KR102318407B1 - Acrylic resin emulsion for hairdressing agent, hairdressing agent containing acrylic resin emulsion for hairdressing agent, and hairdressing method - Google Patents

Abstract

The present invention relates to an acrylic resin for hair dressing obtained by emulsion polymerization of a suitable monomer composition [I] and a monomer composition [II] in order to obtain a hair dressing excellent in a balance between styling performance (hairdressing performance, rehairing performance, tactile property) and to-be-cleaned performance. As an emulsion, the following conditions (i) to (iii) are satisfied:
(i) at least one of the monomer composition [I] and the monomer composition [II] contains a (meth)acrylate-based monomer;
(ii) The glass transition temperature (Tg2) obtained by the formula of Fox of the polymer polymerized using the monomer composition [II] is obtained by the formula of Fox of the polymer polymerized using the monomer composition [I] temperature is more than 30°C above the glass transition temperature (Tg1);
(iii) The mixing ratio (weight ratio) of the monomer composition [I] and the monomer composition [II] is monomer composition [I]: monomer composition [II] = 50:50 to 99:1.

Description

Acrylic resin emulsion for hair dressing, hair dressing containing same, and hairdressing method {Acrylic resin emulsion for hairdressing agent, hairdressing agent containing acrylic resin emulsion for hairdressing agent, and hairdressing method}

The present invention relates to an acrylic resin emulsion useful as a hair dressing (hair styling agent), and more particularly, excellent in water solubility and/or redispersibility in water, and a balance between cleaning performance and styling performance when used as a hair dressing. It relates to an excellent acrylic resin emulsion.

As the hair dressing, there are various formulations such as liquid, gel, foam, spray, cream, and wax.

Usually, a hair dressing contains a polymer (set polymer) for maintaining a desired shape by forming a film on the surface of the hair, and also contains additives provided for various purposes, solvents formulated according to the formulation, bases, etc. It is a blended polymer composition. In recent years, hairdressing agents can freely arrange hair at the time of hairdressing, and as formulations that can be easily modified even after hairdressing, hair creams and hair waxes, which are emulsified formulations using an oil agent and water, have become mainstream.

In addition, performance in styling (preparation of hair) such as performance of giving a desired shape to hair and maintaining it for a long time, excellent appearance performance, and excellent tactile performance are required. The convenience at the time of washing|cleaning and removal is also calculated|required as performance, and various hair dressings are being developed.

For example, Patent Document 1 describes a hair dressing of an aqueous solution type using a polyvinyl alcohol-based resin having a specific structure as a main component of the polymer component, which is the subject, and Patent Document 2 describes an emulsion consisting of beeswax, a surfactant and water. In the composition, there is described a hair cosmetic in which polyvinyl alcohol is blended as a compounding agent.

JP 2009-286724A JP 2011-148721A

In the hair dressing of Patent Document 1, a polyvinyl alcohol-based resin having a specific structure has good curl retention under high humidity conditions, has little stickiness, and has moisturizing properties, so it has a performance with little damage to hair. The hair dressing of document 2 improves the aesthetics at the time of use by mix|blending a polyvinyl alcohol-type resin in an emulsion composition, and has the performance which does not provide unnatural brilliance to the hair after application|coating.

However, the hairstyling agent described in patent document 1 was a point with insufficient combing properties, such as finger combing, a comb, or a brush, and the point of the re-hairdressing property at the time of breaking hairdressing once left room for improvement. Moreover, stickiness was large, and the hair dressing of patent document 2 was what the improvement was calculated|required in a usability|use_condition.

Moreover, favorable hairstyling power and re-hairdressing performance are calculated|required of recent hair dressing, and the hairdressing holding power that the hairstyle once haircut is maintained for a long time is also calculated|required. On the other hand, hairstyling agents having good hairstyling power as described above are often difficult to clean because they contain a lot of oil components such as wax, and require strong rubbing with shampoo or washing twice. Dryness or dryness problems may occur. Moreover, there is also a concern about scalp troubles such as dandruff, itchiness and hair loss due to the oil component remaining when washing is insufficient.

Therefore, coexistence of favorable styling performance (hairdressing property) and favorable to-be-washed property is calculated|required by a hair dressing in recent years.

Therefore, in the present invention, in consideration of these problems, hairdressing performance (hairdressing performance (set power), re-hairdressing performance (reset power, reset retention power)), tactile properties and hairdressing performance to be cleaned in water or lukewarm water, etc. in a well-balanced manner An object of the present invention is to provide an acrylic resin emulsion for hair dressing that is effectively used in the preparation.

Therefore, the inventors of the present invention, as a result of repeated intensive research in view of such circumstances, as an acrylic resin emulsion formed by emulsion polymerization of at least two types of monomer compositions, at least one of which contains a (meth)acrylate-based monomer, The difference in the glass transition temperature of the two polymers when each of these monomer compositions is polymerized is 30° C. or more, and the monomer composition having the higher glass transition temperature is lower than the monomer composition having the lower glass transition temperature. The present invention, by discovering that a hair dressing containing an acrylic resin emulsion obtained by quantitative emulsion polymerization is excellent in a good balance in styling performance (hairdressing performance (set power), rehairing performance (reset power), tactile properties) and to-be-cleaned performance has completed

That is, the summary of this invention is as follows.

[1] It is an acrylic resin emulsion for hair dressings obtained by emulsion polymerization of a monomer composition [I] and a monomer composition [II], wherein the monomer composition [I] and the monomer composition [II] are the following conditions (i) to (iii) acrylic resin emulsion for hair dressing, characterized in that it satisfies;

(i) at least one of the monomer composition [I] and the monomer composition [II] contains a (meth)acrylate-based monomer;

(II) The glass transition temperature (Tg2) obtained by the formula of Fox of the polymer polymerized using the monomer composition [II] is obtained by the formula of Fox of the polymer polymerized using the monomer composition [I] 30°C or more higher than the glass transition temperature (Tg1);

(iii) The compounding ratio (weight ratio) of the said monomer composition [I] and the said monomer composition [II] is monomer composition [I]: monomer composition [II] = 50:50-99:1.

[2] Said glass transition temperature (Tg1) is 0 degreeC or less, and said glass transition temperature (Tg2) is 30 degreeC or more, The acrylic resin emulsion for hair dressings as described in said [1] characterized by the above-mentioned.

[3] The acrylic resin emulsion for hair dressing according to the above [1] or [2], wherein the acrylic resin particles in the acrylic resin emulsion are dispersion-stabilized with a polyvinyl alcohol-based resin.

[4] Said polyvinyl alcohol-type resin contains the side chain 1,2-diol structural unit represented by following formula (1), The acrylic resin emulsion for hair dressings as described in said [3] characterized by the above-mentioned.

(In Formula 1, R ¹ to ^{R 6} each independently represents a hydrogen atom or an organic group, and X represents a single bond or a bonded chain.)

[5] Using only the monomer composition [I] and the monomer composition [II], first emulsion polymerization of the monomer composition [I] is performed, followed by emulsion polymerization of the monomer composition [II], characterized in that The acrylic resin emulsion for hair dressings in any one of said [1]-[4] to say.

[6] The hair dressing containing the acrylic resin emulsion for hair dressing in any one of said [1] - [5], The hair dressing characterized by the above-mentioned.

[7] Hairdressing method including the following process (A) and process (B):

(A) a step of applying the acrylic resin emulsion for hair dressing obtained by emulsion polymerization of the monomer composition [I] and the monomer composition [II] to the hair in an effective hairdressing amount;

(B) a step of trimming the hair into a desired shape in at least one of before, simultaneously with, and after the step (A);

However, the monomer composition [I] and the monomer composition [II] satisfy the following conditions (i) to (iii);

(i) at least one of the monomer composition [I] and the monomer composition [II] contains a (meth)acrylate-based monomer;

(ii) the glass transition temperature (Tg2) obtained by the formula of Fox of the polymer polymerized using the monomer composition [II] is the glass obtained by the formula of Fox of the polymer using the monomer composition [I] more than 30°C above the transition temperature (Tg1);

(iii) The compounding ratio (weight ratio) of the said monomer composition [I] and the said monomer composition [II] is monomer composition [I]:monomer composition [II] =50:50-99:1.

The acrylic resin emulsion for hair dressing of the present invention is excellent in water solubility and / or redispersibility in water, and the hair dressing containing such an acrylic resin emulsion for hair dressing has excellent cleaning performance and has an excellent effect in balance with styling performance. .

