferably 0 占 폚 or lower. If the glass transition temperature is too high, the acrylic resin becomes hard and tends to be broken when dried, thereby reducing the reworking performance. The lower the glass transition temperature is, the better the reverberation tendency tends to be obtained because the polymer comes to have stickiness, but the lower limit is usually -80 캜, preferably -70 캜. The higher the content ratio of the PVA resin [I], the lower the glass transition temperature of the acrylic resin (A) is, in terms of reevaluation, is preferable.

The glass transition temperature of the acrylic resin (A) in the present invention is a value that can be obtained by calculating the glass transition temperature of the homopolymer composed of the respective polymerization components constituting the acrylic resin by Fox's formula, and the acrylic resin (A Can be adjusted by appropriately adjusting the weight ratio of the respective polymerization components constituting the polymerization initiator. When a functional group-containing monomer is used in combination, it may be calculated by Fox's equation based on the main monomer component excluding such functional group-containing monomer.

In the present invention, it is preferable that at least a part of the PVA resin (I) is grafted to the acrylic resin (A), the difference between the measured values in the storage stability and the adhesive strength measurement of the obtained acrylic resin emulsion itself It is preferable from the viewpoint of reducing the number of parts.

When the PVA resin [I] is grafted onto the acrylic resin (A), the value (W) represented by the following formula (2) is preferably 90% by weight or less, more preferably 85% Preferably 80% by weight or less. The lower limit is usually 1% by weight, preferably 5% by weight, more preferably 10% by weight. Such a value is a criterion for the degree of grafting. When the value is too low, there is a tendency that the degree of grafting is low, the protective colloid action during emulsion polymerization is lowered, and the polymerization stability is lowered. , There is a tendency that an emulsion stable at a high concentration tends to be generated.

The value W in the equation (2) is calculated as follows. That is, the target emulsion or the like is dried at room temperature to prepare a film, and the film is extracted for 8 hours in boiling water and acetone for 8 hours, and the resin that has not been grafted is removed. In this case, w ₁ (g) is the absolute dry weight of the film before extraction, and w ₂ (g) is the absolute dry weight of the film after extraction.

W (wt%) = (w ₂ ) / (w ₁ ) x 100 (2)

As a method of adjusting the value W in the above formula (2), the emulsion polymerization temperature is changed (when it is high (W) is high and when it is low (W) is low) By weight of a reducing agent (for example, acidic sodium sulfite or the like) ((W) is increased).

In the present invention, various additives may be added again to the acrylic resin emulsion after emulsion polymerization if necessary. Examples of such additives include organic pigments, inorganic pigments, water-soluble additives, pH adjusters, preservatives, antioxidants, and the like.

In this way, the acrylic resin emulsion of the present invention is obtained. In use, it is preferable to adjust the nonvolatile content to usually 0.1 to 65 wt%. When such an acrylic resin emulsion is used as a cleaning agent, the nonvolatile content is usually 30 to 60% by weight when it is used in combination with other components (resins and additives to be described later), and the use of other resins or additives It is preferable in view of difficulty in limiting. When such an acrylic resin emulsion is used alone as a cleaning agent, it is preferable that the nonvolatile content is usually 1 to 10% by weight from the standpoint of uniformly spreading on the hair.

Thus, the acrylic resin emulsion of the present invention is obtained. Such an acrylic resin emulsion is used for the purpose of a stabilizer, and the stabilizer using the emulsion exhibits a desired performance.

The cleaning agent of the present invention may be an acrylic resin emulsion alone or an acrylic resin emulsion in combination with various additives.

In the cleaning agent of the present invention, the acrylic resin emulsion for regular use of the present invention preferably contains at least 1% by weight (in terms of solid content) of the stabilizer, more preferably at least 3% by weight (in terms of solid content) Is not less than 5% by weight (in terms of solid content). The upper limit is usually 70% by weight (in terms of solid content), preferably 60% by weight (in solid content), more preferably 50% by weight (in terms of solid content). If the amount of the acrylic resin emulsion for regular use of the present invention is too small, the repulsive force tends to decrease, and if it is too much, the cleaning property tends to decrease.

