JP6723771B2 - Acrylic resin emulsion for hairdressing agent and method for producing the same, and hairdressing agent and method for producing the same - Google Patents

Description

The present invention relates to an acrylic resin emulsion for a hair styling agent, a method for producing the same, and a hair styling agent, particularly an acrylic resin emulsion for a hair styling agent, which is suitable for an aqueous hair styling agent such as a hair spray, a hair mist, a hair setting lotion and a hair gel. The present invention relates to a hair styling agent using this.

There are various hair styling agents such as liquid, gel, foam, mist, cream and wax.
Usually, a hair styling agent contains a polymer (setting polymer) as a main component for maintaining a desired shape by forming a film on the hair surface, and further, depending on additives and dosage forms given for various purposes. It is a polymer composition containing a solvent, a base and the like. In recent years, hair creams and hair waxes, which are emulsifiers that use an oil and water, have become the mainstream hair styling agents that can be freely arranged during hair styling and are easy to repair after styling. There is.

And a hair styling agent is required to have a performance of imparting a desired shape to hair and holding it for a long time, and a performance of styling (conditioning hair) such as excellent appearance performance and excellent tactile performance, and various hair styling products are required. Agents are being developed.

For example, in Patent Document 1, hair containing (A) polymer fine particles insoluble in water and ethanol and having tackiness at room temperature, and (B) fine powder insoluble in water and ethanol and not having tackiness at room temperature Cosmetics are disclosed.
Further, in Patent Document 2, (A) a polymer compound having a film-forming ability of 0.05 to 10.0% by mass, and (B) a nonionic surfactant of 0.05 to 5.0% by mass, (C) 0.05 to 10.0% by mass of powder having a particle size of 0.5 to 50 μm, and (D) 25.0 to 80.0% by mass of a propellant. Fees are disclosed.

JP-A-2000-26246 JP, 2002-338441, A

However, in the technique described in Patent Document 1, when the content of the polymer fine particles (A) or the fine powder (B) is increased, the hair cosmetic film becomes a film, and the film is cracked, and flaking or white flaky powder is generated. However, since the whitening occurs due to the aggregation of the fine powder, the content in these cosmetics is very small, and it is not sufficiently satisfactory in terms of hair styling performance.
Further, in the technique described in Patent Document 2, since it is a fog-shaped hair styling agent, an ethanol-soluble polymer is used as a polymer compound having a film-forming ability, and a large amount of a nonionic surfactant is added. Therefore, there is a problem that the water resistance is poor and the set holding power under high humidity is poor.

Therefore, the present invention provides a resin composition which, when used as a hair styling agent, provides a hair styling agent which is excellent in hair styling performance (launching power, feeling of hair bundles), has little stickiness, and has very little flaking. It is an object to provide a hair styling agent using

As a result of repeated studies by the present inventors, in an acrylic resin emulsion used as a base resin for hair styling, (1) suppression of flaking is effective in preventing film formation of the base resin contained in the emulsion. (2) In order to prevent the film formation, it is effective to use two different types of acrylic resin particles, that is, acrylic resin particles having a relatively high glass transition temperature and acrylic resin particles having a relatively low glass transition temperature. That is, (3) the prevention of the film formation is particularly effective for flaking, (4) the inclusion of inorganic particles further enhances the effect of (1), and improves hair styling performance, We have found that prevention of stickiness is effective.

Then, the inventors of the present invention have conducted extensive studies based on the above findings, and as a base resin for hair styling agents, acrylic resin particles having a relatively high glass transition temperature and acrylic resin particles having a relatively low glass transition temperature, The inventors have found that the above problems can be solved by using two different types of acrylic resin particles and further using an acrylic resin emulsion containing inorganic particles, and have completed the present invention.

That is, the present invention includes the following aspects (1) to (9).
(1) Acrylic resin emulsion [I] having a glass transition temperature of -15°C or higher and lower than 0°C, acrylic resin emulsion [II] having a glass transition temperature of 0°C or higher and 60°C or lower, and inorganic particles An acrylic resin emulsion for hair styling, which comprises:
(2) The acrylic resin emulsion for a hair styling agent according to (1) above, wherein the acrylic resin emulsion [I] and the acrylic resin emulsion [II] have an average glass transition temperature of 20° C. or lower. ..
(3) In the above (1) or (2), the difference between the glass transition temperature of the acrylic resin emulsion [I] and the glass transition temperature of the acrylic resin emulsion [II] is 5° C. or more. The acrylic resin emulsion for hairdressing preparations described.
(4) The content ratio (nonvolatile content mass ratio) of the acrylic resin emulsion [I] and the acrylic resin emulsion [II] is [I]/[II]=10/90 to 90/10. The acrylic resin emulsion for hair styling according to any one of (1) to (3) above.
(5) The content of the inorganic particles is 10 to 150 parts by mass with respect to a total of 100 parts by mass of the nonvolatile content of the acrylic resin emulsion [I] and the nonvolatile content of the acrylic resin emulsion [II]. The acrylic resin emulsion for hairdressing preparation according to any one of (1) to (4) above, wherein
(6) The acrylic resin emulsion for a hair styling agent according to any one of (1) to (5), wherein the inorganic particles are silica.
(7) An acrylic resin emulsion [I] having a glass transition temperature of −15° C. or higher and lower than 0° C., an acrylic resin emulsion [II] having a glass transition temperature of 0° C. or higher and 60° C. or lower, and inorganic particles. A hair styling agent characterized by containing.
(8) An acrylic resin emulsion [I] having a glass transition temperature of -15°C or higher and lower than 0°C, an acrylic resin emulsion [II] having a glass transition temperature of 0°C or higher and 60°C or lower, and inorganic particles. A method for producing an acrylic resin emulsion for hair styling, which comprises mixing.
(9) An acrylic resin emulsion [I] having a glass transition temperature of -15°C or higher and lower than 0°C, an acrylic resin emulsion [II] having a glass transition temperature of 0°C or higher and 60°C or lower, and inorganic particles. A method for producing a hair styling agent, which comprises mixing.

According to the present invention, an acrylic resin emulsion [I] having a glass transition temperature of -15°C or higher and lower than 0°C and an acrylic resin emulsion [II] having a glass transition temperature of 0°C or higher and 60°C or lower. When used as a hair styling agent, the hair styling agent has excellent hair styling performance (launching power, feeling of hair bundles), little stickiness, and very little flaking when used as a hair styling agent. Acrylic resin emulsion and hair styling agent for use can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
In the present specification, an acrylic resin is a resin obtained by polymerizing a monomer component containing at least one (meth)acrylic monomer, and (meth)acrylic means acrylic or methacrylic (meth). Acrylate means acrylate or methacrylate, and (meth)acrylic acid means acrylic acid or methacrylic acid.

The acrylic resin emulsion for hair styling agents of the present invention is an acrylic resin emulsion [I] having a glass transition temperature of -15°C or higher and lower than 0°C, and an acrylic resin emulsion having a glass transition temperature of 0°C or higher and 60°C or lower. It contains an emulsion [II] and inorganic particles.
By using two different acrylic resin emulsions [I] and [II] as the base resin, the dispersibility of the inorganic particles is improved, so that the hair styling performance can be improved and stickiness can be suppressed, and the inorganic particles can be suppressed. When the acrylic resin emulsion [I] and the acrylic resin emulsion [II] as the base resin are contained, the resin particles in the acrylic resin emulsion [I] and the acrylic resin emulsion [II] are covered with inorganic particles. ] And the resin particles in the acrylic resin emulsion [II] are suppressed from forming a film on the hair, it is presumed that flaking can be effectively reduced.

Hereinafter, each component will be specifically described.

<Acrylic resin emulsion [I]>
The acrylic resin emulsion [I] used in the present invention comprises acrylic resin particles (a) dispersed in an aqueous medium, and has a glass transition temperature (Tg) of the acrylic resin particles (a). Is an acrylic resin emulsion having a temperature of -15°C or higher and lower than 0°C.

Examples of the monomer component constituting the acrylic resin particles (a) in the acrylic resin emulsion [I] include (meth)acrylic monomer (a-1) and functional group-containing monomer (a-2). be able to.

Examples of the (meth)acrylic monomer (a-1) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth). ) Aliphatic (meth)acrylate monomers such as acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, lauryl (meth)acrylate, octyl (meth)acrylate and stearyl (meth)acrylate, and phenoxy (meth). ) Aromatic (meth)acrylate monomers such as acrylate, trifluoroethyl (meth)acrylate, and the like.
Of these, an aliphatic (meth)acrylate-based monomer having an alkyl group with 1 to 18 carbon atoms is preferable, and an alkyl group with 1 carbon atom is more preferable, because emulsion polymerization is easy and copolymerization is easy. To 12 aliphatic (meth)acrylate monomers, more preferably alkyl group having 4 to 12 carbon atoms (meth)acrylate monomers, particularly preferably n-butyl acrylate and 2-ethylhexyl. It is an acrylate. In addition, a combination of 2-ethylhexyl acrylate and methyl methacrylate and a combination of n-butyl acrylate and methyl methacrylate can be preferably used.