Hereinafter, although this invention is demonstrated in detail, these show an example of preferable embodiment.

Also, in the present invention, (meth)acryl means acryl or methacrylic, (meth)acryloyl means acryloyl or methacryloyl, and (meth)acrylate means acrylate or methacrylate, respectively. , The acrylic resin is a resin obtained by polymerizing a monomer component containing at least one (meth)acrylic monomer.

<Acrylic resin emulsion for hair dressing>

The acrylic resin emulsion for hair dressing of this invention is an acrylic resin emulsion obtained by emulsion-polymerizing a monomer composition [I] and a monomer composition [II], The said monomer composition [I] and a monomer composition [II] are following conditions (i) - (iii) is satisfied:

(i) at least one of the monomer composition [I] and the monomer composition [II] contains a (meth)acrylate-based monomer;

(ii) The glass transition temperature (Tg2) obtained by the formula of Fox of the polymer polymerized using the monomer composition [II] is obtained by the formula of Fox of the polymer polymerized using the monomer composition [I] at least 30°C higher than the glass transition temperature (Tg1);

(iii) The mixing ratio (weight ratio) of the monomer composition [I] and the monomer composition [II] is monomer composition [I]: monomer composition [II] = 50:50 to 99:1.

The acrylic resin emulsion for hair dressing may be an acrylic resin emulsion obtained by emulsion polymerization of only the monomer composition [I] and the monomer composition [II] in two steps, and an acrylic resin obtained by emulsion polymerization in three or more steps using other monomer compositions. It may be an emulsion. When emulsion-polymerizing in 3 steps or more, it can carry out at any timing before, after, or between emulsion polymerization of monomer composition [I] and monomer composition [II].

Among these, an acrylic resin emulsion obtained by emulsion polymerization of only the monomer composition [I] and the monomer composition [II] in two steps as a monomer component is preferable from the viewpoint of a simple operation procedure. Moreover, it is especially preferable from a viewpoint that it can manufacture stably that it is an acrylic resin emulsion obtained by emulsion-polymerizing only monomer composition [I] and monomer composition [II] in two steps in this order. In addition, other than a monomer component, the <other components> mentioned later can be used suitably.

In the present invention, at least one of the monomer composition [I] and the monomer composition [II] needs to contain a (meth)acrylate-based monomer, but preferably both the monomer composition [I] and the monomer composition [II] It is preferable that all contain a (meth)acrylate-type monomer from the point which there exists a tendency for an unreacted material to decrease, and the point which reduces the amount of residual monomers, ie, safety|security increases, and there are few odors.

In the present invention, the glass transition temperature (Tg2) obtained by the formula of Fox of the polymer polymerized using the monomer composition [II] is determined by the formula of Fox of the polymer polymerized using the monomer composition [I]. It is necessary to be a monomer composition [I] and a monomer composition [II] adjusted to be 30° C. or more higher than the glass transition temperature (Tg1), and the difference between the glass transition temperature (Tg1) and the glass transition temperature (Tg2) is preferably is 40°C or higher, particularly preferably 50°C or higher, more preferably 60°C or higher, still more preferably 90°C or higher.

When such a difference between Tg2 and Tg1 is too small, the to-be-cleaned property tends to fall, and it is unpreferable. In addition, the upper limit of the difference between Tg2 and Tg1 is 300 degreeC normally, Preferably it is 200 degreeC.

The Tg1 and Tg2 are calculated based on the glass transition temperature of each homopolymer by the following Fox formula. In addition, the glass transition temperature of the homopolymer in the formula of the following Fox is determined by the monomer species of the homopolymer.

That is, the glass transition temperature (Tga, Tgb, ... Tgn) of the homopolymer can use the values described in "Polymer Handbook 3rd Edition, John Wiley & Sons, Inc, 1989", respectively, and are not described in the document. Regarding the homopolymer of the non-monomer species, it can be confirmed by differential scanning calorimetry (DSC) or the like by polymerizing a homopolymer having an average molecular weight of 10,000 or more and less than 1,000,000. In addition, the said average molecular weight is a weight average molecular weight in polystyrene conversion by gel permeation chromatography (GPC).

From the above, the glass transition temperature (Tg1 and Tg2) of a polymer can be calculated|required from the monomer species and its weight fraction.

In addition, for some monomers, the glass transition temperature (Tg) of the homopolymer cannot be measured, but in this case, when the content of the monomer is about 5% by weight or less, the effect on the polymer properties is small, so the Fox formula is It shall not consider the said monomer as a structural component in this.

Tg: glass transition temperature of the polymer (K)

Tga: the glass transition temperature of the homopolymer of A of the monomer (K)

Wa: weight fraction of A of the monomer

Tgb: the glass transition temperature of the homopolymer of B of the monomer (K)

Wb: weight fraction of polymer B

Tgn: glass transition temperature (K) of homopolymer of monomer N

Wn: weight fraction of monomer N

(Wa+Wb+…Wn = 1)

As said Tg1, it is preferable that it is 0 degrees C or less, Especially preferably, it is -20 degrees C or less, More preferably, it is -30 degrees C or less.

If Tg1 is too high, the acrylic resin particles in the acrylic resin emulsion become too hard to obtain sufficient tackiness, and there is a tendency for re-hairing properties to decrease.

As a lower limit of Tg1, it is -80 degreeC normally, Preferably it is -75 degreeC.

As said Tg2, it is preferable that it is 30 degreeC or more, Especially preferably, it is 40 degreeC or more, More preferably, it is 50 degreeC or more, Especially preferably, it is 60 degreeC or more.

When Tg2 is too low, the acrylic resin particle in the acrylic resin emulsion obtained becomes too soft, and there exists a tendency for continuous hairstyling performance to be difficult to obtain. Moreover, when Tg2 is high, since the cohesive force of the acrylic resin obtained increases locally, there exists a tendency for adhesiveness to come out and to become favorable again.

As an upper limit of Tg2, it is 230 degreeC normally, Preferably it is 150 degreeC.

The mixing ratio (weight ratio) of the monomer composition [I] and the monomer composition [II] in the present invention needs to be monomer composition [I]: monomer composition [II] = 50:50 to 99:1, preferably is 60:40 to 98:2, particularly preferably 65:35 to 97:3, more preferably 70:30 to 95:5.

When there is too much compounding quantity of monomer composition [II] with respect to monomer composition [I], polymerization stability falls and it exists in the tendency for hair-setting property to become inadequate, and when too small, there exists a tendency for the balance of hair-setting property and to-be-washed property to fall.

<Monomer composition [I]>

Monomer composition [I] is demonstrated concretely.

As monomer composition [I], a (meth)acrylic-type monomer (I-1), a functional group containing monomer (I-2), etc. are mentioned, for example. The monomer composition [I] may consist only of one or two or more types of (meth)acrylic monomers (I-1), or may consist only of one or two or more types of functional group-containing monomers (I-2), and may consist of one or two or more types of ( It may contain a meth)acrylic-type monomer (I-1) and 1 or 2 or more types of functional group containing monomer (I-2). Especially, it is preferable to have (meth)acrylic-type monomer (I-1) as a main component.

Examples of the (meth)acrylic monomer (I-1) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t -Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, stearyl (meth) acrylate, etc. Aliphatic (meth)acrylate-based monomers; Aromatic (meth)acrylate-based monomers such as phenoxy (meth)acrylate; and trifluoroethyl (meth)acrylate.

In addition, these can be used individually or in combination of 2 or more types.

Among these, an aliphatic (meth)acrylate-based monomer having an alkyl group having 1 to 18 carbon atoms is preferable, and particularly preferably an alkyl group having 1 to 12 carbon atoms, from the viewpoint of a hair bundle feeling and re-hairing property. An aliphatic (meth)acrylate-based monomer, more preferably an aliphatic (meth)acrylate-based monomer having an alkyl group having 4 to 12 carbon atoms, particularly preferably n-butyl acrylate or 2-ethylhexyl acrylate am. Moreover, the combined use of 2-ethylhexyl acrylate and methyl methacrylate and the combined use of n-butyl acrylate and methyl methacrylate can also be used suitably.

As the functional group-containing monomer (I-2), for example, 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, an acetoacetyl group-containing monomer, a hydroxy A hydroxyl group-containing monomer, a carboxyl group-containing monomer, etc. are mentioned.