In the cleaning agent of the present invention, it is preferable that the acrylic resin emulsion is blended with various kinds of blending components used as a commonly used cleaning agent such as an emulsion, a polyhydric alcohol, a lower alcohol, a surfactant, an ultraviolet absorber, a fragrance, , A refreshing agent, a vitamin, a plant extract, and the like, depending on the purpose.

Examples of the above-mentioned emulsifiable concentrates include oils such as sunflower oil, cottonseed oil, soybean oil, olive oil, palm oil, castor oil, jojoba oil, camellia oil and mink oil; beeswax, carnauba wax, candelilla wax, rice bran wax Such as ceresin, paraffin wax, liquid paraffin, liquid isoparaffin, microcrystalline wax, polyethylene powder, polyethylene wax, Fischer-Tropsch wax, petroleum jelly, squalene, etc., waxes such as cellulosic wax, spermaceti and lanolin There may be mentioned stearic acid, myristic acid, myristic acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, 2-ethylbutanoic acid, isopentanoic acid, 2-methylpentanoic acid, And higher fatty acids such as lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, lanolin alcohol, behenyl alcohol, and settered alcohols Stearyl palmitate, octyldodecyl myristate, octyldodecyl oleate, ethyl isostearate, isopropyl isostearate, isopropyl myristate, isopropyl myristate, isopropyl myristate, myristyl myristate, cetyl palmitate, oleyl oleate, octyldodecyl myristate, Ethylhexanoate, glyceryl tri-2-ethylhexanoate, glyceryl triisopalmitate, pentaerythritol tetra-2-ethylhexanoate, isocetyl octanoate, isocetane octanoate There may be mentioned fatty acid ester oils such as allyl, isocetyl isostearate, octyldodecyl isostearate, and octyldodecyl dimethyloctanoate, methylpolysiloxane, highly polymerized methylpolysiloxane, methylphenylpolysiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, octamethylcyclotetra Siloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, methylcyclopolysiloxane, alcohols There may be mentioned modified silicone, alkyl-modified silicone, amino-modified silicone, such as silicone oils such as epoxy-modified silicone. These may be used alone, or two or more of them may be used in combination.

The content of such an emulsion is usually 0.5 to 50% by weight, particularly preferably 1 to 40% by weight, in view of emulsification, in the amount of the regular antidumping agent. From the viewpoint of the high yield of the pure water and the sticky feeling, it is preferable that the content is as small as possible. However, by using the acrylic resin emulsion of the present invention, the amount of the emulsion to be used can be reduced or unused.

Examples of the polyhydric alcohols include ethylene glycol, dipropylene glycol, propylene glycol, isoprene glycol, glycerin, diglycerin, 1,3-butylene glycol, 1,2-pentanediol, 1,2-octanediol, 1,2-decanediol, and the like. These may be used alone, or two or more of them may be used in combination.

The content of such polyhydric alcohol is preferably from 0.1 to 20% by weight, particularly preferably from 0.5 to 15% by weight, in terms of the feeling of use feeling.

The acrylic resin emulsion for regular use of the present invention can be obtained by, for example, diluting an acrylic resin emulsion with water, a polyhydric alcohol, a lower alcohol or the like and using it as a liquid phase type of a precursor or by blending the oil into a acrylic resin emulsion with a surfactant and water Or may be used as a viscous liquid type or a cream type type correcting agent by blending an emulsified dispersion.

The stabilizing agent containing the acrylic resin emulsion for stabilizer of the present invention can be used for, for example, the following stabilization. The acrylic resin emulsion for regular use preparation of the present invention containing the acrylic resin (A) dispersed and stabilized by the polyvinyl alcohol-based resin [I] is applied to the hair of the effective amount of the repellent, and during or before the application of the acrylic resin emulsion for the regular- The hair is trimmed to a desired shape. By so doing, it is possible to easily form a desired hair shape.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded. In the examples, " part " and "% "

First, various acrylic resin emulsions were prepared as follows. The nonvolatile content and viscosity of the acrylic resin emulsion were measured by the following method, and the glass transition temperature was measured by the method described above.

<Non-volatile matter>

In a flat form prescribed in JIS R 3503 (1994), 1 g of a sample is spread over a dish of aluminum foil molded in a small area such as a weighing bottle 50 mm x 30 mm, and accurately weighed. Place the container in the center of the thermostat, dry it at 105 ° C ± 2 ° C for 60 ± 5 minutes, cool it in a desiccator, and weigh the weight. Then, it was calculated by the following equation.