Examples of the functional group-containing monomer (a-2) include a monomer having two or more vinyl groups in the molecular structure, a glycidyl group-containing monomer, an allyl group-containing monomer, a hydrolyzable silyl group-containing monomer, and an acetoacetyl group-containing monomer. , Hydroxyl group-containing monomers, carboxyl group-containing monomers and the like.

Examples of the monomer having two or more vinyl groups in the molecular structure include divinylbenzene, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, ethylene glycol di(meth)acrylate, 1,2-propylene glycol di( (Meth)acrylate, 1,3-propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tri Methylolpropane tri(meth)acrylate, allyl(meth)acrylate and the like can be mentioned.
Among these, ethylene is preferable because the fusion strength between the acrylic resin particles in the acrylic resin emulsion [I] can be reduced and the hardness (feeling) of the film on the hair can be easily adjusted. Glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di (Meth)acrylate, neopentyl glycol di(meth)acrylate and trimethylolpropane tri(meth)acrylate are preferable.

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

Examples of the allyl group-containing monomer include triallyloxyethylene, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, tetraallyloxyethane, and other monomers having two or more allyl groups, allyl glycidyl ether, and allyl acetate. Etc.

Examples of the hydrolyzable silyl group-containing monomer include vinyl-based silyl group-containing monomers such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, and vinylmethyldimethoxysilane; γ-(meth) (Meth)acryloxy system such as acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropylmethyldiethoxysilane Examples include silyl group-containing monomers.
Among the hydrolyzable silyl group-containing monomers, the adhesive strength between the acrylic resin particles in the acrylic resin emulsion [I] is reduced, and the hardness (touch) of the film on the hair is easily adjusted. It is preferable to use vinyltrimethoxysilane, vinyltriethoxysilane, and γ-(meth)acryloxypropyltrimethoxysilane from the viewpoint that the above can be achieved.
Further, in terms of excellent copolymerizability with the (meth)acrylate-based monomer, it is preferable to use the (meth)acryloxy-based silyl group-containing monomer.

Examples of the acetoacetyl group-containing monomer include acetoacetic acid vinyl ester, acetoacetic acid allyl ester, diacetoacetic acid allyl ester, acetoacetoxyethyl (meth)acrylate, acetoacetoxyethyl crotonate, acetoacetoxypropyl (meth)acrylate, acetoacetoxy. Examples include propyl crotonate and 2-cyanoacetoacetoxyethyl (meth)acrylate.

Examples of the hydroxyl group-containing monomer include (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

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-glycolic acid, and silicic acid. Examples include cinnamic acid.
Among these, (meth)acrylic acid is preferably used from the viewpoint that emulsion stability during emulsion polymerization is imparted and high dispersibility of the inorganic particles can be obtained.

These monomers may be used alone or in combination of two or more.

The content of the (meth)acrylic monomer (a-1) and/or the functional group-containing monomer (a-2) is 70 to 100% by mass with respect to the total amount of monomers constituting the acrylic resin particles (a). Is more preferable, 80 to 100% by mass is more preferable, and 90 to 100% by mass is still more preferable. If the content is too low, the production stability of the acrylic resin emulsion for hair styling tends to decrease.

In the monomer component constituting the acrylic resin particles (a) in the acrylic resin emulsion [I], the content ratio of the (meth)acrylic monomer (a-1) constitutes the acrylic resin particles (a). It is preferably 80 to 100% by mass, more preferably 85 to 99.99% by mass, and still more preferably 90 to 99.9% by mass, based on the total amount of the monomer components.
If the content ratio of the (meth)acrylic monomer (a-1) is too low, the production stability of the acrylic resin emulsion for hair styling tends to decrease.

In the monomer component constituting the acrylic resin particles (a) in the acrylic resin emulsion [I], the content ratio of the functional group-containing monomer (a-2) is the monomer constituting the acrylic resin particles (a). The content is preferably 0 to 20% by mass, more preferably 0.01 to 15% by mass, and still more preferably 0.1 to 10% by mass, based on the entire components.
If the content ratio is too high, the production stability of the acrylic resin emulsion for hair styling tends to decrease, and if it is too low, flaking tends to occur.

Moreover, when the functional group-containing monomer (a-2) is a monomer having two or more vinyl groups in the molecular structure, the content of the monomer having two or more vinyl groups in the molecular structure is an acrylic resin. It is preferably 0.01 to 20% by mass, more preferably 0.05 to 15% by mass, and still more preferably 0.1 to 10% by mass, based on the entire monomer components constituting the particles (a). ..

When the functional group-containing monomer (a-2) is a hydrolyzed silyl group-containing monomer, the content of the hydrolyzed silyl group-containing monomer is such that the total amount of the monomer components constituting the acrylic resin particles (a) is It is preferably 0.01 to 15% by mass, more preferably 0.02 to 12% by mass, and further preferably 0.05 to 10% by mass.

In addition, as long as the effects of the present invention are not impaired, a small amount of styrene-based monomers such as styrene and α-methylstyrene; and vinyl formate, vinyl acetate, vinyl propionate, and valerin are included as constituent components of the acrylic resin particles (a). Vinyl ester monomers such as vinyl acetate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl versaticate and vinyl 2-ethylhexanoate are used. May be.

The acrylic resin emulsion [I] can be obtained, for example, by emulsion polymerization. In the emulsion polymerization, in addition to the emulsifier and the polymerization component, known components, for example, other components other than monomers such as a polymerization initiator, a polymerization modifier and a plasticizer can be used.
The amounts of other components other than these monomers used can be appropriately selected according to the purpose within a range that does not impair the effects of the present invention.

Examples of the emulsifier include a surfactant, a water-soluble polymer having a protective colloid ability, a water-soluble oligomer and the like.

Preferred examples of the above-mentioned surfactant include anionic surfactants such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate, nonionic surfactants such as those having a pluronic type structure and those having a polyoxyethylene type structure. Examples include activators and cationic surfactants such as amine salt type and quaternary ammonium salt type. Further, as the surfactant, a reactive surfactant having a radical-polymerizable unsaturated bond in the structure can also be used. These can be used alone or in combination of two or more.

Examples of the water-soluble polymer having the protective colloid ability include polyvinyl alcohol, 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 increasing the viscosity of the emulsion and changing the particle size of the emulsion to change the viscosity.

As the water-soluble oligomer, for example, a polymer or a copolymer having a hydrophilic group such as a sulfonic acid group, a carboxyl group, a hydroxyl group, and an alkylene glycol group is preferable, and a polymer having an average degree of polymerization of about 10 to 500 or Copolymers are preferred. Specific examples of the water-soluble oligomer include, for example, amide-based copolymers such as 2-methacrylamido-2-methylpropanesulfonic acid copolymer, sodium methacrylate-4-styrenesulfonate copolymer, and styrene/maleic acid copolymer. Examples thereof include polymers, melamine sulfonic acid formaldehyde condensates, poly(meth)acrylic acid salts and the like. Further, specific examples include water-soluble oligomers obtained by previously polymerizing a monomer having a sulfonic acid group, a carboxyl group, a hydroxyl group, an alkylene glycol group or the like, or a radically polymerizable reactive emulsifier alone or with another monomer. To be These may be used alone or in combination of two or more.

In the present invention, among the above emulsifiers, sodium lauryl sulfate and sodium dodecylbenzenesulfonate are preferably used from the viewpoint of good polymerization stability.

The amount of the emulsifier used is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 100 parts by mass of the monomer that constitutes the acrylic resin particles (a). Is 0.5 to 8 parts by mass.
If the amount of the emulsifier used is too small, the dispersion stability of the monomer component is lowered, and the polymerization stability tends to be lowered.If the amount used is too large, the viscosity of the acrylic resin emulsion becomes high and the production stability is high. Tends to decline.

As the above-mentioned 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 initiators, and peroxides. Hydrogen, peroxides such as butyl peroxide; and redox polymerization initiators in which these are combined 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, a combination of an inorganic peroxide such as a persulfate, an organic peroxide, an azo-based initiator and a reducing agent is preferable, and it is preferable to use a persulfate in terms of easy redox polymerization.

The amount of the polymerization initiator used varies depending on the type of the monomer component used and the polymerization conditions, but is usually 0.01 to 0.5 parts by mass, particularly 0.05 to 1 part by mass, relative to 100 parts by mass of the monomer component. Is preferred.