Among these, it is preferable to use the monomer which has two or more vinyl groups in a molecular structure, or a hydrolysable silyl group containing monomer from a viewpoint of improving the to-be-cleaned property without impairing hairdressing property.

Examples of the monomer having two or more vinyl groups in the molecular structure include divinylbenzene, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, ethylene glycol di(meth)acrylate, 1,2 -Propylene glycol di(meth)acrylate, 1,3-propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl Glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, allyl (meth)acrylate, etc. are mentioned.

Among these, ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and trimethylolpropane tri(meth)acrylate are (meth)acrylic monomer (I-1) or monomer composition [II] It is preferable from a viewpoint of being excellent in copolymerizability with the (meth)acrylate-type monomer contained in.

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

As said allyl group containing monomer, For example, the monomer which has two or more allyl groups, such as triallyloxyethylene, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, tetraallyloxyethane, allylglycy Dil ether, allyl acetate, etc. are mentioned.

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)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropylmethyldie (meth)acryloxy type silyl group containing monomers, such as oxysilane, are mentioned.

Among these, the (meth)acryloxy silyl group-containing monomer is preferable from the viewpoint of excellent copolymerizability with the (meth)acrylic monomer (I-1) or the (meth)acrylate monomer contained in the monomer composition [II]. do.

Examples of the acetoacetyl group-containing monomer include acetoacetic acid vinyl ester, acetoacetic acid allyl ester, diacetoacetic acid allyl ester, acetoacetoxyethyl (meth)acrylate, acetoacetoxyethyl crotnate, acetoacetoxypropyl (meth)acrylate, acetoacetoxypropyl crotonate, 2-cyanoacetoacetoxyethyl (meth)acrylate, etc. are mentioned.

As said hydroxyl group containing monomer, For example, (meth)acrylates, such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. These are mentioned, and 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferable from a viewpoint of the protective colloidal action at the time of emulsion polymerization, and to-be-cleaned property.

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 cinnamic acid. etc. are mentioned, Among these, acrylic acid and methacrylic acid are preferable from a viewpoint of the protective colloidal action at the time of emulsion polymerization and to-be-cleaned property.

As a content rate of the said (meth)acrylic-type monomer (I-1), it is preferable that it is 80-100 weight% with respect to the whole monomer composition [I], Especially preferably, it is 85-99.99 weight%, More preferably, it is 90 ~ 99.9% by weight.

When there are too few content rates of such a (meth)acrylic-type monomer (I-1), there exists a tendency for sufficient hairstyling performance not to be exhibited. Moreover, when 2 or more types of monomers are included as a (meth)acrylic-type monomer (I-1), it is preferable that the total content rate of these monomers is the said range.

The content ratio of the functional group-containing monomer (I-2) is preferably 0 to 20% by weight, particularly preferably 0.01 to 15% by weight, and still more preferably 0.1 to 10% by weight relative to the entire monomer composition [I]. % by weight.

When there is too much such a content rate, the acrylic resin becomes too hard, sufficient adhesive force does not come out, and there exists a tendency for hairstyling property to fall, and when there is too little, there exists a tendency for the effect of to-be-cleaned hard to be exhibited. Moreover, when 2 or more types of monomers are included as a functional group containing monomer (I-2), it is preferable that the total content ratio of these monomers is the said range.

In addition, when the functional group-containing monomer (I-2) contains a monomer having two or more vinyl groups in the molecular structure, the content ratio of the monomer having two or more vinyl groups in the molecular structure is the monomer composition [I] as a whole. , It is preferably 0.01 to 10% by weight, particularly preferably 0.05 to 5% by weight, and still more preferably 0.1 to 3% by weight.

In addition, when the functional group-containing monomer (I-2) contains a hydrolyzed silyl group-containing monomer, the content of the hydrolyzed silyl group-containing monomer is 0.01 to 5% by weight based on the entire monomer composition [I]. Preferably, it is 0.02 to 3 weight % especially preferably, More preferably, it is 0.05 to 2 weight %.

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, vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, and pivalic acid Vinyl ester-based monomers such as vinyl, vinyl capric acid, vinyl laurate, vinyl stearate, vinyl benzoate, Versatic acid vinyl, and 2-ethylhexanoate can be used.

<Monomer composition [II]>

The monomer composition [II] will be specifically described.

As monomer composition [II], a (meth)acrylic-type monomer (II-1), a functional group containing monomer (II-2), etc. are mentioned, for example. The monomer composition [II] may consist only of one or two or more types of (meth)acrylic monomers (II-1), or may consist of only one or two or more types of functional group-containing monomers (II-2), and may consist of one or two or more types of (meth) ) may include an acrylic monomer (II-1) and a monomer (II-2) containing one or two or more functional groups. Especially, it is preferable to have (meth)acrylic-type monomer (II-1) as a main component.

As said (meth)acrylic-type monomer (II-1), similarly to the said (meth)acrylic-type monomer (I-1), for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl ( meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, octyl Aliphatic (meth)acrylate-based monomers such as (meth)acrylate and stearyl (meth)acrylate; Aromatic (meth)acrylate-based monomers such as phenoxy (meth)acrylate; (meth)acrylic acid trifluorine Ethyl etc. are mentioned. In addition, these can be used individually or in combination of 2 or more types.

Among these, from the viewpoint of hair bundle feeling and re-hairing property, an aliphatic (meth)acrylate monomer having an alkyl group having 1 to 18 carbon atoms is preferable, and particularly preferably an aliphatic (meth)acrylate monomer having an alkyl group having 1 to 12 carbon atoms. An acrylate-based monomer, more preferably an aliphatic (meth)acrylate-based monomer having an alkyl group having 1 to 4 carbon atoms, particularly preferably methyl methacrylate, ethyl methacrylate, propyl methacrylate, n- butyl methacrylate.

Moreover, using methyl methacrylate as a main component in combination with another (meth)acrylate can also be used suitably.

As the functional group-containing monomer (II-2), as in the functional group-containing monomer (I-2), for example, a monomer having two or more vinyl groups in the molecular structure, a glycidyl group-containing monomer, an allyl group-containing monomer, a valence A decomposable silyl group-containing monomer, an acetoacetyl group-containing monomer, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, etc. are mentioned.

Among these, it is preferable to copolymerize the monomer which has two or more vinyl groups in a molecular structure, or a hydrolysable silyl group containing monomer from a viewpoint of improving the to-be-cleaned property without impairing hairdressing property.

Examples of the monomer having two or more vinyl groups in the molecular structure include divinylbenzene, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, ethylene glycol di(meth)acrylate, 1,2 -Propylene glycol di(meth)acrylate, 1,3-propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl Glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, allyl (meth)acrylate, etc. are mentioned.

Among these, ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and trimethylolpropane tri(meth)acrylate are (meth)acrylic monomer (II-1) or monomer composition [I] It is preferable from a viewpoint of being excellent in copolymerizability with the (meth)acrylate-type monomer contained in.

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

As said allyl group containing monomer, For example, the monomer which has two or more allyl groups, such as triallyloxyethylene, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, tetraallyloxyethane, allylglycy Dil ether, allyl acetate, etc. are mentioned.

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. Monomer; γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropylmethyl (meth)acryloxy type silyl group containing monomers, such as diethoxysilane, are mentioned.

Among these, a (meth)acryloxy-based silyl group-containing monomer is preferable from the viewpoint of excellent copolymerizability with the (meth)acrylic-based monomer (II-1) or the (meth)acrylate-based monomer contained in the monomer composition [I]. do.

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, acetoacetoxypropyl crotonate, 2-cyanoacetoacetoxyethyl (meth)acrylate, etc. are mentioned.

As said hydroxyl group containing monomer, For example, (meth)acrylates, such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. These are mentioned, and 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferable from a viewpoint of the protective colloidal action at the time of emulsion polymerization and to-be-cleaned property.

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 cinnamic acid. etc. are mentioned, Among these, acrylic acid and methacrylic acid are preferable from a viewpoint of the protective colloidal action at the time of emulsion polymerization and to-be-cleaned property.

As a content rate of the said (meth)acrylic-type monomer (II-1), it is preferable that it is 80-100 weight% with respect to the whole monomer composition [II], Especially preferably, it is 85-99.99 weight%, More preferably, it is 90 ~ 99.9% by weight.

When the content rate of such a (meth)acrylic-type monomer (II-1) is in the said range, there exists a tendency for sufficient hairstyling performance to be exhibited. Moreover, when 2 or more types of monomers are included as (meth)acrylic-type monomer (II-1), it is preferable that the total content rate of these monomers is the said range.