N = (Wd / Ws) x 100

(Where N is the nonvolatile content (%), Wd is the weight (g) of the dried sample, and Ws is the weight (g) of the sample before drying.

<Viscosity>

(For example, a BL type viscometer manufactured by Tokyo Keiki Co., Ltd.). About 500 ml of the sample is put into the sample container so that the bubbles are not mixed, and the sample container is held so that the liquid level of the sample becomes lower than the liquid surface of the heat transfer medium of the constant temperature bath. If necessary, mix with glass rod and measure at sample temperature 23 ± 1 ℃. The viscosity was calculated by the following equation (two significant figures).

η = Kn × θ

(Where m is the viscosity (mPa · s), Kn is the conversion multiplier attached to the viscometer, and? Is the average of the viscometer indicating values of two measurements).

Example 1: Preparation of acrylic resin emulsion (1)

In a reaction container made of SUS having a cooling tube and a stirring blade, a PVA resin (average saponification degree: 99 mol%, average degree of polymerization: 300, average molecular weight: 300, 10 parts of the 1,2-diol structural unit content 8 mol% / manufactured by Nippon Gosei Kogyo Co., Ltd.), 0.2 part of sodium hydrogen sulfite and 0.4 part of sodium carbonate and triethanol were completely dissolved and the temperature was raised to 75 캜. (I) emulsified with 77 parts of deionized water, 5 parts of unmodified PVA resin (manufactured by Nippon Gosei Kogyo K.K., trade name: Goseonol GL05) and 100 parts of 2-ethylhexyl acrylate, and 10% APS (Ii) was prepared. To the reaction vessel, 10% of (i) and 30% of (ii) were added and reacted for 45 minutes. Subsequently, 90% of the remainder of (i) and 60% of (ii) were added dropwise over 3.5 hours and polymerized at 75-78 캜. After completion of the dropwise addition, 5% of (ii) was added, and the temperature was maintained for 1.5 hours. Then, 5% of (ii) was added again and the temperature was maintained for 1.5 hours. Thereafter, the resultant was cooled to obtain acrylic resin emulsion 1 (nonvolatile matter 46%; viscosity 125 mPa.s (B rheometer 12 rpm, 23.degree. C.); acrylic resin-glass transition temperature (Tg) = -70.degree. The acrylic resin emulsion (1) was dispersed and stabilized.

Example 2: Preparation of acrylic resin emulsion (2)

In Example 1, 100 parts of 2-ethylhexyl acrylate was changed to 90 parts of 2-ethylhexyl acrylate and 10 parts of methyl methacrylate, and as the unmodified PVA resin, "Gosenol GL05" (trade name, manufactured by Nippon Gosei Kogyo Co., Acrylic resin emulsion (2) (nonvolatile matter content: 43%, viscosity: 160 mPa.s (s)) was obtained in the same manner as in Example 1 except that the trade name "Goseonol EG05" was changed to "Goseonol EG05" (trade name) manufactured by Nippon Gosei Co., (B type viscometer 12 rpm, 23 deg. C); acrylic resin-glass transition temperature (Tg) = -60 deg. The acrylic resin emulsion (2) was dispersed and stabilized.

Example 3: Preparation of acrylic resin emulsion (3)

In the same manner as in Example 2 except that 0.3 part of ethylene glycol dimethacrylate (trade name: Acryester ED, manufactured by Mitsubishi Rayon Co., Ltd.) was further added as an acrylic monomer in Example 2, an acrylic resin emulsion 3 (Glass transition temperature (Tg) of acrylic resin = -60 占 폚) was obtained in the same manner as in Example 1 (nonvolatile matter 44%; viscosity 210 mPa.s (B rheometer 12 rpm, 23 deg. The acrylic resin emulsion (3) was dispersion-stabilized.