The polymerization regulator can be appropriately selected from known ones. Examples of such a polymerization regulator include a chain transfer agent and a buffer.

Examples of the chain transfer agent 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 and thiol. Examples thereof include 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 can be carried out stably, and it is desirable to use it for adjusting the degree of polymerization of the acrylic resin particles (a).

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

As the plasticizer, an ethylene glycol plasticizer, an ethylene glycol alkyl ether plasticizer, a benzoate plasticizer, an adipate plasticizer, a phthalic acid plasticizer, a phosphoric acid plasticizer, or the like can be used.

Emulsion polymerization is carried out in an aqueous medium in the presence of an emulsifying agent, if necessary, by using other components other than the above-mentioned monomers for the monomers constituting the acrylic resin particles (a). Is
(1) A method of charging a reaction vessel with the total amount of a monomer, an emulsifier, a polymerization initiator, and other components as necessary, and heating the mixture to perform polymerization
(2) First, a reaction vessel is charged with an aqueous medium, a part of a monomer and an emulsifier, the temperature is raised, and then a part of a polymerization initiator is added and polymerized, and then the remaining monomer, emulsifier and polymerization start. Method of polymerizing by adding dropwise or divided addition of the agent,
(3) A method in which an aqueous medium, an emulsifier, a polymerization initiator, etc. are charged in a reaction vessel and the temperature is raised, and then all of the monomers and the polymerization initiator are added dropwise or dividedly and polymerized.
Etc. Among them, the methods (2) and (3) are preferable because the polymerization temperature can be easily controlled.

Here, the aqueous medium refers to water or an alcoholic solvent mainly containing water, and preferably water.

The polymerization conditions in the above-mentioned polymerization method are not particularly limited, but examples thereof include the following polymerization conditions.
In the above method (1), a temperature range of about 40 to 100° C. is usually suitable, and it is preferable to carry out the polymerization reaction for about 1 to 8 hours after the start of temperature increase.
In the above method (2), first, 1 to 50 mass% of the monomer and 1 to 50 mass% of the polymerization initiator are polymerized at 40 to 90° C. for 0.1 to 4 hours, and then the remaining monomer is continuously polymerized. , And the rest of the polymerization initiator are added dropwise or in portions over a period of about 1 to 5 hours to carry out the polymerization reaction, followed by aging at the same temperature for about 1 to 3 hours.
In the method (3), water and 0 to 100% by mass of the polymerization initiator are charged into the polymerization vessel, the temperature is raised to 40 to 90° C., and the monomer and the remaining polymerization initiator (when the total amount is initially charged). It is preferable to add (except for) except for 2 to 5 hours or to add them in portions, and then age at 1 to 3 hours at the same temperature.

In the above-mentioned polymerization method, from the viewpoint of polymerization stability, an emulsifier (or a part of the emulsifier) is dissolved in a monomer constituting the acrylic resin particles (a), or emulsified and dispersed with an emulsifier and an aqueous medium in advance. It is preferable to keep the O/W type emulsion liquid.
The method for preparing the emulsion is not particularly limited, but after the emulsifier is dissolved in water, the monomer that constitutes the acrylic resin particles (a) is charged and the mixture is stirred and emulsified, or the emulsifier is dissolved in water. After that, a method of charging the monomer with stirring and the like can be mentioned.

Stirring at the time of emulsification of the emulsified liquid can be performed using a homodisper or a stirrer equipped with stirrer blades such as turbine blades and propeller blades.
The temperature at the time of emulsification is not a problem as long as the mixture does not react during the emulsification, and usually about 5 to 60°C is suitable.

The nonvolatile content concentration of the acrylic resin emulsion [I] is preferably 1 to 65% by mass from the viewpoint of reducing the production cost of the acrylic resin emulsion [I] and the production stability of the acrylic resin emulsion [I]. %, more preferably 20 to 60% by mass, and particularly preferably 30 to 50% by mass.
In addition, the non-volatile content means a residue remaining after heating and drying the emulsion, and the weight before and after heating and drying can be usually determined according to the calculation method described in JIS K 6828-1.

The average particle diameter of the acrylic resin particles (a) in the acrylic resin emulsion [I] produced as described above is preferably 50 to 1000 nm, more preferably 60 to 800 nm, and particularly preferably 70. ~ 600 nm. When the average particle diameter is less than 50 nm, the nonvolatile content concentration of the acrylic resin emulsion [I] tends to be too low. If the average particle size is larger than 1000 nm, the particle size distribution tends to be broad, the particle size ratio balance with the inorganic particles is lost, the effect of suppressing flaking is reduced, and the acrylic resin emulsion for hairdressing is stored. Stability tends to decrease.

The average particle size of the acrylic resin particles (a) is, when the particle size is less than 500 nm, a dynamic light scattering particle size distribution measuring device, for example, "NICOMP 380" manufactured by Particle Sizing Systems (product). If the particle size is 500 nm or more, use a laser analysis/scattering type particle size distribution measuring device, for example, "LA-950" (trade name) manufactured by Horiba Ltd. You can The measurement of the particle size is a known and commonly used technique.

In the present invention, the glass transition temperature (Tg) of the acrylic resin emulsion [I] needs to be -15°C or higher and lower than 0°C. If the glass transition temperature of the acrylic resin emulsion [I] is too high, the film formed on the hair tends to be fragile and the texture tends to be poor, and flaking tends to increase. If the glass transition temperature is too low, the acrylic resin emulsion The fusion strength between [I] is increased, and flaking due to film peeling during combing tends to deteriorate.
The glass transition temperature of the acrylic resin emulsion [I] is preferably −14° C. or higher and −2° C. or lower, and more preferably −13° C. or higher and −3° C. or lower.

In the present invention, the glass transition temperature (Tg) of the acrylic resin emulsion [I] is the glass transition temperature of the acrylic resin particles (a) in the acrylic resin emulsion [I], and It is calculated by a formula.

(In the formula, Tg: the glass transition temperature (K) of the polymer formed from the monomer A, the monomer B,..., And the monomer N,
Tga: glass transition temperature (K) of homopolymer of monomer A,
Wa: mass fraction of monomer A,
Tgb: glass transition temperature (K) of homopolymer of monomer B,
Wb: mass fraction of monomer B,
Tgn: glass transition temperature (K) of homopolymer of monomer N,
Wn: mass fraction of monomer N,
However, Wa+Wb+...+Wn=1
Is. )

In the present invention, the method of adjusting the glass transition temperature of the acrylic resin emulsion [I] is not particularly limited, and the glass transition temperature when each homopolymer of the polymerization monomer component to be used is appropriately determined by the Fox equation. Then, the composition ratio of the polymerized monomer components may be determined.

<Acrylic resin particles [II]>
The acrylic resin emulsion [II] used in the present invention is obtained by dispersing acrylic resin particles (b) in an aqueous medium, and has a glass transition temperature (Tg) of 0° C. or higher and 60° C. or lower. It is an acrylic resin emulsion.

Examples of the monomer constituting the acrylic resin particles (b) in the acrylic resin emulsion [II] include (meth)acrylic monomer (b-1) and functional group-containing monomer (b-2). You can
The (meth)acrylic monomer (b-1) is the same as the above (meth)acrylic monomer (a-1), and the functional group-containing monomer (b-2) is the above (meth). The same thing as the acrylic monomer (a-2) can be used.

The content of the (meth)acrylic monomer (b-1) and/or the functional group-containing monomer (b-2) is 70 to 100% by mass with respect to the total amount of monomers constituting the acrylic resin particles (b). Is preferable, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass. If the content is too low, the production stability of the acrylic resin emulsion for hair styling tends to decrease.

In the monomer component constituting the acrylic resin particles (b) in the acrylic resin emulsion [II], the content ratio of the (meth)acrylic monomer (b-1) constitutes the acrylic resin particles (b). It is preferably 80 to 100% by mass, more preferably 85 to 99.99% by mass, and still more preferably 90 to 99.9% by mass, based on the total amount of the monomer components.
If the content of the (meth)acrylic monomer (b-1) is too low, the production stability of the acrylic resin emulsion for hair styling tends to decrease.

In the monomer component constituting the acrylic resin particles (b) in the acrylic resin emulsion [II], the content ratio of the functional group-containing monomer (b-2) is the monomer constituting the acrylic resin particles (b). The content is preferably 0 to 20% by mass, more preferably 0.01 to 15% by mass, and still more preferably 0.1 to 10% by mass, based on the entire components.
If the content ratio is too high, the production stability of the acrylic resin emulsion for hair styling tends to decrease, and if it is too low, flaking tends to deteriorate.

Moreover, when the functional group-containing monomer (b-2) is a monomer having two or more vinyl groups in the molecular structure, the content of the monomer having two or more vinyl groups in the molecular structure is an acrylic resin. The content is preferably 0.01 to 20% by mass, more preferably 0.05 to 15% by mass, and still more preferably 0.1 to 10% by mass, based on the whole monomer components constituting the particles (b). ..