The content ratio of the functional group-containing monomer (II-2) is preferably 0 to 20% by weight, particularly preferably 0.01 to 15% by weight, and still more preferably 0.1 to 10% by weight with respect to the entire monomer composition [II]. % by weight. When there is too much such a content rate, there exists a tendency for polymerization stability to fall, and when too small, there exists a tendency for the effect of to-be-cleaned to be hard to understand. Moreover, when 2 or more types of monomers are included as a functional group containing monomer (II-2), it is preferable that the total content ratio of these monomers is the said range.

In addition, when the functional group-containing monomer (II-2) contains a monomer having two or more vinyl groups in the molecular structure, the content ratio of the monomer having two or more vinyl groups in the molecular structure is based on the monomer composition [II] as a whole. , It is preferably 0.01 to 10% by weight, particularly preferably 0.05 to 5% by weight, and still more preferably 0.1 to 3% by weight.

In addition, when the functional group-containing monomer (II-2) contains a hydrolyzed silyl group-containing monomer, the content of the hydrolyzed silyl group-containing monomer is 0.01 to 5 wt% with respect to the entire monomer composition [II]. Preferably, it is 0.02 to 3 weight% especially preferably, More preferably, it is 0.05 to 2 weight%.

In addition, within a range that does not impair the effects of the present invention, a small amount of styrene-based monomers such as styrene and α-methylstyrene; vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, pivalic acid; Vinyl ester-based monomers such as vinyl, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl basatic acid, and vinyl 2-ethylhexanoate can be used.

<Other ingredients>

In the acrylic resin emulsion according to the present invention, in addition to the above-mentioned monomer composition [I] and monomer composition [II], other components may be suitably used as needed. As such another component, an emulsifier, a polymerization initiator, a polymerization regulator, a plasticizer etc. are mentioned, for example, Among these, it is preferable to use an emulsifier. As such an emulsifier, Preferably, it is a water-soluble polymer, Especially preferably, it is polyvinyl alcohol-type resin (it is also described as "PVA-type resin" hereafter).

Further, in the present invention, it is preferable that the acrylic resin particles in the acrylic resin emulsion are dispersed and stabilized by the polyvinyl alcohol-based resin from the viewpoint of improving the to-be-cleaned property.

In addition, the said dispersion-stabilized state is a dispersed state which maintains a uniform state without sedimentation and separation even if the emulsion is left still at 23 degreeC for 1 month.

As said PVA-type resin, PVA-type resin which has the specific average saponification degree and average polymerization degree shown below is preferable.

As an average degree of saponification of PVA-type resin, it is preferable that it is 70-99.9 mol%, Especially preferably, it is 80-99.5 mol%, More preferably, it is 85-99 mol%.

If the average degree of saponification is too low, it is difficult for the polymerization to proceed stably, and even if the polymerization is completed, the storage stability of the emulsion tends to decrease. shows a tendency to disintegrate.

In addition, in this specification, an average degree of saponification can be calculated|required according to the calculation method of saponification degree described in JISK6726 (1994).

Moreover, as an average degree of polymerization of PVA-type resin, it is preferable that it is 50-3,000, Especially preferably, it is 100-2,000, More preferably, it is 200-1,000, Especially preferably, it is 200-500.

If the average degree of polymerization is too low, the protective colloidal ability at the time of emulsion polymerization becomes insufficient, and polymerization tends to be difficult to proceed stably. .

In addition, in this specification, the average degree of polymerization can be calculated|required according to the calculation method of the average degree of polymerization described in JISK6726 (1994).

In the present invention, PVA-based resin means PVA itself or, for example, modified with various modified species, and the degree of modification is usually 20 mol% or less, preferably 15 mol% or less, more preferably It is preferably 10 mol% or less.

Examples of the modified PVA-based resin include anion-modified PVA-based resin modified with an anionic group including a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group; a cation-modified PVA-based resin modified with a cationic group such as a quaternary ammonium group; acetoacetyl group , a modified PVA-based resin modified with various functional groups such as , diacetoneacrylamide group, mercapto group, and silanol group; PVA-based resin containing a 1,2-diol structural unit in a side chain;

As the PVA-based resin, a PVA-based resin containing a 1,2-diol structural unit in the side chain is preferable in terms of excellent dispersion stability when polymerizing a (meth)acrylic monomer, and particularly preferably represented by the formula (1) It is a PVA-type resin containing the 1,2-diol structural unit to be used.

[Formula 1]

(In Formula 1, R ¹ to ^{R 6} each independently represents a hydrogen atom or an organic group, and X represents a single bond or a bonded chain.)

In Formula 1, R ¹ to ^{R 6} each independently represents a hydrogen atom or an organic group. R ¹ ~R ⁶ are both preferably a hydrogen atom but, when the amount of the extent of not impairing the resin properties are also significantly organic rep. Although it does not specifically limit as said organic group, For example, a C1-C4 alkyl group, such as a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, is preferable, If necessary, it may have a substituent such as a halogen group, a hydroxyl group, an ester group, a carboxylic acid group, and a sulfonic acid group.

In formula (1), X is a single bond or a bond chain, and it is preferable that it is a single bond from a viewpoint of set holding power, no stickiness, matching with hair, etc. Although it does not specifically limit as said bonding chain, Hydrocarbons, such as alkylene, alkenylene, alkynylene, phenylene, and naphthylene (These hydrocarbons may be substituted with halogens, such as fluorine, chlorine, and an undo.) Other, -O-, -(CH ₂ O) _m -, -(OCH ₂ ) _m -, -(CH ₂ O) _m CH ₂ -, -CO-, -COC O-, -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-, etc. are mentioned. Here, each R is independently an arbitrary substituent, preferably a hydrogen atom or an alkyl group. In addition, m is a natural number. Among them, an alkylene group having 6 or less carbon atoms or -CH ₂ OCH ₂ - is preferable, and a methylene group or -CH ₂ OCH ₂ - is more preferable from the viewpoints of viscosity stability and heat resistance during production.

The PVA-based resin containing the 1,2-diol structural unit represented by the above formula (1) is, for example, (a) saponifying a copolymer of vinyl acetate and 3,4-diacetoxy-1-butene Method, (b) A method of saponifying and decarboxylating a copolymer of vinyl acetate and vinylethylene carbonate, (c) A copolymer of vinyl acetate and 2,2-dialkyl-4-vinyl-1,3-dioxolane It can be obtained by a method of saponifying and deketalizing the coal, (d) a method of saponifying a copolymer of vinyl acetate and glycerin monoallyl ether.

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 1 to 15 mol%, particularly preferably 1 to 12 mol%; More preferably, it is 2-10 mol%, Especially preferably, it is 2-9 mol%.

When the content of such 1,2-diol structural units is too low, the mechanical stability of the emulsion tends to decrease, and when it is too high, the stability during polymerization decreases, and it tends to be difficult to obtain a stable emulsion with a high nonvolatile content. .

Further, the content of side chain 1,2-diol unit in the PVA-based resin is, though completely saponified PVA ¹ H-NMR spectrum can be obtained from (solvent:: DMSO-d _6, internal standard tetramethylsilane), specifically can be calculated from the peak area derived from the hydroxyl group proton, methine proton, methylene proton, the main chain methylene proton, or the hydroxyl group proton connected to the main chain in the 1,2-diol unit.

In addition, the average degree of saponification of the PVA-based resin containing the 1,2-diol structural unit represented by the formula (1) is preferably 85 mol% or more, more preferably 86.5 to 99.8 mol%, particularly preferably 95 to 99 mol%.

When the average degree of saponification is too small, the stability of the emulsion during polymerization is lowered, and it tends to be difficult to obtain the desired emulsion.

The average degree of polymerization of the PVA-based resin containing the 1,2-diol structural unit represented by the formula (1) is preferably 50 to 3,000, more preferably 100 to 2,500, still more preferably 200 to 2,000, and particularly preferably Usually 200-500.

If the average degree of polymerization is too small, it tends to be difficult to industrially manufacture the PVA-based resin, and when it is too large, the viscosity of the emulsion tends to become too high or the polymerization stability of the emulsion tends to decrease.

Moreover, PVA-type resin sets it as aqueous solution using an aqueous medium normally, and this is used about the process of emulsion polymerization. Here, the aqueous medium refers to water or an alcoholic solvent mainly composed of water, and water is preferable.