Example 4: Preparation of acrylic resin emulsion (4)

In Example 1, 100 parts of 2-ethylhexyl acrylate was changed to 75 parts of 2-ethylhexyl acrylate and 25 parts of methyl methacrylate, and then "Gosenol GL05" (trade name, manufactured by Nippon Gosei Kogyo Co., Acrylic resin emulsion 4 (nonvolatile matter content: 46%; viscosity: 540 mPa.s (g)) was obtained in the same manner as in Example 1, except that the trade name "GOSENOL EG05" was changed to "GOSEENOL EG05" (trade name, manufactured by Nippon Gosei Co., (B type viscometer 12 rpm, 23 deg. C); acrylic resin-glass transition temperature (Tg) = -43 deg. The acrylic resin emulsion (4) was stabilized in dispersion.

Example 5: Preparation of acrylic resin emulsion (5)

In the same manner as in Example 4 except that 0.2 part of acryester ED (ethylene glycol dimethacrylate) was added as an acrylic monomer in Example 4, an acrylic resin emulsion 5 (nonvolatile matter 43%, viscosity 420 mPa 占 퐏 (B type viscometer 12 rpm, 23 占 폚); glass transition temperature (Tg) of acrylic resin = -43 占 폚). The acrylic resin emulsion (5) was dispersed and stabilized.

Example 6: Preparation of acrylic resin emulsion (6)

In Example 1, 100 parts of 2-ethylhexyl acrylate was changed to 60 parts of 2-ethylhexyl acrylate and 40 parts of methyl methacrylate, and then "Gosenol GL05" (trade name, manufactured by Nippon Gosei Kogyo Co., Acrylic resin emulsion 6 (nonvolatile matter content: 44%; viscosity: 470 mPa.s (1) (trade name, manufactured by Nippon Gosei Kogyo K.K.) was used in place of the acrylic resin emulsion B-type viscometer 12 rpm, 23 deg. C); glass transition temperature (Tg) of acrylic resin = -24 deg. The acrylic resin emulsion 6 was stabilized in dispersion.

Example 7: Preparation of acrylic resin emulsion (7)

92 parts of deionized water, 0.2 part of sodium hydrogen sulfite and 0.4 part of sodium carbonate and triethanol were completely dissolved in a reaction container made of SUS having a cooling tube and a stirring blade, and the temperature was raised to 75 캜. A mixture of 77 parts of deionized water and a PVA-based resin (average saponification degree: 89 mol%, average degree of polymerization: 340, content of 1,2-diol bond in side chain: 3 mol% / Nippon Gosei Kogyo Co., (I) was prepared by emulsifying 45 parts of n-butylacrylate and 45 parts of methyl methacrylate, and 2.7 parts (ii) of a 10% aqueous APS solution. And 30% of (ii) were added and reacted for 45 minutes. Then 90% of the remainder of (i) and 60% of (ii) were added dropwise over 3.5 hours and polymerized at 75-78 ° C. After completion of the dropwise addition, 5% of (ii) was added, and the temperature was maintained for 1.5 hours. Then, 5% of (ii) was added again and the temperature was maintained for 1.5 hours. Thereafter, the solution was cooled to obtain an acrylic resin emulsion 7 (nonvolatile matter content 45%; viscosity 600 mPa.s (B type viscometer 12 rpm, 23 deg. C); acrylic resin temperature Tg = 3 deg. The acrylic resin emulsion (7) was dispersed and stabilized.

Example 8: Preparation of acrylic resin emulsion (8)

In a reaction container made of SUS having a cooling tube and a stirring blade, 169 parts of deionized water and a PVA resin (average saponification degree: 99 mol%, average degree of polymerization: 300, side chains of 1, 7 parts of 2-diol bond content 8 mol% / Nippon Kosei Kogyo K.K.), 0.2 part of sodium hydrogen sulfite and 0.4 part of sodium carbonate and triethanol were completely dissolved and the temperature was raised to 75 캜. 54.7 parts of n-butyl acrylate, 44.8 parts of methyl methacrylate and 0.5 part of 2-acetoacetoxyethyl methacrylate (i) and 2.7 parts (ii) of a 10% aqueous APS solution were prepared, 100% of (i) and 90% of (ii) were added dropwise over 4.5 hours and polymerized at 75-78 캜. After completion of the dropwise addition, 5% of (ii) was added, and the temperature was maintained for 1.5 hours. Then, 5% of (ii) was added again and the temperature was maintained for 1.5 hours. Thereafter, the resultant was cooled to obtain an acrylic resin emulsion 8 (nonvolatile matter content 45%; viscosity 500 mPa.s (B-type viscometer 12 rpm, 23 ° C); acrylic resin-glass transition temperature (Tg) = 9 ° C). The acrylic resin emulsion 8 had dispersion stabilized.