Moreover, when the functional group-containing monomer (b-2) is a hydrolyzed silyl group-containing monomer, the content of the hydrolyzed silyl group-containing monomer is such that the total amount of the monomer components constituting the acrylic resin particles (b) is It is preferably 0.01 to 15% by mass, more preferably 0.02 to 12% by mass, and further preferably 0.05 to 10% by mass.

In addition, as long as the effects of the present invention are not impaired, a small amount of styrene-based monomers such as styrene and α-methylstyrene; Using vinyl ester monomers such as vinyl acetate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl versatate, and vinyl 2-ethylhexanoate. Good.

The acrylic resin emulsion [II] can be obtained, for example, by emulsion polymerization, and the components used in the emulsion polymerization, the content thereof, the conditions of the emulsion polymerization and the like are the same as those of the acrylic resin emulsion [I] described above. The same is true.

The average particle size of the acrylic resin particles (b) in the acrylic resin emulsion [II] is preferably 50 to 1000 nm, more preferably 60 to 800 nm, and particularly preferably 70 to 600 nm. When the average particle diameter is less than 50 nm, the nonvolatile content concentration of the acrylic resin emulsion [I] tends to be too low. When the average particle size is larger than 1000 nm, the particle size distribution tends to be broad, the particle size ratio balance with the inorganic particles is lost, and the flaking suppressing effect tends to be reduced. Further, the storage stability of the acrylic resin emulsion for hair styling tends to decrease.
The average particle diameter of the acrylic resin particles (b) can be measured by the same method as the average particle diameter of the acrylic resin particles (a).

In the present invention, the glass transition temperature (Tg) of the acrylic resin emulsion [II] needs to be 0° C. or higher and 60° C. or lower. If the glass transition temperature of the acrylic resin emulsion [II] is too high, the film formed on the hair is too hard and brittle to give a poor touch, and flaking tends to be deteriorated. The system resin emulsion [II] is likely to form a film, or the acrylic resin emulsion [I] is likely to form a film, and flaking tends to be deteriorated.
The glass transition temperature (Tg) of the acrylic resin emulsion [II] is preferably 0° C. or higher and 55° C. or lower, and more preferably 0° C. or higher and 50° C. or lower.

In the present invention, the glass transition temperature (Tg) of the acrylic resin emulsion [II] is the glass transition temperature of the acrylic resin particles (b) in the acrylic resin emulsion [II], and It is calculated by a formula.

In the present invention, the method for adjusting the glass transition temperature of the acrylic resin emulsion [II] is not particularly limited, and the glass transition temperature when each homopolymer of the polymerization monomer component to be used is appropriately determined by the Fox equation. Then, the composition ratio of the polymerized monomer components may be determined.

<Inorganic particles>
Examples of the inorganic particles used in the present invention include metal oxides such as titanium oxide, zinc oxide, zirconium oxide and magnesium oxide, metal carbonates such as calcium carbonate and magnesium carbonate, silicic acid, silica, talc and clay. Are listed. Among them, silica is preferable from the viewpoint of hair styling performance and high dispersibility.

Silica is silicon dioxide (SiO ₂ ) produced mainly from chlorosilanes, sodium silicate, and the like. Silica is roughly classified into crystalline silica such as quartz and cristobalite and amorphous silica such as diatomaceous earth. Examples of the amorphous silica include colloidal silica and fumed silica. In the present invention, it is more preferable to use amorphous silica such as colloidal silica and fumed silica because the dispersibility is good.

The average particle size of the inorganic particles is preferably 5 to 500 nm, more preferably 7 to 300 nm, and further preferably 10 to 200 nm. If the average particle size of the inorganic particles is too small, stains and stiffening tend to occur, while if too large, flaking tends to occur and hair tends to whiten.

In the present invention, the average particle size of the inorganic particles is the acrylic resin particles (a) in the acrylic resin emulsion [I] and the acrylic resin in the acrylic resin emulsion [II] from the viewpoint of preventing flaking. It is preferable that the average particle diameter of the resin particles (b) is smaller. This is because the inorganic particles are dispersed in the gaps between the acrylic resin particles, and the acrylic resin particles are covered with the inorganic particles to form a structure in which the acrylic resin particles are hard to form a film. Therefore, it is presumed that flaking due to film peeling during combing is prevented. Therefore, when the average particle size of the inorganic particles is smaller than the average particle size of the acrylic resin particles (a) and the acrylic resin particles (b), flaking does not occur, the friction coefficient is high, and there is no stickiness, and It has excellent hair styling performance (launching power and hair restyling performance).
On the other hand, when the average particle size of the inorganic particles is larger than the average particle size of the acrylic resin particles (a) and the acrylic resin particles (b), the balance of the state of covering the acrylic resin particles with the inorganic resin particles is lost, A continuous layer of the film is likely to be formed, flaking may occur, and whitening of the entire hair due to scattered light due to the size of the inorganic particles itself tends to occur.

The average particle size of the inorganic particles can be measured by using a particle size distribution measuring device of a dynamic light scattering type, for example, Particle Sizing Systems “NICOMP 380” (trade name).

Specific examples of the inorganic particles that can be used in the present invention include "Snowtex 40", "Snowtex XL", "Snowtex YL", "Snowtex ZL", and "Snow" manufactured by Nissan Chemical Industries, Ltd. "Tex MP-1040", "Snowtex MP-2040", "Snowtex MP-3040" and "Snowtex MP-4540M" (all are trade names), "Quatron PL-1" manufactured by Fuso Chemical Industry Co., Ltd., "Quatron PL-3", "Quatron PL-7" and "Quatron PL-10H" (all are trade names), and "AEROSIL200" and "AEROSIL300" (all trade names) manufactured by Nippon Aerosil Co., Ltd. Can be mentioned.

<Acrylic resin emulsion for hair dressing>
The acrylic resin emulsion for hairdressing composition of the present invention is characterized by containing the above-mentioned acrylic resin emulsion [I], acrylic resin emulsion [II] and inorganic particles.

In the acrylic resin emulsion for hairdressing agent of the present invention, the content of the acrylic resin emulsion [I] is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass. Further, the content of the acrylic resin emulsion [II] is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass. If the contents of the acrylic resin emulsion [I] and the acrylic resin emulsion [II] are too small, the dispersion stability of the inorganic particles is lowered, it becomes difficult to obtain sufficient hair styling performance, and flaking tends to be easily deteriorated. On the other hand, if it is too large, the content of the inorganic particles becomes relatively small, so that the flaking suppressing effect tends to decrease.

In addition, the total content of the acrylic resin emulsion [I] and the acrylic resin emulsion [II] is preferably 0.2 to 30% by mass, and more preferably 1 to 15% by mass.
If the total content of the acrylic resin emulsion [I] and the acrylic resin emulsion [II], which are the base resin, is too small, the dispersion stability of the inorganic particles decreases, and it becomes difficult to obtain sufficient hair styling performance, and However, flaking tends to deteriorate, and if it is too large, the viscosity tends to be high and the handleability tends to deteriorate, or the storage stability tends to deteriorate. Further, since the content of the inorganic particles is relatively small, the flaking suppressing effect tends to be lowered.

The content ratio (nonvolatile content mass ratio) of the acrylic resin emulsion [I] and the acrylic resin emulsion [II] is preferably [I]/[II]=10/90 to 90/10, and 15/85. ˜85/15 is more preferable, and 20/80 to 80/20 is further preferable. If the content ratio (nonvolatile content mass ratio) of the acrylic resin emulsion [I] and the acrylic resin emulsion [II] is too small, the polymer tends to be hard and brittle on the hair, and flaking tends to occur. The polymer tends to form a film on the above, and flaking tends to occur easily.

In the present invention, when the average glass transition temperature of the glass transition temperature of the acrylic resin emulsion [I] and the glass transition temperature of the acrylic resin emulsion [II] is 20° C. or less, flaking can be suppressed. Is preferable, 15° C. or lower is more preferable, and 8° C. or lower is further preferable.
Moreover, the lower limit of the average glass transition temperature of the glass transition temperature of the acrylic resin emulsion [I] and the glass transition temperature of the acrylic resin emulsion [II] is not particularly limited, but it is preferably −15° C. or higher, −14 C. or higher is more preferable.

The average glass transition temperature is an average value of the glass transition temperatures, and can be calculated as an average value from the glass transition temperature of each acrylic resin particle and its mixing ratio.