Although it does not specifically limit about the quantity (non-volatile matter) of PVA-type resin in the said aqueous solution, From a viewpoint of handling easiness, it is preferable that it is 5 to 30 weight%.

It is preferable that the usage-amount of the said PVA-type resin is 0.01-40 weight part with respect to a total of 100 weight part of monomer composition [I] and monomer composition [II], Especially preferably, it is 0.1-30 weight part, More preferably, 0.5 to 20 parts by weight.

When the amount of the PVA-based resin used is too small, the amount of protective colloid during emulsion polymerization is insufficient, and polymerization stability tends to decrease. have.

Examples of the emulsifier other than the PVA-based resin include anionic, cationic, and nonionic surfactants, water-soluble polymers having protective colloidal properties other than PVA-based resins, and water-soluble oligomers.

Examples of the surfactant include anionic surfactants such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate, and those having a Pluronic structure or a polyoxyethylene structure. An ionic surfactant is mentioned. Further, as the surfactant, a reactive surfactant having a radically polymerizable unsaturated bond in its structure can also be used. These can be used individually or in combination of 2 or more types.

The use of the surfactant has the effect of smoothly advancing the emulsion polymerization and making it easier to control (effect as an emulsifier), or suppressing the generation of coarse particles or block-like substances generated during polymerization. However, when many of these surfactants are used as emulsifiers, the graft ratio tends to decrease. For this reason, when using surfactant, it is preferable that the usage-amount is an auxiliary quantity with respect to PVA-type resin, ie, to reduce it as much as possible.

Examples of the water-soluble polymer having a protective colloidal ability other than the PVA-based resin include hydroxyethyl cellulose, polyvinyl pyrrolidone, and methyl cellulose. These are used individually or in combination of 2 or more types. These are effective in changing the viscosity of the emulsion by changing the emulsion thickening or the particle diameter 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, and an alkylene glycol group is preferable, and among them, a polymer or copolymer having a degree of polymerization of about 10 to 500 is particularly suitable. . Specific examples of the water-soluble oligomer include, for example, amide copolymers such as 2-methacrylamide-2-methylpropanesulfonic acid copolymer, sodium methacrylate-4-styrenesulfonate copolymer, and styrene/maleic acid copolymer. , melamine sulfonic acid formaldehyde condensate, poly (meth) acrylate, and the like. Specific examples 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 radically polymerizable reactive emulsifier in advance alone or with another monomer. These are used individually or in combination of 2 or more types.

As the polymerization initiator, those that can be used for ordinary emulsion polymerization can be used, for example, inorganic peroxides such as potassium persulfate, sodium persulfate, ammonium persulfate; organic peroxides, azo initiators, hydrogen peroxide, butyl peroxide Peroxides, such as; And, the redox polymerization initiator etc. which combined these with reducing agents, such as acidic sodium sulfite and L-ascorbic acid, etc. are mentioned. These can be used individually or in combination of 2 or more types.

Among these, ammonium persulfate and potassium persulfate are preferable from a viewpoint of superposition|polymerization being easy.

As said polymerization regulator, it can select suitably from a well-known thing. As these polymerization regulators, a chain transfer agent, a buffer, etc. are mentioned, for example.

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 dodecylmercaptan and lauryl. Mercaptans, such as a mercaptan, a normal mercaptan, thioglycolic acid, thioglycolic acid octyl, and thioglycerol, etc. are mentioned. These can be used individually or in combination of 2 or more types. Use of a chain transfer agent is effective at the point which superposes|polymerizes stably, and it is preferable to use in order to adjust the polymerization degree of an acrylic resin.

As said buffer, sodium acetate, ammonium acetate, dibasic sodium phosphate, sodium citrate etc. are mentioned, for example. These can be used individually or in combination of 2 or more types.

As said plasticizer, an adipate type plasticizer, a phthalic acid type plasticizer, a phosphoric acid type plasticizer, etc. can be used.

The usage-amount of these other components can be suitably selected according to the objective in the range which does not impair the effect of this invention.

<Method for producing acrylic resin emulsion>

The manufacturing method of the acrylic resin emulsion obtained by emulsion-polymerizing monomer composition [I] and monomer composition [II] in this order in two steps is demonstrated.

The acrylic resin emulsion of the present invention uses, for example, a PVA-based resin as a dispersion stabilizer, first emulsion-polymerizes the monomer composition [I] to obtain a first emulsion, and then prepares the monomer composition [II] 1 The method of emulsion polymerization in an emulsion is mentioned.

Usually, emulsion polymerization is performed using said other component, such as a polymerization initiator, a polymerization regulator, an auxiliary|assistant emulsifier, as needed, in addition to PVA-type resin and the said monomer component. In addition, reaction conditions for polymerization can be suitably selected according to the kind, purpose, etc. of a monomer.

As a method of emulsion polymerization, for example, a monomer dropping emulsion polymerization method in which water and a PVA-based resin are put into a reaction can, the temperature is raised, and a monomer component and a polymerization initiator are added dropwise; An emulsion monomer dropping emulsion polymerization method in which a water-soluble polymer having a protective colloidal ability other than a resin and/or a PVA-based resin is dispersed and emulsified with water and then the dispersion/emulsified monomer is added dropwise, but when using a hydrophobic monomer From the viewpoints of reactivity, management and controllability of the polymerization process, the emulsion monomer dropping polymerization method is advantageous.

In addition, in order to impart stability to the emulsion and impart water solubility and/or redispersibility to water, it is also possible to post-add a PVA-based resin and/or a water-soluble polymer having a protective colloidal ability other than the PVA-based resin at the end of the polymerization reaction.

More specifically, the emulsion polymerization process will be described below.

In the monomer dropping emulsion polymerization, for example, first, water, a PVA-based resin, and, if necessary, an auxiliary emulsifier are added to a reaction can, and the temperature is raised (usually 40 to 90° C.), and then, the monomer composition [I] A part (normally 0.1 to 50% by weight, preferably 1 to 30% by weight relative to the total amount of the monomer composition [I]) and a polymerization initiator are added to this reaction can to conduct initial polymerization. Next, the remaining monomer composition of the monomer composition [I] is added to the reaction can while being added dropwise or at a time, and polymerization proceeds while further adding a polymerization initiator as necessary. Next, the monomer composition [II] is added to the reaction can collectively or dropwise, and polymerization proceeds while adding a polymerization initiator again as necessary. When it is judged that the polymerization reaction is complete, the reaction can is cooled, and the target acrylic resin emulsion can be taken out.

In addition, in the emulsion monomer dropwise emulsion polymerization method, for example, first, water, optionally a PVA-based resin, and an auxiliary emulsifier are added to a reaction can, and the temperature is raised (usually 40 to 90° C.), and then PVA-based A water-soluble polymer having a protective colloidal ability other than a resin and/or a PVA-based resin, a part of the monomer composition [I] emulsified and dispersed with an auxiliary emulsifier and water as necessary (based on the total amount of the monomer composition [I], usually 0.1 to 50 weight %, preferably 1 to 30% by weight) and a polymerization initiator are added to this reaction can to conduct initial polymerization. Next, the remaining monomer composition of the monomer composition [I] is added to the reaction can while being added dropwise or at a time, and polymerization proceeds while further adding a polymerization initiator as necessary. Then, a water-soluble polymer having a protective colloidal ability other than the PVA-based resin and/or the PVA-based resin, as necessary, a monomer composition [II] emulsified and dispersed with an auxiliary emulsifier and water is added to the reaction can in batches or while dropping, as needed. Then, the polymerization proceeds while adding the polymerization initiator again. When it is judged that the polymerization reaction is complete, the reaction can is cooled, and the target acrylic resin emulsion can be taken out.

In addition, without performing the initial polymerization, the whole amount of the monomer composition [I] and the polymerization initiator are added dropwise to the reaction can, and then the whole amount of the monomer composition [II] and the polymerization initiator are added dropwise to the reaction can while the method is added. can also be carried out. Moreover, when the said reaction temperature is less than 70 degreeC, it is preferable to set it as a Redox polymerization reaction system using a reducing agent together from a viewpoint that reaction progresses smoothly.