Example 9: Preparation of acrylic resin emulsion (9)

In the same manner as in Example 4 except that 0.05 parts of KBM 503 (? -Methacryloxypropyltrimethoxysilane) was added as a monomer component in Example 4, an acrylic resin emulsion 9 (nonvolatile matter content: 44%; The glass transition temperature (Tg) of the acrylic resin = -43 占 폚) was obtained at a viscosity of 550 mPa 占 퐏 (B-type viscometer 12 rpm at 23 占 폚). The acrylic resin emulsion (9) was stabilized in dispersion.

Example 10: Preparation of acrylic resin emulsion (10)

10 parts of a 20% aqueous solution of unmodified PVA resin (trade name: Goseonol GL05, manufactured by Nippon Gosei Kogyo K.K.) was added to 100 parts of the acrylic resin emulsion (1) obtained in Example 1 to obtain an acrylic resin emulsion 10) (nonvolatile matter 44%; viscosity 140 mPa.s (B-type viscometer 12 rpm, 23.degree. C.); acrylic resin-glass transition temperature (Tg) = -70.degree. The acrylic resin emulsion 10 was stabilized in dispersion.

&Lt; Comparative Example 1 &

(Average saponification degree: 99 mol%, average degree of polymerization: 300, content of 1,2-diol bond in the side chain: 8 mol% / Nippon Gosei Kogyo K.K.) containing 1,2-diol structural units in the side chain And diluted with deionized water to prepare a 45% and 3% PVA resin solution of non-volatile components. The dispersion state of the PVA resin solution of Comparative Example 1 was stabilized.

&Lt; Comparative Example 2 &

(Trade name: &quot; Coponyl WU-6406 &quot;, manufactured by Nippon Gosei Co., Ltd., nonvolatile content: 56%, viscosity: 1200 mPa 쨌 s; glass transition temperature of acrylic resin: 68 ° C) was diluted with deionized water to prepare an acrylic resin emulsion having 45% and 3% nonvolatile contents. The state of the acrylic resin emulsion of Comparative Example 2 was stabilized in dispersion.

&Lt; Preparation of corrective agent test solution (A) &gt;

In Examples 1 to 10, the acrylic resin emulsions (1) to (10) were diluted with deionized water so that the nonvolatile content became 3%, respectively, and used as a regular developer test solution (A). For the above Comparative Examples 1 and 2, those having a nonvolatile content of 3% were used to prepare a cleaning agent test solution (A).

The settling performance (set force), the re-settling performance (re-set force), and the tactile property were evaluated using the above-described correcting agent test solution (A) as follows.

<Progressive performance (set force)>

0.5 g of the above-described regular-test solution (A) was uniformly coated with a dropper and uniformly spread with vinyl gloves with a fingertip to the parent hair (length 20 cm x weight 1.2 g; The fingers were trimmed with fingers to a width of about 1 cm, dried at 100 ° C for 1 minute in a ventilation drier, and held by hand at an angle of about 45 ° from the top of the staple with the binding side facing downward, The sensory evaluation was carried out. The evaluation method is as follows.

(Evaluation standard)

○ ... It is still being shaken even if it shakes a little.

△ ... When shaking a little, the ends of the hair spread a little.

× ... Unordered, or slightly shaken, the tip ends are scattered.

In the above evaluation, &quot;? &Quot; is excellent in performance and &quot; DELTA &quot; is practically acceptable. Also, &quot; x &quot;

<Financial performance (reset)>

The hatching speed after the evaluation of the repulsive force was released with fingers and disturbed again with a comb, and then the hatching speed was again made with a finger. The evaluation method is as follows.

(Evaluation standard)

○ ... (Again)

△ ... It gets tidy, but the hair spreads a bit.

× ... It does not become a dominant mode and does not stop.

In the above evaluation, &quot;? &Quot; is excellent in performance and &quot; DELTA &quot; is practically acceptable. Also, &quot; x &quot;

<Tactile property>

The sensation of touch with the fingers was evaluated with respect to the sense of tidiness of the hair at the time of evaluating the fiscal performance. The evaluation method is as follows.

(Evaluation standard)

○ ... Moist and smooth.

△ ... I'm a little crazy.

× ... It is pretty stupid.

In the above evaluation, &quot;? &Quot; is excellent in performance and &quot; DELTA &quot; is practically acceptable. Also, &quot; x &quot;

&Lt; Preparation of corrective agent test solution (B) &gt;

The acrylic resin emulsions (1) to (10) were used as they were in Examples 1 to 10, and in Comparative Test Examples 1 and 2, Respectively.

<Cleaning performance>

The correcting agent test solution (B) was applied to a PET (polyethylene terephthalate) film having a thickness of 50 占 퐉 with a 40 占 퐉 applicator and dried at 100 占 폚 for 5 minutes to obtain a coating film having a thickness of about 15 占 퐉 (at the time of drying). Deionized water was dropped one drop by a syringe on the coating film, and lightly pulsed for 10 times (10 weeks) so as to draw a circle with a diameter of about 1 cm with a finger, pulp weses (manufactured by Nippon Sage Kureci Co., Ltd., Wipe &quot; (registered trademark)), and the degree of cleaning of the solution of the stabilizing agent on the coating film was visually evaluated. The evaluation method is as follows.

(Evaluation standard)

○ ... More than 70% could be wiped 100%.

△ ... More than 20% and less than 70%.

× ... It was able to wipe less than 0 and less than 20%.

In the above evaluation, &quot;? &Quot; is excellent in performance and &quot; DELTA &quot; is practically acceptable. Also, &quot; x &quot;

It can be seen from Examples 1 to 10 that the stabilizer using the acrylic resin emulsion in which the dispersion stabilized with the PVA resin of the present invention is used has excellent balance between the styling performance (performance of repetition, reworking performance, and tactility) Able to know.

On the other hand, in Comparative Example 1 in which the PVA resin was used as an aqueous solution, the cleaning performance and the cleaning performance were good, but the reverberation and the tactility were poor. In Comparative Example 2 using an acrylic resin emulsion obtained by using a non-PVA surfactant, the cleaning performance was good and the retroreflective performance and the tactile property were good. However, the cleaning performance was poor, and as a corrective agent, Level.

Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. The present application is based on Japanese Patent Application (Special Application No. 2012-275244) filed on December 18, 2012 and Japanese Patent Application (Application No. 2013-173245) filed on August 23, 2013, the content of which is incorporated herein by reference &Lt; / RTI &gt;

(Industrial applicability)

INDUSTRIAL APPLICABILITY The acrylic resin emulsion for regularizers of the present invention has a good balance of styling performance (regular performance, re-tailoring performance, tactile property) and cleaning performance, so that various compounding agents can be used in combination, Is applicable.

Claims (7)

An acrylic resin emulsion for regularizers containing an acrylic resin (A) dispersed and stabilized by a polyvinyl alcohol-based resin [I]. The method according to claim 1,
The polyvinyl alcohol-based resin [I] is an acrylic resin emulsion for regularizing agent containing a side chain 1,2-diol structural unit represented by the following general formula (1).
(General formula (1))

(In the formula (1), R ¹ to R ⁶ each independently represent a hydrogen atom or an organic group, and X represents a single bond or a bonding chain.) The method of claim 2,
The content of the side chain 1,2-diol structural unit in the polyvinyl alcohol-based resin [I] containing the side chain 1,2-diol structural unit represented by the above formula (1) is 1 to 15 mol% . 4. The method according to any one of claims 1 to 3,
Wherein the acrylic resin (A) is obtained by polymerizing a monomer component containing 40 wt% or more of an aliphatic (meth) acrylate monomer having 4 to 12 carbon atoms in the alkyl group. 5. The method according to any one of claims 1 to 4,
Wherein the acrylic resin (A) has a glass transition temperature of 70 DEG C or lower. A regularizing agent containing the acrylic resin emulsion for regularizers according to any one of claims 1 to 5.  (A) dispersed and stabilized by a polyvinyl alcohol-based resin (I), and a step of applying an effective amount of an acrylic resin emulsion for a regularizing agent to the hair, And a step of arranging the hair to a desired shape before and after the step.