Further, from the viewpoint of preventing flaking, the difference (Tg _[II] -Tg _[I] ) between the glass transition temperatures of the acrylic resin emulsion [I] and the acrylic resin emulsion [II] is 5° C. or more. Is preferable, 7-70 degreeC is more preferable, 10-65 degreeC is more preferable. When Tg _[II] -Tg _[I] is 5° C. or higher, the effect of suppressing film formation of the acrylic resin is further obtained, and thus flaking can be prevented. If the difference in glass transition temperature (Tg _[II] -Tg _[I] ) is less than 5°C, flaking tends to occur.

In the acrylic resin emulsion for hairdressing agent of the present invention, the content of the inorganic particles is 10 to 150 parts by mass based on 100 parts by mass of the total nonvolatile content of the acrylic resin emulsion [I] and the acrylic resin emulsion [II]. Is preferred, 12 to 140 parts by mass is more preferred, and 15 to 130 parts by mass is even more preferred. If the content of the inorganic particles relative to the total amount of the non-volatile components of the acrylic resin emulsion [I] and the acrylic resin emulsion [II] is too small, flaking and hair styling performance tend to be poor, and if too large, the flare will be reduced. King tends to get worse.

The acrylic resin emulsion for hairdressing agent of the present invention may contain other additives as long as the effect thereof is not impaired. Examples of other additives include organic pigments, inorganic pigments, water-soluble additives, pH adjusters, preservatives, antioxidants and the like.

Examples of organic pigments include Red No. 2, Red No. 3, Red No. 102, Red No. 104, Red No. 105, Red No. 106, Red No. 201, Red No. 202, Red No. 213, Red No. 214, Red No. 215. , Red 218, Red 223, Red 226, Red 227, Red 230, Red 231, Red 232, Red 401, Red 404, Red 405, Red 501, Red 502, Red 503, Red 504, Red 505, Red 506, Yellow 4, Yellow 5, Yellow 201, Yellow 202, Yellow 203, Yellow 204, Yellow 402, Yellow 403, Yellow 404 , Yellow 405, Yellow 406, Yellow 407, Green 3, Green 201, Green 202, Green 204, Green 205, Green 402, Blue 1, Blue 2, Blue 201, Blue No. 204, Blue No. 205, Blue No. 403, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 205, Orange No. 206, Orange No. 207, Orange No. 401, Orange No. 402, Orange No. 403, Purple No. 201 , Purple No. 401, black No. 401 and the like. The organic pigment may be a dye such as an acid dye or a basic dye described above, or a lake pigment such as a dye aluminum.

Examples of the inorganic pigments include colored pigments such as iron oxide, ultramarine blue, chromium oxide and carbon black; white pigments such as zinc oxide, titanium oxide and calcium carbonate; extender pigments such as talc, mica and kaolin.

Examples of water-soluble additives include water, ethanol; polyhydric alcohols such as 1,3-butylene glycol and propylene glycol; film-forming polymers such as vinylpyrrolidone-based polymers and polyvinyl alcohol; carboxyvinyl polymers, cellulose ethers and the like. Viscous polymers; moisturizers such as hyaluronic acid, collagen, and pantothenyl alcohol.

Examples of the pH adjuster include, for example, citric acid, lactic acid, glycolic acid, succinic acid, acetic acid, malic acid, tartaric acid, fumaric acid, phosphoric acid, hydrochloric acid, triethanolamine, isopropanolamine, 2-amino-2- Methyl-1,3-propanediol, arginine, sodium hydroxide, potassium hydroxide and the like can be mentioned.

Examples of the preservative include, for example, parabens such as methylparaben, ethylparaben and butylparaben, isopropylmethylphenol, chlorhexidine gluconate solution, trichlorocarbanilide, phenoxyethanol, phenolic acid such as carboxylic acid, hexachlorophene, benzoic acid and the like. Examples thereof include salts, undecylenic acid, salicylic acid, sorbic acid and salts thereof, dehydroacetic acid and salts thereof, Photosensitizer No. 101, Photosensitizer No. 201, Photosensitizer No. 401, hinokitiol, triclosan and the like.

Examples of the antioxidant include dibutylhydroxytoluene, sulfite, and the like.

The acrylic resin emulsion for hairdressing agents can be obtained by blending the acrylic resin emulsion [I], the acrylic resin emulsion [II], inorganic particles, and desired additives in a solvent and uniformly mixing them.

Water is preferably used as the solvent, and examples of water include ion-exchanged water, purified water, and distilled water.

As the mixing conditions, it is sufficient that the components to be blended are uniformly mixed, and it is also possible to stir and mix using an Ultra Disperser, a TK homomixer, or the like. The liquid temperature at the time of mixing may be room temperature (about 25° C.) to 80° C.

<Hairdresser>
The hair styling agent of the present invention comprises an acrylic resin emulsion [I] having a glass transition temperature of -15°C or higher and lower than 0°C, an acrylic resin emulsion [II] having a glass transition temperature of 0°C or higher and 60°C or lower, and Contains inorganic particles.
For details of the acrylic resin emulsion [I] having a glass transition temperature of -15°C or higher and lower than 0°C, the acrylic resin emulsion [II] having a glass transition temperature of 0°C or higher and 60°C or lower, and inorganic particles, The same as above.

In the hair styling agent of the present invention, flaking is suppressed when the average glass transition temperature of the glass transition temperature of the acrylic resin emulsion [I] and the glass transition temperature of the acrylic resin emulsion [II] is 20° C. or less. The temperature is preferably 15° C. or lower, more preferably 8° C. or lower.
Moreover, the lower limit of the average glass transition temperature of the glass transition temperature of the acrylic resin emulsion [I] and the glass transition temperature of the acrylic resin emulsion [II] is not particularly limited, but it is preferably −15° C. or higher, −14 C. or higher is more preferable.

Further, from the viewpoint of preventing flaking, the difference (Tg _[II] -Tg _[I] ) between the glass transition temperatures of the acrylic resin emulsion [I] and the acrylic resin emulsion [II] is 5° C. or more. Is more preferable, further preferably 7 to 70°C, more preferably 10 to 65°C. When Tg _[II] -Tg _[I] is 5° C. or higher, the effect of suppressing film formation of the acrylic resin can be further obtained. If the difference in glass transition temperature (Tg _[II] -Tg _[I] ) is less than 5°C, flaking tends to occur.

In the hair styling agent of the present invention, an acrylic resin emulsion [I] having a glass transition temperature of -15°C or higher and lower than 0°C and an acrylic resin emulsion [II] having a glass transition temperature of 0°C or higher and 60°C or lower. The total content (non-volatile content) of the above is preferably 0.05% by mass or more in the hair styling agent, more preferably 0.1% by mass or more, and further preferably 0.5% by mass or more. The upper limit is usually 20% by mass, preferably 10% by mass, more preferably 5% by mass.
The total of the acrylic resin emulsion [I] having a glass transition temperature of -15°C or higher and lower than 0°C and the acrylic resin emulsion [II] having a glass transition temperature of 0°C or higher and 60°C or lower in the hair styling agent. If the content (nonvolatile content) is too low, the dispersion of the inorganic particles is not sufficient and the hair styling property tends to decrease, while if it is too high, flaking tends to occur, and detergency tends to decrease. ..

In the hair styling agent of the present invention, the content ratio (nonvolatile content mass ratio) of the acrylic resin emulsion [I] and the acrylic resin emulsion [II] is [I]/[II]=10/90 to 90/10. 15/85 to 85/15 are more preferable, and 20/80 to 80/20 are still more preferable. If the content ratio (nonvolatile content mass ratio) of the acrylic resin emulsion [I] and the acrylic resin emulsion [II] is too small, the polymer tends to be hard and brittle on hair and flaking tends to occur, and if it is too large. The polymer tends to form on the hair and flaking tends to occur.

In the hair styling agent of the present invention, the content of the inorganic particles is preferably 10 to 150 parts by mass based on 100 parts by mass of the total nonvolatile content of the acrylic resin emulsion [I] and the acrylic resin emulsion [II]. , 12 to 140 parts by mass are more preferable, and 15 to 130 parts by mass are even more preferable. If the content of the inorganic particles relative to the total amount of the non-volatile components of the acrylic resin emulsion [I] and the acrylic resin emulsion [II] is too small, flaking and hair styling performance tend to be poor, and if too large, the flare will be reduced. King tends to get worse.

The hair styling agent of the present invention also includes a hair styling agent containing the acrylic resin emulsion [I], the acrylic resin emulsion [II], and inorganic particles, and the acrylic resin emulsion for hair styling of the present invention. It is a waste.

<Method for producing hair styling agent>
The hair styling agent of the present invention is an acrylic resin emulsion [I] having a glass transition temperature of -15°C or higher and lower than 0°C, and an acrylic resin having a glass transition temperature of 0°C or higher and 60°C or lower. Into the resin-based resin emulsion [II] and inorganic particles, various compounding ingredients used in known general hair styling agents, such as oils, polyhydric alcohols, lower alcohols, surfactants, ultraviolet absorbers, fragrances, antioxidants, moisturizers An agent, a cooling agent, vitamins, a plant extract, an organic pigment, an inorganic pigment, a water-soluble additive, a pH adjusting agent, an antiseptic, an antioxidant and the like can be appropriately mixed and produced according to the purpose.