In the emulsion polymerization of the monomer composition [I], polymerization is continued for usually 5 minutes to 1 hour (preferably 10 minutes to 30 minutes) at the time when the total amount of the monomer composition [I] is added, followed by polymerization of the monomer composition [I] At a point in time when the polymerization rate of is exceeded 90% (preferably 95%), the polymerization is completed, and it can be considered that the first emulsion is obtained, and emulsion polymerization of the monomer composition [II] can be continued.

In the present invention, the acrylic resin emulsion obtained by emulsion polymerization is typically uniform milky white, and the average particle diameter of the acrylic resin in the acrylic resin emulsion is preferably 0.2 to 2 µm, more preferably 0.3 to 1.5 μm.

In addition, here, an average particle diameter can be measured by a conventional method, for example, laser analysis/scattering type particle size distribution measuring apparatus "LA-950S2" (made by Horiba Corporation).

In the present invention, at least a part of the PVA-based resin is grafted to the acrylic resin, the obtained storage stability of the acrylic resin emulsion itself before drying and the difference in measurement values in the measurement of adhesive strength is reduced from the viewpoint of desirable.

When the PVA-based resin is grafted onto the acrylic resin, the value (W) expressed by the following formula (2) is preferably 90% by weight or less, more preferably 85% by weight or less, and still more preferably 80% by weight. is below. Moreover, as a minimum, it is 1 weight% normally, Preferably it is 5 weight%, More preferably, it is 10 weight%. Such a value serves as a criterion for the degree of grafting, and if this value is too low, the degree of grafting is low, the protective colloidal action during emulsion polymerization is lowered, and polymerization stability tends to be lowered, etc. If it is too high, it tends to become difficult to produce a stable emulsion at a high concentration.

The value (W) of the formula (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 in boiling water and acetone for 8 hours, respectively, to remove ungrafted resin or the like. In this case, the absolute film dry weight before extraction is w ₁ (g), and the total film dry weight after extraction is w ₂ (g), and is calculated by the following formula (2).

As a method of adjusting the value (W) of the said Formula (2), the method of changing an emulsion polymerization temperature, the perlactate used as a catalyst for polymerization, the method of using a trace amount reducing agent together, etc. are mentioned. For example, the value (W) can be made high by making emulsion polymerization temperature high, and the value (W) can be made low by making it low. Moreover, when acidic sodium sulfite etc. are used as a reducing agent, the value (W) becomes high.

In this invention, various additives can further be added to the acrylic resin emulsion after emulsion polymerization as needed. Examples of such additives include organic pigments, inorganic pigments, water-soluble additives, pH adjusters, preservatives, and antioxidants.

In this way, the acrylic resin emulsion according to the present invention is obtained, and when using the acrylic resin emulsion, it is preferably adjusted to 0.1 to 65% by weight as a nonvolatile matter normally.

In addition, when using such an acrylic resin emulsion as a hair dressing, when using together other compounding components called resin and an additive mentioned later, it is 30 to 60 weight% normally as a non-volatile matter, and the use of another resin or additive is It is preferable at the point which is hard to restrict|limit.

Moreover, when using such an acrylic resin emulsion independently as a hair dressing, it is preferable at the point which it is easy to apply|coat uniformly with respect to hair that it is 1 to 10 weight% of a non-volatile matter normally.

By the above method, the acrylic resin emulsion according to the present invention is obtained. Such an acrylic resin emulsion is used for hair dressing, and the hair dressing using the emulsion exhibits desired performance such as styling properties, re-hair-hairing performance, tactile properties, and to-be-cleaned performance.

The hair dressing which concerns on this invention can contain the above-mentioned acrylic resin emulsion, what used the acrylic resin emulsion independently may be sufficient, and what used the acrylic resin emulsion and various compounding agents together may be sufficient.

The hair dressing of the present invention WHEREIN: It is preferable that the acrylic resin emulsion for hair dressing of this invention contains 1 weight% or more (solid content conversion) in a hair dressing, More preferably, it is 3 weight% or more (solid content conversion), further Preferably it is 5 weight% or more (in conversion of solid content). Moreover, as an upper limit, Preferably it is 70 weight% (solid content conversion), More preferably, it is 60 weight% (solid content conversion), More preferably, it is 50 weight% (solid content conversion). When there are too few acrylic resin emulsions for hair dressings of this invention, there exists a tendency for hairstyling power to fall, and when there is too much, there exists a tendency for washability to fall easily.

In the hair dressing of the present invention, various compounding components used as a well-known general hair dressing agent in the acrylic resin emulsion are, for example, oil agents, polyhydric alcohols, lower alcohols, surfactants, ultraviolet absorbers, fragrances, antioxidants, and moisturizing agents. , a refreshing agent, vitamins, plant extracts, etc. can be prepared by appropriately mixing according to the purpose.

Examples of the oil agent include oils and fats such as sunflower oil, cottonseed oil, soybean oil, olive oil, palm oil, castor oil, jojoba oil, camellia oil, mink oil; beeswax, carnauba wax, candelilla wax wax), rice bran wax, shellac wax, whale wax, lanolin, etc.; ceresin, paraffin wax, liquid paraffin, liquid isoparaffin, microcrystalline wax ), polyethylene powder, polyethylene wax, Fischer Tropsch wax, petrolatum, squalene and other hydrocarbon oils; lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, 2-ethyl part higher fatty acids such as carbonic acid, isopentanoic acid, 2-methylpentanoic acid, 2-ethylpentanoic acid, isostearic acid, and 12-hydroxystearic acid; lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol ( oleyl alcohol), lanolin alcohol, behenyl alcohol, and cetstearyl alcohol; ethyl oleate, isopropyl myristate, isopropyl palmitate, myristyl myristate, cetyl palmitate, oleyl oleate, octyl myristate Dodecyl, octyldodecyl oleate, ethyl isostearate, isopropyl isostearate, cetyl 2-ethylhexanoate, cetylstearyl 2-ethylhexanoate, glyceryl tri-2-ethylhexanoate, glyceryl triisopalmitate, tetra Fatty acid ester oils such as pentaerythritol -2-ethylhexanoate, isocetyl octanoate, isotearyl octanoate, isocetyl isostearate, octyldodecyl isostearate, and octyldodecyl dimethyloctanoate; methylpolysiloxane, highly polymerized Methylpolysiloxane, methylphenylpolysiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, methylcyclopolysiloxane, alcohol-modified silicone, alkyl-modified silicone, amino-modified silicone and silicone oils such as epoxy-modified silicone. These can be used independently or can use 2 or more types together.

It is preferable that content of such an oil agent is 0.5 to 50 weight% from a viewpoint of emulsification normally in the hair dressing total amount, Especially preferably, it is 1 to 40 weight%. Moreover, although it is preferable to set it as possible as little content as possible from a viewpoint of reducing the oil content or stickiness of a hairdressing agent, by using the acrylic resin emulsion of this invention, the usage-amount of an oil agent can be reduced or not used.

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, and the like can be exemplified. These may be used independently, or 2 or more types can be used for them.

It is preferable that content of such polyhydric alcohol is 0.1 to 20 weight% from a viewpoint of a usability|use_condition in the hair dressing total amount, Especially preferably, it is 0.5 to 15 weight%.

The acrylic resin emulsion for hair dressing of the present invention is, for example, diluting the acrylic resin emulsion with water, polyhydric alcohol, lower alcohol, etc. and using it as a liquid hair dressing, or emulsifying the oil in the acrylic resin emulsion with a surfactant and water. It can be used or used as a hair dressing of a viscous liquid type or a cream type by blending the dispersed product.

＜Hairdressing method＞

As a hairdressing method using the hair dressing containing the acrylic resin emulsion for hair dressing which concerns on this invention, the hairdressing method including the following processes (A) and (B) is mentioned, for example:

(A) The step of applying the acrylic resin emulsion for hair dressing obtained by emulsion polymerization of the monomer composition [I] and the monomer composition [II] to the hair in an effective hairdressing amount;

(B) A step of trimming the hair into a desired shape in at least one of before, simultaneously with, and after the step (A).

However, the monomer composition [I] and the monomer composition [II] satisfy the following conditions (i) to (iii):

(i) at least one of the monomer composition [I] and the aforementioned monomer composition [II] contains a (meth)acrylate-based monomer;

(ii) The glass transition temperature (Tg2) obtained by the formula of Fox of the polymer polymerized using the monomer composition [II] is obtained by the formula of Fox of the polymer polymerized using the monomer composition [I] temperature is more than 30°C above the glass transition temperature (Tg1);

(iii) The compounding ratio (weight ratio) of the said monomer composition [I] and the said monomer composition [II] is monomer composition [I]: monomer composition [II] = 50:50-99:1.