Examples of the oil include oils and fats such as sunflower oil, cottonseed oil, soybean oil, olive oil, coconut oil, castor oil, jojoba oil, camellia oil, mink oil; beeswax, carnauba wax, candelilla wax, rice bran wax, shellac wax, whale wax, lanolin. And other waxes; cerecin, paraffin wax, liquid paraffin, liquid isoparaffin, microcrystalline wax, polyethylene powder, polyethylene wax, Fischer-Tropsch wax, petrolatum, squalane, and other hydrocarbon oils; lauric acid, myristic acid, palmitic acid, stearin Higher fatty acids such as acids, oleic acid, behenic acid, 2-ethylbutanoic acid, isopentanoic acid, 2-methylpentanoic acid, 2-ethylpentanoic acid, isostearic acid, 12-hydroxystearic acid; lauryl alcohol, myristyl alcohol, cetyl alcohol, Higher alcohols such as stearyl alcohol, oleyl alcohol, lanolin alcohol, behenyl alcohol and cetostearyl alcohol; ethyl oleate, isopropyl myristate, isopropyl palmitate, myristyl myristate, cetyl palmitate, oleyl oleate, octyldodecyl myristate, oleic acid Octyldodecyl, ethyl isostearate, isopropyl isostearate, cetyl 2-ethylhexanoate, cetostearyl 2-ethylhexanoate, glyceryl tri-2-ethylhexanoate, glyceryl triisopalmitate, pentaerythritol tetra-2-ethylhexanoate, octane Fatty acid ester oils such as isocetyl acid, isostearyl octanoate, isocetyl isostearate, octyldodecyl isostearate, octyldodecyl dimethyloctanoate; methyl polysiloxane, highly polymerized methyl polysiloxane, methylphenyl polysiloxane, octamethyl trisiloxane, decamethyl Silicone oils such as tetrasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, methylcyclopolysiloxane, alcohol-modified silicone, alkyl-modified silicone, amino-modified silicone, epoxy-modified silicone, etc. it can. These may be used alone or in combination of two or more.

From the viewpoint of emulsification, the content of such an oil agent is usually preferably 0.5 to 50% by mass, and particularly preferably 1 to 40% by mass in the total amount of the hair styling agent. Further, from the viewpoint of reducing the oiliness and stickiness of the hair styling agent, it is preferable to keep the content as low as possible. However, by using the inorganic particle-containing acrylic resin emulsion for hair styling agent of the present invention, the amount of the oil agent used Can be reduced or unused.

Examples of the polyhydric alcohol include ethylene glycol, dipropylene glycol, propylene glycol, isoprene glycol, glycerin, diglycerin, 1,3-butylene glycol, 1,2-pentanediol, 1,2-hexanediol, 1, 2-octanediol, 1,2-decanediol, etc. can be illustrated. These may be used alone or in combination of two or more.

The content of the polyhydric alcohol is preferably 0.1 to 20% by mass, and particularly preferably 0.5 to 15% by mass in the total amount of the hair styling agent from the viewpoint of feeling of use.

The hair styling agent of the present invention includes an acrylic resin emulsion [I] having a glass transition temperature of -15°C or higher and lower than 0°C and an acrylic resin emulsion [II] having a glass transition temperature of 0°C or higher and 60°C or lower. , And can be produced by mixing the inorganic particles, as the mixing method,
(1) A method of blending and mixing the acrylic resin emulsion [I], the acrylic resin emulsion [II], and inorganic particles,
(2) A method of preparing an acrylic resin emulsion in which the acrylic resin emulsion [I] and the acrylic resin emulsion [II] are mixed in advance, and mixing and mixing this with inorganic particles,
(3) A method of preparing an acrylic resin emulsion containing inorganic particles in which the acrylic resin emulsion [I], the acrylic resin emulsion [II], and inorganic particles are mixed in advance, and using this.
However, the method (3) is preferable from the viewpoint that the inorganic particles are well dispersed, the hair styling performance is improved, and flaking is reduced.

As the mixing conditions, it is sufficient that the respective components are uniformly mixed, and it is also possible to stir and mix using an ultra disperser, a TK homomixer or the like. The liquid temperature at the time of mixing may be room temperature (about 25°C) to 40°C.

The acrylic resin emulsion for a hair styling agent of the present invention is particularly suitable for an aqueous hair styling agent such as a hair spray, a hair mist, a hair set lotion and a hair gel, and these hair styling agents can be prepared by a known method.

The hair styling agent of the present invention can be used for hair styling, for example, as follows.
That is, the hair styling agent of the present invention is applied to hair in an effective hair styling amount, and the hair is shaped into a desired shape during or before and after the application. By styling hair in this way, a desired hairstyle can be easily formed. The hair styling agent of the present invention has excellent hair styling performance (launching power, hair bundle feeling), little stickiness, and very little flaking.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded. In the examples, "part" and "%" mean mass basis.

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 above method.

<Nonvolatile content>
1 g of the sample is spread on an aluminum foil dish container shaped to have the same bottom area as a flat balance bottle 50 mm×30 mm defined in JIS R 3503 (1994), and the sample is accurately weighed. The container is placed in the center of a constant temperature bath, dried at 105° C.±2° C. for 60±5 minutes, allowed to cool in a desiccator, and its mass is measured.
Then, the nonvolatile content (N) was calculated by the following formula.
N(%)=(Wd/Ws)×100
(In the formula, N is the nonvolatile content (%), Wd is the mass (g) of the sample after drying, and Ws is the mass (g) of the sample before drying.)

<Average particle size of acrylic resin particles>
It is a volume average particle diameter obtained when an autocorrelation function measured by a dynamic light scattering method (DLS) at a temperature of 23° C. and a scattering angle of 90° is cumulant fitting, and is made by Particle Sizing Systems, “NICOMP 380”. Was measured.

<Glass transition temperature>
It was calculated by the following Fox equation.

(In the formula, Tg: the glass transition temperature (K) of the polymer formed from the monomer A, the monomer B,..., And the monomer N,
Tga: glass transition temperature (K) of homopolymer of monomer A,
Wa: mass fraction of monomer A,
Tgb: glass transition temperature (K) of homopolymer of monomer B,
Wb: mass fraction of monomer B,
Tgn: glass transition temperature (K) of homopolymer of monomer N,
Wn: mass fraction of monomer N,
However, Wa+Wb+...+Wn=1
Is. )

<Production Example 1: Preparation of acrylic resin emulsion [I-1]>
Ion-exchanged water (53.0 parts) and sodium citrate (0.2 parts) were charged into a SUS reaction can equipped with a cooling tube and a stirring blade to completely dissolve them, and the temperature was raised to 80°C.
Ion-exchanged water (51.3 parts), sodium lauryl sulfate (2.4 parts), and n-butyl acrylate (62.0 parts) and methyl methacrylate (32 parts) as the (meth)acrylic monomer (a-1) component in advance. 0.0 part), a functional group-containing monomer (a-2) component as an emulsified product of methacrylic acid (3.0 parts) and ethylene glycol dimethacrylate (3.0 parts), and 3% KPS (excess). An aqueous solution of potassium sulfate (10.3 parts) (ii) was prepared. First, 37% of (ii) was added to the reaction vessel, and after 10 minutes, the total amount of (i) and 55% of (ii) were added dropwise over 3.5 hours to polymerize at 78 to 82°C.
After completion of the dropping, the temperature was raised to 88 to 90° C., 10 minutes after the completion of the dropping, 4% of (ii) was added, the temperature was maintained for 35 minutes, and 4% of (ii) was further added, The temperature was held for 45 minutes.
Thereafter, the mixture was cooled to 55 to 60° C., and 1.7 parts of a 10% aqueous solution of tertiary butyl hydroperoxide (NOF CORPORATION, “Perbutyl H-69”) and 2.8 parts of a 5% aqueous sodium hydrogen sulfite solution, respectively. It was added and reacted for 60 minutes. Then, the mixture was cooled to about 30° C., neutralized with 10% ammonia water to a pH of about 7 to 9, filtered through a 150-mesh nylon mesh, and the acrylic resin emulsion [I-1] (nonvolatile content 45 0.7%, average particle diameter 230 nm, glass transition temperature -13°C) were obtained.

<Production Example 2: Preparation of acrylic resin emulsion [I-2]>
Acrylic resin emulsion in the same manner as in Production Example 1 except that n-butyl acrylate (57.0 parts) and methyl methacrylate (37.0 parts) were used as the (meth)acrylic monomer (a-1) component. [I-2] (nonvolatile matter 45.6%, average particle diameter 180 nm, glass transition temperature -7°C) was obtained.

<Production Example 3: Preparation of acrylic resin emulsion [II-1]>
Acrylic resin emulsion in the same manner as in Production Example 1 except that n-butyl acrylate (37.0 parts) and methyl methacrylate (57.0 parts) were used as the (meth)acrylic monomer (a-1) component. [II-1] (nonvolatile matter 45.7%, average particle diameter 310 nm, glass transition temperature 25° C.) was obtained.

<Production Example 4: Preparation of acrylic resin emulsion [II-2]>
Acrylic resin emulsion in the same manner as in Production Example 1 except that n-butyl acrylate (24.0 parts) and methyl methacrylate (70.0 parts) were used as the (meth)acrylic monomer (a-1) component. [II-2] (nonvolatile matter 45.5%, average particle size 310 nm, glass transition temperature 50° C.) was obtained.

<Production Example 5: Preparation of acrylic resin emulsion [II-3]>
Acrylic resin emulsion in the same manner as in Production Example 1 except that n-butyl acrylate (52.5 parts) and methyl methacrylate (41.5 parts) were used as the (meth)acrylic monomer (a-1) component. [II-3] (nonvolatile matter 45.4%, average particle diameter 280 nm, glass transition temperature 0° C.) was obtained.

<Production Example 6: Preparation of acrylic resin emulsion [I′-1]>
Ion-exchanged water (53.0 parts), sodium citrate (0.2 parts) and sodium lauryl sulfate (0.8 parts) were added to a SUS reaction can equipped with a cooling tube and stirring blades and completely dissolved. Then, the temperature was raised to 80°C.
Ion-exchanged water (51.3 parts), sodium lauryl sulfate (1.5 parts), and n-butyl acrylate (65.0 parts) and methyl methacrylate (26 parts) as the (meth)acrylic monomer (a-1) component in advance. 0.0 part), a functional group-containing monomer (a-2) component as an emulsion of methacrylic acid (3.0 parts) and ethylene glycol dimethacrylate (6.0 parts) (i), and 3% KPS (excess). An aqueous solution of potassium sulfate (8.0 parts) (ii) was prepared. First, 5% of (i) and 23% of (ii) were added to the reaction vessel, polymerized for 20 minutes, and the remaining 95% of (i) and 67% of (ii) were added dropwise over 3 hours. Polymerization at 78-82°C.
After completion of the dropping, the temperature was raised to 88 to 90° C., 10 minutes after the completion of the dropping, 5% of (ii) was added, the temperature was kept for 35 minutes, and 5% of (ii) was further added, The temperature was held for 45 minutes.
Thereafter, the mixture was cooled to 55 to 60° C., and 1.6 parts of a 10% aqueous solution of tertiary butyl hydroperoxide (“Perbutyl H-69” manufactured by NOF CORPORATION) and 2.6 parts of a 5% aqueous ascorbic acid solution were added, respectively. And reacted for 60 minutes. Then, the mixture was cooled to about 30° C., neutralized with 10% ammonia water so that the pH was about 7 to 9, filtered through a 150th nylon mesh, and the acrylic resin emulsion [I′-1] (nonvolatile content 46.2%, average particle diameter 110 nm, glass transition temperature -20°C) were obtained.

(Example 1)
Acrylic resin emulsion [I-1] 0.81 part (nonvolatile matter; 0.37 part) as acrylic resin emulsion [I] and acrylic resin emulsion [II] as acrylic resin emulsion [I] in a polyethylene cup (100 ml) Resin emulsion [II-1] 0.81 part (nonvolatile matter; 0.37 part) and colloidal silica (Nissan Chemical Co., Ltd. "Snowtex MP-1040" (nonvolatile matter concentration 40%, average particle diameter 120 nm). A magnetic stirrer was prepared by diluting 0.38 part (nonvolatile matter; 0.15 part) with ion-exchanged water (18.0 parts) so that the total amount of acrylic resin particles and inorganic particles was 4.5%. The resulting mixture was stirred and mixed for 30 minutes to obtain an acrylic resin emulsion, wherein the content ratio (nonvolatile content mass ratio) of the acrylic resin emulsion [I] and the acrylic resin emulsion [II] was [I]/[II]. = 50/50, the average glass transition temperature of the glass transition temperature of the acrylic resin emulsion [I] and the glass transition temperature of the acrylic resin emulsion [II] was 4.7° C. The obtained acrylic resin emulsion was It was in a uniform state.

(Example 2)
As the acrylic resin emulsion [I], 1.22 parts (nonvolatile content; 0.56 parts) of the acrylic resin emulsion [I-1], and as the acrylic resin emulsion [II], the acrylic resin emulsion [II-2] 0. An acrylic resin emulsion was prepared in the same manner as in Example 1 except that 42 parts (nonvolatile content; 0.19 part) was used. The content ratio (nonvolatile component mass ratio) of the acrylic resin emulsion [I] and the acrylic resin emulsion [II] is [I]/[II]=75/25, and the glass transition temperature of the acrylic resin emulsion [I] The average glass transition temperature of the glass transition temperatures of the acrylic resin emulsion [II] was 0.3°C. The obtained resin emulsion was in a uniform state.

(Example 3)
Acrylic resin emulsion [I] as acrylic resin emulsion [I-1] 0.41 part (nonvolatile matter; 0.19 part), acrylic resin emulsion [II] as acrylic resin emulsion [II-3] 1. An acrylic resin emulsion was prepared in the same manner as in Example 1 except that 23 parts (nonvolatile matter; 0.56 part) was used. The content ratio (nonvolatile content mass ratio) of the acrylic resin emulsion [I] and the acrylic resin emulsion [II] is [I]/[II]=25/75, and the glass transition temperature of the acrylic resin emulsion [I]. And the average glass transition temperature of the glass transition temperatures of the acrylic resin emulsion [II] was −3.4° C. The obtained resin emulsion was in a uniform state.

(Example 4)
An acrylic resin emulsion was prepared in the same manner as in Example 1 except that the compounding amount of colloidal silica was 2.60 parts (nonvolatile content; 1.04 parts). The content ratio (nonvolatile content mass ratio) of the acrylic resin emulsion [I] and the acrylic resin emulsion [II] is [I]/[II]=50/50, and the glass transition temperature of the acrylic resin emulsion [I]. The average glass transition temperature of the acrylic resin emulsion [II] and the glass transition temperature was 4.7°C. The obtained resin emulsion was in a uniform state.

(Example 5)
An acrylic resin emulsion was prepared in the same manner as in Example 1 except that colloidal silica having an average particle diameter of 10 nm (“Snowtex 40” (nonvolatile matter; 40%) manufactured by Nissan Chemical Industries, Ltd.) was used. The content ratio (nonvolatile content mass ratio) of the acrylic resin emulsion [I] and the acrylic resin emulsion [II] is [I]/[II]=50/50, and the glass transition temperature of the acrylic resin emulsion [I]. The average glass transition temperature of the acrylic resin emulsion [II] and the glass transition temperature was 4.7°C. The obtained resin emulsion was in a uniform state.

(Example 6)
Acrylic resin emulsion [I-1] 0.81 part (nonvolatile matter; 0.37 part) as acrylic resin emulsion [I] and acrylic resin emulsion [II-2] 0 as acrylic resin emulsion [II] An acrylic resin emulsion was prepared in the same manner as in Example 1 except that 0.81 part (nonvolatile matter; 0.37 part) was used. The content ratio (nonvolatile content mass ratio) of the acrylic resin emulsion [I] and the acrylic resin emulsion [II] is [I]/[II]=50/50, and the glass transition temperature of the acrylic resin emulsion [I]. The average glass transition temperature of the glass transition temperatures of the acrylic resin emulsion [II] was 15.1°C. The obtained resin emulsion was in a uniform state.

(Example 7)
As the acrylic resin emulsion [I], 0.81 part (nonvolatile content: 0.37 part) of the acrylic resin emulsion [I-2] and as the acrylic resin emulsion [II], the acrylic resin emulsion [II-1] An acrylic resin emulsion was prepared in the same manner as in Example 1 except that 81 parts (nonvolatile content: 0.37 part) was used. The content ratio (nonvolatile content mass ratio) of the acrylic resin emulsion [I] and the acrylic resin emulsion [II] is [I]/[II]=50/50, and the glass transition temperature of the acrylic resin emulsion [I]. The average glass transition temperature of the acrylic resin emulsion [II] and the glass transition temperature was 8.1°C. The obtained resin emulsion was in a uniform state.