By hairdressing in this way, a desired hair shape can be easily formed. And since the hair dressing of this invention is excellent in water solubility and/or redispersibility to water, it can wash away easily.

In addition, the effective hairstyling amount of the said acrylic resin emulsion for hair dressings is preferable from a viewpoint that 0.01-1g can be hairstyling efficiently per hair bundle of length 20cm x weight 1.2g.

Example

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to the following Example unless the summary is exceeded.

In addition, in the Example, "part" and "%" mean a weight basis.

First, various acrylic resin emulsions were prepared as follows. In addition, the nonvolatile matter and the viscosity of the acrylic resin emulsion were measured by the following method, and the glass transition temperature was measured according to the above method.

＜Non-volatile matter＞

1 g of the sample was spread and accurately measured in a container of an aluminum foil plate molded to the same bottom area as a flat weighing bottle 50 mm×30 mm prescribed in JIS R 3503 (1994). The container was placed in the center of the thermostat, dried at 105°C±2°C for 60±5 minutes, cooled in a desiccator and weighed.

Then, it computed by the following formula.

N = (Wd / Ws)×100

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

<Viscosity>

It measured with a Brookfield type viscometer (For example, the Tokyo Keigi Co., Ltd. make, BL type|mold viscometer). About 500 ml of the sample was placed in the sample container so that air bubbles were not mixed, and the sample container was held so that the liquid level of the sample was lower than the liquid level of the heat transfer medium in the constant temperature bath. If necessary, the mixture was mixed with a glass rod and the sample temperature was measured at 23±1°C.

The viscosity was computed by the following formula (two significant digits).

η = Kn×θ

(Here, η is the viscosity (mPa·s), Kn is the conversion multiplier attached to the viscometer, and θ is the average of the viscometer readings of two measurements.)

<Example 1: Acrylic resin emulsion (a)>

Using the following monomer composition [I] and monomer composition [II], the emulsion X, the emulsion Y, and the solution Z shown as follows were prepared beforehand.

Monomer composition [I]: 75 parts of 2-ethylhexyl acrylate, 16 parts of methyl methacrylate, 0.9 parts of ethylene glycol dimethacrylate (manufactured by Mitsubishi Rayon, trade name "Acryester ED"), Tg1 = -52 ℃

-Monomer composition [II]: 9 parts of methyl methacrylate, 0.1 part of ethylene glycol dimethacrylate (manufactured by Mitsubishi Rayon; trade name "Acryester ED"), Tg2 = 105°C

Emulsion X: 64 parts of deionized water, unmodified PVA-based resin (average degree of saponification of 88 mol%, average degree of polymerization 500/manufactured by Nippon Kosei Kogyo Co., Ltd.) 4.5 parts, monomer composition [I] at 1200 rpm using a turbine blade 20 minutes, emulsified.

Emulsion Y: 7 parts of deionized water, 0.5 parts of unmodified PVA-based resin (average degree of saponification of 88 mol%, average degree of polymerization of 500/manufactured by Nippon Kosei Kogyo Co., Ltd.), monomer composition [II] at 1200 rpm using a turbine blade 20 minutes, emulsified

・Solution Z: 2.7 parts of 10% APS (ammonium persulfate) aqueous solution

PVA (average degree of saponification of 99 mol%, average degree of polymerization 300; The content of the 1,2-diol structural unit of the side chain is 8 mol%, 10 parts (manufactured by Nippon Kosei Kogyo Co., Ltd.), 0.2 parts of sodium hydrogensulfite, and 0.4 parts of sodium carbonate trihydrate were completely dissolved, and the temperature was raised to 75°C.

To the reaction can, first, 11% of emulsion X and 30% of solution Z were added at once and stirred for 45 minutes, then 89% of the remaining emulsion X and 53% of solution Z were added dropwise over 3.1 hours, and the dropping was completed Then, stirring was continued for 10 minutes to obtain a first emulsion.

Then, the total amount of the emulsion Y and 7% of the solution Z were added dropwise over 0.4 hours, and 10 minutes after the completion of the dropping, 5% of the solution Z was added at once, and after another 35 minutes, 5% of the solution Z was added at once for 45 minutes. stirred. During the polymerization, polymerization was carried out so that the internal temperature of the polymerization solution was maintained at 75 to 80°C. Next, the internal temperature is 55° C., and 1.7 parts of a 10% aqueous solution of perbutyl H-69 (manufactured by NOF Corporation) is added at once, and 3.4 parts of a 5% aqueous solution of vitamin C is divided into two portions and added at intervals of 30 minutes, a total of 1 The mixture was stirred while maintaining an internal temperature of 50 to 55°C to obtain a second emulsion.

The obtained second emulsion was cooled to obtain an acrylic resin emulsion (a) (43% non-volatile content; viscosity 420 mPa·s (B-type viscometer 12 rpm, 23°C)). In addition, the acrylic resin emulsion (a) was dispersion-stabilized.

<Example 2: Acrylic resin emulsion (b)>

In Example 1, the monomer composition [I] 68 parts of 2-ethylhexyl acrylate, 23 parts of methyl methacrylate, 0.9 parts of ethylene glycol dimethacrylate (manufactured by Mitsubishi Rayon; trade name "Acryester ED"); In the same manner as in Example 1, except that Tg1 = -43°C, an acrylic resin emulsion (b) (43% nonvolatile content; viscosity 1000mPa·s (B-type viscometer 3312rpm, 23°C)) was obtained. The acrylic resin emulsion (b) was dispersion-stabilized.

<Comparative Example 1: Acrylic resin emulsion (a')>

The emulsion liquid X and the solution Z shown below were prepared previously using the following monomer composition [I].

Monomer composition [I]: 75 parts of 2-ethylhexyl acrylate, 35 parts of methyl methacrylate, 1 part of ethylene glycol dimethacrylate (manufactured by Mitsubishi Rayon; trade name "Acryester ED"), Tg1 = -43 ℃

Emulsion X: 71 parts of deionized water, 5 parts of unmodified PVA-based resin (average degree of saponification of 88 mol%, average degree of polymerization of 500/manufactured by Nippon Kosei Kogyo Co., Ltd.), monomer composition [I] at 1200 rpm using a turbine blade 20 minutes, emulsified.

・Solution Z: 2.7 parts of 10% APS (ammonium persulfate) aqueous solution

In a reaction can made from SUS equipped with a cooling tube and a stirring blade, in deionized water (72 parts), a PVA-based resin containing a 1,2-diol structural unit in the side chain (average degree of saponification of 99 mol%, average degree of polymerization 300, side chain 1,2-diol structural unit content of 8 mol% 10 parts (manufactured by Nippon Kosei Kogyo Co., Ltd.), 0.2 parts of sodium hydrogensulfite, and 0.4 parts of sodium carbonate trihydrate were completely dissolved, and the temperature was raised to 75°C.

To the reaction can, first 10% of emulsion X and 30% of solution Z were added at once and stirred for 45 minutes, then 90% of the remaining emulsion X and 60% of solution Z were added dropwise over 3.5 hours, internal temperature 75 After 10 minutes of termination at -80°C, 5% of solution Z was added at once, and after another 35 minutes, 5% of solution Z was added at once, followed by stirring for 45 minutes. During the polymerization, polymerization was carried out so that the internal temperature of the polymerization solution was maintained at 75 to 80°C. Next, the internal temperature is 55° C., 1.7 parts of a 10% aqueous solution of perbutyl H-69 (manufactured by NOF Corporation) is added at once, and 3.4 parts of a 5% aqueous solution of vitamin C is divided into two portions and added at intervals of 30 minutes, a total of 1 It stirred while maintaining the internal temperature of 50-55 degreeC.

Then, it cooled and obtained the acrylic resin emulsion (a') (43% of non-volatile matter; viscosity 490mPa*s (B-type viscometer 12rpm, 23 degreeC)). The acrylic resin emulsion (a') of Comparative Example 1 was dispersion-stabilized.

<Comparative example 2: acrylic resin emulsion (b')>

In Comparative Example 1, the monomer composition [I] 68 parts of 2-ethylhexyl acrylate, 32 parts of methyl methacrylate, 1 part of ethylene glycol dimethacrylate (manufactured by Mitsubishi Rayon; trade name "Acryester ED") 1 part; Tg1 = -35 ° C., except that in the same manner as in Comparative Example 1, to obtain an acrylic resin emulsion (b') (non-volatile content 43%; viscosity 810 mPa s (B-type viscometer 12 rpm, 23 ° C)). The acrylic resin emulsion (b') of Comparative Example 2 was dispersion-stabilized.

<Production of hair dressing solution for styling performance test>

For Examples 1 and 2, acrylic resin emulsion (a) and acrylic resin emulsion (b), respectively, for Comparative Examples 1 and 2, acrylic resin emulsion (a') and acrylic resin emulsion (b'), respectively All were diluted using deionized water so that a nonvolatile matter might be 3%, and it was set as the hair dressing solution for styling performance tests, respectively.

Using the hair dressing solution for a styling performance test, hairstyling performance (set power), rehairing performance (reset power, reset retention power), and tactile property were evaluated as follows.

<hairdressing performance (set power)>

0.5 g of the hair dressing solution for the styling performance test was uniformly applied to the hair bundle (length 20 cm × weight 1.2 g; Ketabaya) with a dropper, and then applied to mix more evenly with a finger wearing a vinyl glove. Prepare the bundle with your fingers so that the width of the bundle is about 1 cm, dry it in a blow dryer at 100°C × 1 minute, then hold the end of the hair with your hand at an angle of about 45° from the top with the side facing down, and the hair bundle is fixed. A sensory evaluation was performed to see if it was being done. The evaluation method is as follows.

(Evaluation standard)

○… Even if you shake it a little, it stays well-groomed.

△… Shake it a little to spread the ends of the hair a little.

×… If it is not organized or shakes a little, the ends of the hair are scattered.

<Reset performance (reset power)>

After unraveling the hair bundle after performing the said hairstyling power evaluation with a finger and making it disturb with a comb again, the hair bundle state at the time of making a hair bundle with a finger was sensory-evaluated again. The evaluation method is as follows.

(Evaluation standard)

○… Again the hair bundles are arranged (refined).

△… Tidyed up, but hair bundles spread slightly.

×… It is not bristle and does not straighten.

In addition, in the above evaluation, "○" indicates excellent performance, and "Δ" is practically acceptable. In addition, "x" means that the performance is inferior.

<Reset performance (reset holding power)>

The hair bundle state at the time of lightly whisking the hair bundle after performing the said rehairing performance (reset power) evaluation was sensory-evaluated. The evaluation method is as follows.

(Evaluation standard)

○… Hair bundles are kept in order and almost do not collapse (re-haircutting is maintained).

△… Hair bundles are slightly spread.

×… Hair bundles are largely scattered (re-hairing is not maintained).

<Tactility>

The feeling of touch with a finger was evaluated for the settling feeling of the hair at the time of said re-hair-growth performance (reset power) evaluation. The evaluation method is as follows.

(Evaluation standard)

○… moist and smooth

△… It's a little crumbly.

×… It's quite clunky.

<Preparation of hair dressing solution for to-be-cleaned performance test>

For Examples 1 and 2, acrylic resin emulsion (a) and acrylic resin emulsion (b), respectively, in Comparative Examples 1 and 2, acrylic resin emulsion (a') and acrylic resin emulsion (b'), respectively , was used as it was, and it was set as the hair dressing solution for to-be-cleaned performance tests, respectively.

<Performance to be cleaned (hot water)>

The hair dressing solution for cleaning performance test was applied to a 50 μm thick PET (polyethylene terephthalate) film with a 100 μm applicator, dried at 23° C., 50% RH for 30 minutes, and a coating film with a thickness of about 25 μm (drying) got On the coating film, pour 1 drop of deionized water at 60°C with a dropper and rub lightly once to draw a circle with a diameter of about 1 cm with your finger. registered trademark)). Thereafter, another drop of 60°C deionized water was poured with a dropper, and the operation of rubbing with a finger was repeated 10 times in total. The washing|cleaning degree of the hair dressing solution in the form of a coating film was evaluated visually. The evaluation method is as follows.

(Evaluation standard)

○… More than 70% and 100% could be wiped off.

△… More than 30% and less than 70% could be wiped off.

×… More than 0 and less than 30% were able to be wiped off.

<Performance to be cleaned (cold water)>

The hair dressing solution for cleaning performance test is applied to a 50 μm thick PET (polyethylene terephthalate) film with a 100 μm applicator, dried at 23° C., 50% RH for 30 minutes, and a coating film with a thickness of about 25 μm (drying) got On the coating film, pour 1 drop of 15°C deionized water with a dropper, and after 1 minute, tap lightly with your finger 10 times, registered trademark)). The washing|cleaning degree of the coating-film form hair dressing solution was evaluated visually. The evaluation method is as follows.

(Evaluation standard)

○… More than 70% and 100% could be wiped off.

△… More than 30% and less than 70% could be wiped off.

×… More than 0 and less than 30% were able to be wiped off.

The result of the test using the composition of Examples 1 and 2 and Comparative Examples 1 and 2, a glass transition temperature, and a hair dressing solution is shown in Table 1.

It can be seen that in the hair dressing using the acrylic resin emulsion obtained by the two-stage polymerization of Examples 1 and 2, the styling performance (hairdressing performance, rehairing performance, and tactile properties) and the cleaning performance are excellent in a good balance.

On the other hand, in the acrylic resin emulsions obtained by the non-multistage polymerization of Comparative Examples 1 and 2, although the hairdressing performance, re-hairing property, and tactile properties were good, it was found that the cleaning performance, particularly the cleaning ability in cold water, was inferior.

Although this invention was detailed also demonstrated with reference to specific embodiment, it is clear for those skilled in the art that various changes and correction can be added without deviating from the mind and range of this invention. This application is based on the JP Patent application (Japanese Patent Application No. 2014-044861) for which it applied on March 7, 2014, The content is taken in here as a reference.

(Industrial Applicability)

Since the acrylic resin emulsion for hair dressing of the present invention is excellent in a well-balanced manner in styling performance (hairdressing performance, rehairing performance, tactile property) and to-be-cleaned performance, various compounding agents can be used in combination, so that it can be used in various formulations. It is useful and applicable.

Claims (7)

The emulsion polymer of monomer composition [I] and the emulsion polymer of monomer composition [II] are contained, The acrylic resin emulsion for hair dressings characterized by the above-mentioned,
The acrylic resin particles in the acrylic resin emulsion are dispersed and stabilized by a polyvinyl alcohol-based resin,
Acrylic resin emulsion for hair dressing, characterized in that the monomer composition [I] and the monomer composition [II] satisfy the following conditions (i) to (iii):
(i) at least one of the monomer composition [I] and the monomer composition [II] contains a (meth)acrylate-based monomer;
(ii) the glass transition temperature (Tg2) of the emulsion polymer of the monomer composition [II] obtained by Fox's formula is 30 ℃ or higher, the glass transition temperature (Tg1) is -80 ℃ to 0 ℃, the glass transition temperature (Tg2) is 30 ℃ to 230 ℃;
(iii) The mixing ratio (weight ratio) of the monomer composition [I] and the monomer composition [II] is monomer composition [I]: monomer composition [II] = 50:50 to 99:1. The method according to claim 1,
The polyvinyl alcohol-based resin is an acrylic resin emulsion for hair dressing, characterized in that it contains a side chain 1,2-diol structural unit represented by the following formula (1).
[Formula 1]

(In Formula 1, R ¹ to ^{R 6} each independently represents a hydrogen atom or an organic group, and X represents a single bond or a bonded chain, wherein the organic group is an alkyl group having 1 to 4 carbon atoms, and the bonding chain has 6 carbon atoms. The following alkylene groups or -(CH ₂ O)CH ₂ -). As a manufacturing method of the acrylic resin emulsion for hair dressing of claim 1 or 2,
Using only the above monomer composition [I] and the above monomer composition [II], first emulsion polymerization of the above monomer composition [I] is performed, then the above monomer composition [II] is added to emulsion polymerization of the above monomer composition [II]. A method for producing an acrylic resin emulsion for hair dressing, characterized in that the The acrylic resin emulsion for hair dressings of Claim 1 or 2 is contained, The hair dressing characterized by the above-mentioned. Hairdressing method including the following process (A) and process (B):
(A) The process of apply|coating the acrylic resin emulsion for hair dressings of Claim 1 or 2 to hair;
(B) A step of trimming the hair into a desired shape in at least any one of before, simultaneously with, and after the step (A). delete delete