(Comparative Example 1)
Acrylic resin emulsion [I'-1] 0.80 parts (nonvolatile matter; 0.37 parts) as acrylic resin emulsion [I], and acrylic resin emulsion [II-1] as acrylic resin emulsion [II]. An acrylic resin emulsion was prepared in the same manner as in Example 1 except that 0.81 part (nonvolatile matter; 0.37 part) was used. The content ratio (nonvolatile content mass ratio) of the acrylic resin emulsion [I] and the acrylic resin emulsion [II] is [I]/[II]=50/50, and the glass transition temperature of the acrylic resin emulsion [I]. The average glass transition temperature of the glass transition temperature of the acrylic resin emulsion [II] was 0.7°C. The obtained resin emulsion was in a uniform state.

With respect to the acrylic resin emulsions of Examples 1 to 7 and Comparative Example 1, hair styling performance and flaking were evaluated by the following evaluation methods. The results are shown in Table 1.

<Hairdressing performance>
Weigh 2.0 g of the acrylic resin emulsion obtained above with a balance and spread it thinly on the entire palm, and apply it evenly so that it cuts into one side of the head using a wig for a cut model. It evaluated by the following evaluation criteria.
〔Evaluation criteria〕
◯: Hair styling was sufficient Δ: Hair styling was weak x: Hair styling was not

<flaking>
After weighing 2.0 g of the acrylic resin emulsion obtained above with a balance and spreading it thinly over the entire palm, using a wig for a cut model, applying it so that one side of the head is centered and stroked, It was left standing for 12 hours or more at room temperature (23 to 28°C). After standing still, the applied hair was combed 5 times with a plastic comb. The state of the wig after combing was visually observed and evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
⊚: No flaking occurred at all ◯: Very small amount of flaking occurred only Δ: Very small amount of flaking occurred, or slightly large amount of flaking occurred ×: Very small flaking Occurrence of many kings, or a large amount of flaking was noticeable XX: Flaking was noticeable on the entire hair, or the entire hair was whitened

From the results of Table 1, an acrylic resin emulsion [I] having a glass transition temperature of -15°C or higher and lower than 0°C, an acrylic resin emulsion [II] having a glass transition temperature of 0°C or higher and 60°C or lower, and an inorganic substance It was found that all of Examples 1 to 7 containing particles have excellent hair styling performance, little stickiness, and no or very little flaking.
On the other hand, it was found that Comparative Example 1 in which the glass transition temperature of the acrylic resin emulsion [I] did not satisfy the range defined by the present invention had a large amount of flaking and was inferior to Example 1.

Furthermore, a hair styling agent was prepared as described below, and hair styling performance and flaking were evaluated by the following evaluation methods.

(Example 8)
A hair styling agent (hair lotion) was prepared by a conventional method according to the following formulation.
<Hair lotion formulation>
Acrylic resin emulsion [I-1] 2.2% by mass
Acrylic resin emulsion [II-1] 2.2% by mass
Silica 0.4 mass%
Polyoxypropylene sorbit 10.0% by mass
Phenoxyethanol 0.3 mass%
Ethanol 10.0% by mass
Acrylic resin alkanolamine liquid 3.0 mass%
Xanthan gum 0.3% by mass
Purified water balance 100% by mass in total

(Example 9)
A hair styling agent (hair gel) was prepared by a conventional method according to the following formulation.
<Hair gel formulation>
Acrylic resin emulsion [I-1] 1.5% by mass
Acrylic resin emulsion [II-1] 1.5 mass%
Silica 2.0 mass%
Sodium/magnesium silicate 2.5 mass%
Glycerin 6.0 mass%
Xanthan gum 0.2 mass%
Citric acid 0.08% by mass
Ethanol 15.0% by mass
Purified water balance 100% by mass in total

(Example 10)
A hair styling agent (hair wax) was prepared by a conventional method according to the following formulation.
<Hair wax formulation>
Acrylic resin emulsion [I-1] 5.5 mass%
Acrylic resin emulsion [II-2] 5.5 mass%
Silica 1.0% by mass
Candelilla wax 3.0 mass%
Vaseline 7.0 mass%
Liquid paraffin 6.5% by mass
Polyoxyethylene cetyl ether 6.0% by mass
Sorbitan stearate 7.0% by mass
Phenoxyethanol 0.8 mass%
Paraoxybenzoic acid ester 0.3% by mass
Glycerin 3.0 mass%
Triethanolamine 0.1% by mass
Carboxy vinyl polymer 0.3% by mass
Fragrance 0.09 mass%
Purified water balance 100% by mass in total

The hair styling agents obtained in Examples 8 to 10 were evaluated for hair styling performance and flaking by the following evaluation methods.

<Hairdressing performance>
2.0 g of the hair styling agent obtained in Examples 8 to 10 (weighed with a balance) is uniformly applied to the whole of the short hair wig (hair having a length of about 20 cm at the top of the crown cut into a general hairstyle). Was applied to. Then, the hair was raked from the side of the head of the wig toward the top of the head, and the hair was adjusted so that the hair was raised right above.
Immediately after styling, the rise of hair was observed. The angle of the hair bundle consisting of the hair in the middle of the temporal part and the crown of the wig is 0° when the hair is directly below, and 180° when the hair is directly above. The hair styling performance was measured and evaluated according to the following criteria.
〔Evaluation criteria〕
◯ (good hair styling performance): angle of 130° or more Δ (poor hair styling performance): angle of 80° or more and less than 130° × (poor hair styling performance): angle of less than 80°

The evaluation results of the hair styling performance of the hair styling agents obtained in Examples 8 to 10 were all “◯” (good hair styling performance).

<flaking>
The hair styling agents obtained in Examples 8 to 10 were weighed at 2.0 g on a balance and spread thinly over the entire palm, and a cut model wig was used to apply the hair styling agent with one side of the head centered. Then, it was left to stand for 12 hours or more at room temperature (23° C.). After standing still, the applied hair was combed 5 times with a plastic comb. The state of the wig after combing was visually observed and evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
⊚: No flaking occurred at all ◯: Very small amount of flaking occurred only Δ: Very small amount of flaking occurred, or slightly large amount of flaking occurred ×: Very small flaking Occurrence of many kings, or a large amount of flaking was noticeable XX: Flaking was noticeable on the entire hair, or the entire hair was whitened

The evaluation results of flaking of the hair styling agents obtained in Examples 8 and 9 were “◯”, and the evaluation results of flaking of the hair styling agents obtained in Example 10 were “⊚”.

The acrylic resin emulsion for a hair styling agent and the hair styling agent using the same of the present invention are particularly suitable for an aqueous hair styling agent such as a hair spray, a hair mist, a hair setting lotion and a hair gel.

Claims (9)

Acrylic resin emulsion [I] having a glass transition temperature of -15°C or higher and lower than 0°C, acrylic resin emulsion [II] having a glass transition temperature of 0°C or higher and 60°C or lower, and inorganic particles. An acrylic resin emulsion for hair styling, characterized by: The acrylic resin emulsion for a hair styling agent according to claim 1, wherein the acrylic resin emulsion [I] and the acrylic resin emulsion [II] have an average glass transition temperature of 20°C or lower. The acrylic for hairdressing preparation according to claim 1 or 2, wherein the difference between the glass transition temperature of the acrylic resin emulsion [I] and the glass transition temperature of the acrylic resin emulsion [II] is 5°C or more. -Based resin emulsion. The content ratio (nonvolatile content mass ratio) of the acrylic resin emulsion [I] and the acrylic resin emulsion [II] is [I]/[II]=10/90 to 90/10. The acrylic resin emulsion for hair styling according to any one of claims 1 to 3. The content of the inorganic particles is 10 to 150 parts by mass with respect to a total of 100 parts by mass of the nonvolatile content of the acrylic resin emulsion [I] and the nonvolatile content of the acrylic resin emulsion [II]. The acrylic resin emulsion for hair styling according to any one of claims 1 to 4. The said inorganic particle|grains are silica, The acrylic resin emulsion for hairdressing agents of any one of Claims 1-5 characterized by the above-mentioned. Acrylic resin emulsion [I] having a glass transition temperature of -15°C or higher and lower than 0°C, acrylic resin emulsion [II] having a glass transition temperature of 0°C or higher and 60°C or lower, and inorganic particles. A hair styling agent characterized by: Mixing acrylic resin emulsion [I] having a glass transition temperature of -15°C or higher and lower than 0°C, acrylic resin emulsion [II] having a glass transition temperature of 0°C or higher and 60°C or lower, and inorganic particles. A method for producing an acrylic resin emulsion for hair styling, which comprises: Mixing acrylic resin emulsion [I] having a glass transition temperature of -15°C or higher and lower than 0°C, acrylic resin emulsion [II] having a glass transition temperature of 0°C or higher and 60°C or lower, and inorganic particles. A method for producing a hair styling agent, comprising: