CN106068117A - Hair mousse acrylic resin emulsion and containing its hair mousse and method of haircuting - Google Patents

Abstract

The present invention for be used for obtaining mouldability (performance of haircuting, again haircut performance, touch sensitivity) be washed the harmonious good and excellent hair mousse of aspect of performance and hair mousse acrylic resin emulsion applicable, that monomer composition [I] and monomer composition [II] are carried out emulsion be polymerized and obtain, it is characterized in that, meet following condition (i)～(iii).I at least one in () monomer composition [I] and monomer composition [II] comprises (methyl) acrylic ester monomer.(ii) glass transition temperature (Tg2) of the polymer obtained by Fox formula when using monomer composition [II] polymerization is higher more than 30 DEG C than the glass transition temperature (Tg1) of the polymer obtained by Fox formula when using monomer composition [I] polymerization.(iii) monomer composition [I] is [I] with the compounding ratio (weight ratio) of monomer composition [II]: [II]=50:50～99:1.

Description

Hair mousse acrylic resin emulsion and containing its hair mousse and haircut Method

Technical field

The present invention relates to the acrylic resin emulsion useful as hair mousse (forming hair agent), more specifically, relate to And redispersibility in water solublity and/or water is excellent, when hair mousse, be washed performance with mouldability harmonious excellent Acrylic resin emulsion.

Background technology

There are liquid, curry shape, cystose, shape vaporific, white, the various dosage forms such as wax-like in hair mousse.

Generally, hair mousse is to keep the polymer of desired shape (to determine for by forming overlay film in hair surface Type polymer) as main component, and then it is compounded with additive, molten according to dosage form compounding given with various purposes The polymer composition of agent, base etc..For hair mousse, in recent years, as being free to when haircuting haircut and whole Also the dosage form easily reformed after Faing, to employ the emulsifying dosage form i.e. hair cream of oil preparation and water, pomade becomes main flow.

Further, for hair mousse, it is desirable to hair to be given desired shape and the performance kept for a long time, excellent outward appearance The performance of moulding (adjustment hair) aspects such as performance, excellent sense of touch performance, in addition, also requires that and washes after use from hair Wash, simplicity when removing hair mousse as performance, develop various hair mousse.

Such as, patent documentation 1 has been recorded the polyvinyl alcohol resin employing ad hoc structure as host i.e. polymer The hair mousse of the aqueous solution type of the main component of composition；Cera Flava, surfactant is being comprised it addition, patent documentation 2 has been recorded With compounding polyvinyl alcohol in the emulsification composition of water as the cosmetic hair of compounding agent.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2009-286724 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2011-148721 publication

Summary of the invention

The problem that invention is to be solved

The polyvinyl alcohol resin of the ad hoc structure of the hair mousse of above-mentioned patent documentation 1 possesses and has under high humidity conditions Good curl retention, glutinous greasy less and there is moisturizing power, hair damage the performance lacked etc；It addition, above-mentioned patent The hair mousse of document 2 improves taste during use by being compounded polyvinyl alcohol resin in emulsification composition, possesses not Hair after coating can be given the performance of factitious brightness etc.

But, the hair mousse described in patent documentation 1 combs the insufficient side of clear and coherent degree of (finger), comb or brush etc. at hands Face, the haircuting property aspect again broken once haircut, there is also room for improvement；It addition, the hair mousse described in patent documentation 2 Glutinous greasy greatly, using in terms of sense, seek further to improve.

And then, hair mousse in recent years requires good power of haircuting and performance of haircuting again, and then also requires once to haircut The retentivity of haircuting that kept for a long time etc of hair style.On the other hand, for having good power of haircuting as described above Hair mousse, owing to being compounded the oil component such as substantial amounts of wax, therefore most is wanting in washing off, it is necessary to rub with the hands consumingly with shampoo etc. Wash, or washing etc. again, therefore, produce the worry that scalp is chapped from the cold, is dried.During it addition, wash insufficient, also worry oil component That residual is caused, dandruff, itch, the worry etc. of the scalp such as alopecia.

Therefore, hair mousse expectation in recent years takes into account good mouldability (haircuting property) and good being washed property.

Therefore, the present invention, in view of such problem, its object is to, it is provided that: in mouldability (performance of haircuting (sizing Power), again haircut performance (again shaping force, shape retentivity again), touch sensitivity with utilize water, warm water etc. to be washed aspect of performance equal The hair mousse acrylic resin emulsion effectively used in the hair mousse that weighing apparatus property is good and excellent.

For solving the scheme of problem

And, the present inventor etc. furthers investigate the most repeatedly, found that: containing following acrylic resin The hair mousse of emulsion mouldability (performance of haircuting (shaping force), again haircut performance (shaping force again), touch sensitivity) be washed Aspect of performance is harmonious good and excellent, and described acrylic resin emulsion is at least 2 kinds of monomer compositions to be carried out emulsion gather The acrylic resin emulsion closed and obtain, its at least one comprises (methyl) acrylic ester monomer, by above-mentioned combination of monomers The difference of the glass transition temperature of 2 kinds of polymer when thing is polymerized respectively is more than 30 DEG C, and it is so that glass transition temperature Spend the high amount that monomer composition is below the monomer composition that glass transition temperature is low to carry out emulsion polymerization and obtain, from And complete the present invention.

That is, the purport of the present invention is as described below.

[1] a kind of hair mousse acrylic resin emulsion, it is characterised in that be by monomer composition [I] and monomer group Compound [II] carries out emulsion polymerization and obtains,

Aforementioned monomer compositions [I] and aforementioned monomer compositions [II] meet following condition (i)～(iii).

In (i) aforementioned monomer compositions [I] and aforementioned monomer compositions [II] at least any one comprises (methyl) third Olefin(e) acid esters monomer.

(ii) aforementioned monomer compositions [II] polymerization is used and the vitrification obtained by Fox formula of the polymer that obtains is turned Temperature (Tg2) is than using aforementioned monomer compositions [I] polymerization and the vitrification obtained by Fox formula of the polymer that obtains is turned Temperature (Tg1) is high more than 30 DEG C.

(iii) aforementioned monomer compositions [I] is monomer group with the compounding ratio (weight ratio) of aforementioned monomer compositions [II] Compound [I]: monomer composition [II]=50:50～99:1.

[2] according to the hair mousse acrylic resin emulsion described in aforementioned [1], it is characterised in that foregoing glass turns Temperature (Tg1) is less than 0 DEG C, and foregoing glass transition temperature (Tg2) is more than 30 DEG C.

[3] according to the hair mousse acrylic resin emulsion described in aforementioned [1] or [2], it is characterised in that acrylic compounds Acrylic resin granule in resin emulsion passes through polyvinyl alcohol resin by decentralized stabilization.

[4] according to the hair mousse acrylic resin emulsion described in aforementioned [3], it is characterised in that aforementioned polyvinyl alcohol It is that resin contains the side chain 1,2-diol structure unit shown in following formula (1).

(in formula (1), R¹～R⁶Separately representing hydrogen atom or organic group, X represents singly-bound or bonding chain.)

[5] according to the hair mousse acrylic resin emulsion according to any one of aforementioned [1]～[4], it is characterised in that Only using aforementioned monomer compositions [I] and aforementioned monomer compositions [II], the emulsion first carrying out aforementioned monomer compositions [I] is gathered Close, then carry out the emulsion polymerization of aforementioned monomer compositions [II].

[6] a kind of hair mousse, it is characterised in that containing the hair mousse acrylic acid according to any one of aforementioned [1]～[5] Resin emulsion.

[7] one is haircuted method, and it includes following operation (A) and operation (B).

Operation (A), the hair mousse that monomer composition [I] and monomer composition [II] are carried out emulsion polymerization and obtained is with third The effectively amount of haircuting of olefin(e) acid resin emulsion coats hair；

Operation (B), before foregoing sequence (A), simultaneously and afterwards at least any one time inscribe hair adjusted For desired shape.

Wherein, aforementioned monomer compositions [I] and aforementioned monomer compositions [II] meet following condition (i)～(iii).

In (i) aforementioned monomer compositions [I] and aforementioned monomer compositions [II] at least any one comprises (methyl) third Olefin(e) acid esters monomer.

(ii) aforementioned monomer compositions [II] polymerization is used and the vitrification obtained by Fox formula of the polymer that obtains is turned Temperature (Tg2) is than using aforementioned monomer compositions [I] polymerization and the vitrification obtained by Fox formula of the polymer that obtains is turned Temperature (Tg1) is high more than 30 DEG C.

(iii) aforementioned monomer compositions [I] is monomer group with the compounding ratio (weight ratio) of aforementioned monomer compositions [II] Compound [I]: monomer composition [II]=50:50～99:1.

The effect of invention

Redispersibility in the water solublity of the hair mousse acrylic resin emulsion of the present invention and/or water is excellent, contains The hair mousse of above-mentioned hair mousse acrylic resin emulsion be washed performance become excellent, have equilibrium with mouldability Property also excellent effect.

Detailed description of the invention

Hereinafter, the present invention, an example preferred embodiment expressed below are described in detail.

It should be noted that in the present invention, (methyl) acrylic acid refers to acrylic or methacrylic acid, (methyl) acryloyl Referring to acryloyl or methacryl, (methyl) acrylate refers to acrylate or methacrylate；Acrylic resin Refer to the resin obtained by the polymerizing monomer components containing at least one (methyl) acrylic monomer.

＜ hair mousse acrylic resin emulsion ＞

The hair mousse acrylic resin emulsion of the present invention is monomer composition [I] and monomer composition [II] to be carried out The acrylic resin emulsion that emulsion is polymerized and is obtained, aforementioned monomer compositions [I] and monomer composition [II] meet following Condition (i)～(iii).

In (i) monomer composition [I] and monomer composition [II] at least any one comprises (methyl) esters of acrylic acid Monomer.

(ii) glass transition temperature obtained by Fox formula of the polymer using monomer composition [II] to be polymerized and to obtain The glass transition temperature obtained by Fox formula of the polymer that degree (Tg2) obtains than using monomer composition [I] to be polymerized (Tg1) high more than 30 DEG C.

(iii) monomer composition [I] is monomer composition [I] with the compounding ratio (weight ratio) of monomer composition [II]: Monomer composition [II]=50:50～99:1.

Hair mousse acrylic resin emulsion can be only by monomer composition [I] and monomer composition [II] with 2 rank The polymerization of Duan Jinhang emulsion and the acrylic resin emulsion that obtains, it is also possible to for use other monomer compositions with 3 stages more than The acrylic resin emulsion carrying out emulsion polymerization and obtain.During with 3 stage emulsion carried out above polymerization, can be in combination of monomers Thing [I] and monomer composition [II] emulsion polymerization before, afterwards or between any time under carry out.

Wherein, from the aspect of simple operating steps, be preferably the most only using as monomer component monomer composition [I] and The acrylic resin emulsion that monomer composition [II] obtains so that 2 stages carried out emulsion polymerization.It addition, from can stably make The aspect made is set out, and particularly preferably only monomer composition [I] and monomer composition [II] is carried out with 2 stages according to this order The acrylic resin emulsion that emulsion is polymerized and is obtained.It should be noted that in addition to monomer component, it is also possible to suitably use ＜ described later other compositions ＞.

In the present invention, in monomer composition [I] and monomer composition [II] at least any one must comprise (methyl) Acrylic ester monomer, preferably has the tendency tailed off and levels of residual monomers to reduce, i.e. safety uprises from unreacted reactant The aspect that aspect, stink are few is set out, and both preferred monomers compositions [I] and monomer composition [II] are containing (methyl) acrylic acid Esters monomer.

In the present invention, it is necessary to the monomer composition [I] obtained for adjusting in such a way and monomer composition [II]: Use monomer composition [II] polymerization and glass transition temperature (Tg2) ratio obtained by Fox formula of the polymer that obtains is made With monomer composition [I] polymerization the glass transition temperature (Tg1) obtained by Fox formula of the polymer that obtains high 30 DEG C with On, glass transition temperature (Tg1) is preferably more than 40 DEG C with the difference of glass transition temperature (Tg2), particularly preferably 50 DEG C Above, more preferably more than 60 DEG C, especially preferably more than 90 DEG C.

When the difference of above-mentioned Tg2 Yu Tg1 is too small, there is the tendency that being washed property reduces, for the most preferred.It should be noted that Tg2 It is usually 300 DEG C with the upper limit of the difference of Tg1, preferably 200 DEG C.

Above-mentioned Tg1 and Tg2 is to be calculated based on the glass transition temperature of each homopolymer by following Fox formula.Need It is noted that the glass transition temperature of the homopolymer in following Fox formula is determined by the monomeric substance of this homopolymer.

That is, the glass transition temperature (Tga, Tgb, Tgn) of homopolymer can use respectively Value described in " PolymerHandbook the 3rd edition, John Wiley&Sons, Inc, 1989 ", does not remember about in the document The homopolymer of monomeric substance carried, can by mean molecule quantity be 10,000 less than 1,000,000 homopolymer be polymerized, it is poor to utilize Show that scanning amount heat determination (DSC) etc. confirms.It should be noted that aforementioned mean molecule quantity is for utilizing gel permeation chromatography (GPC) with the weight average molecular weight of polystyrene conversion.

More than by, according to monomeric substance and its weight fraction can obtain polymer glass transition temperature (Tg1 and Tg2)。

It should be noted that for a part of monomer, the glass transition temperature (Tg) of homopolymer sometimes cannot be measured, on In the case of stating, when the content of this monomer is about below 5 weight %, the impact on polymeric properties is few, does not the most consider this monomer As the constituent in Fox formula.

$\frac{1}{Tg}=\frac{Wa}{Tga}+\frac{Wb}{Tgb}+...+\frac{Wn}{Tgn}$

The glass transition temperature (K) of Tg: polymer

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

Wa: the weight fraction of monomer A

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

Wb: the weight fraction of monomer B

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

Wn: the weight fraction of monomer N

(Wa+Wb+ ...+Wn=1)

As above-mentioned Tg1, preferably less than 0 DEG C, particularly preferably less than-20 DEG C, more preferably less than-30 DEG C.

When Tg1 is too high, the acrylic resin granule in acrylic resin emulsion becomes really up to the mark, it is impossible to obtain sufficiently Cohesive, has the tendency that haircuting property reduces again.

As the lower limit of Tg1, usually-80 DEG C, it is preferably-75 DEG C.

As above-mentioned Tg2, preferably more than 30 DEG C, particularly preferably more than 40 DEG C, more preferably more than 50 DEG C, especially It is preferably more than 60 DEG C.

When Tg2 is too low, the acrylic resin granule in gained acrylic resin emulsion becomes too soft, and has and is difficult to obtain Continuous print is haircuted the tendency of performance.It should be noted that during Tg2 height, the aggregation force local of gained acrylic resin increases, because of This demonstrates cohesive, has the tendency that the change of haircuting property is good again.

As the upper limit of Tg2, usually 230 DEG C, preferably 150 DEG C.

Monomer composition [I] in the present invention is necessary for monomer group with the compounding ratio (weight ratio) of monomer composition [II] Compound [I]: monomer composition [II]=50:50～99:1, preferably 60:40～98:2, particularly preferably 65:35～97:3, More preferably 70:30～95:5.

When monomer composition [II] is too much relative to the compounding amount of monomer composition [I], polymerization stability reduces, and haircuts Property become insufficient tendency, have the harmonious tendency reduced of haircuting property and being washed property time very few.

＜ monomer composition [I] ＞

Monomer composition [I] is specifically described.

As monomer composition [I], such as, can enumerate: (methyl) acrylic monomer (I-1), containing monomer (I-2) etc..Monomer composition [I] can be only made up of one kind or two or more (methyl) acrylic monomer (I-1), it is also possible to Only it is made up of one kind or two or more (I-2) containing monomer, it is also possible to comprise one kind or two or more (methyl) acrylic acid Class monomer (I-1) and one kind or two or more containing monomer (I-2).Wherein, preferably with (methyl) acrylic monomer (I- 1) it is main component.

As above-mentioned (methyl) acrylic monomer (I-1), such as, can enumerate: (methyl) acrylic acid methyl ester., (methyl) Ethyl acrylate, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) third Olefin(e) acid 2-Octyl Nitrite, (methyl) cyclohexyl acrylate, (methyl) lauryl acrylate, (methyl) 1-Octyl acrylate, (methyl) Fat family (methyl) acrylic ester monomer such as stearyl acrylate ester；Fragrance family such as (methyl) acrylic acid benzene oxygen ester (methyl) Acrylic ester monomer；(methyl) acrylic acid trifluoro ethyl ester etc..It should be noted that they can be used alone or are applied in combination Two or more.

Wherein, from the viewpoint of topknot sense, again haircuting property, the preferably carbon number of alkyl is the aliphatic of 1～18 System (methyl) acrylic ester monomer, the particularly preferably carbon number of alkyl are fatty family (methyl) acrylic acid of 1～12 Esters monomer, and then fatty family (methyl) acrylic ester monomer that carbon number is 4～12 of preferably alkyl, the most excellent Elect n-butyl acrylate, 2-EHA as.Alternatively, it is also possible to use 2-EHA and methyl aptly The combination of the combination of acrylic acid methyl ester., n-butyl acrylate and methyl methacrylate.

As containing monomer (I-2), such as, can enumerate: molecular structure has more than 2 vinyls monomer, Monomer containing glycidyl, the monomer containing pi-allyl, the monomer containing hydrolyzable silyl group, the monomer containing acetoacetyl, The monomer of hydroxyl, carboxylic monomer etc..

Wherein, never reduce from the viewpoint of haircuting property and being washed property improve, be preferably used in molecular structure and there are 2 The monomer of above vinyl or the monomer containing hydrolyzable silyl group.

As above-mentioned molecular structure has the monomer of more than 2 vinyls, can list such as: divinylbenzene, benzene Dioctyl phthalate diallyl, triallyl cyanurate, triallyl isocyanurate, ethylene glycol bisthioglycolate (methyl) acrylate, 1,2-third Glycol two (methyl) acrylate, 1,3-propylene glycol two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1, 6-hexanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylic acid Ester, (methyl) allyl acrylate etc..

Wherein, from (methyl) acrylate contained with (methyl) acrylic monomer (I-1), monomer composition [II] From the viewpoint of the copolymerizable excellence of class monomer, preferably ethylene glycol bisthioglycolate (methyl) acrylate, 1,2-PD two (methyl) third Olefin(e) acid ester, 1,3-propylene glycol two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,6-HD two (first Base) acrylate, neopentyl glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate.

As the above-mentioned monomer containing glycidyl, can list such as: (methyl) glycidyl acrylate, (first Base) glycidyl base ether, (methyl) acrylic acid 3,4-epoxycyclohexyethylSiOi ester etc..

As the above-mentioned monomer containing pi-allyl, can list such as: triolefin propoxy, diallyl maleate, cyanogen Uric acid triallyl, triallyl isocyanurate, tetraallyloxyethane etc. have the monomer of more than 2 pi-allyls, pi-allyl Glycidyl ether, allyl acetate etc..

As the above-mentioned monomer containing hydrolyzable silyl group, can list such as: vinyltrimethoxy silane, vinyl Triethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) the ethylene base system such as silane, vinyl methyl dimethoxysilane contain The monomer of silicyl；γ-(methyl) acryloxypropyl trimethoxy silane, γ-(methyl) acryloxypropyl first Base dimethoxysilane, γ-(methyl) acryloxypropyl triethoxysilane, γ-(methyl) acryloxypropyl first (methyl) the acryloyl-oxy base systems such as the base diethoxy silane monomer containing silicyl.

Wherein, from (methyl) acrylate contained with (methyl) acrylic monomer (I-1), monomer composition [II] From the viewpoint of the copolymerizable excellence of class monomer, preferably (methyl) the acryloyl-oxy base system monomer containing silicyl.

As the above-mentioned monomer containing acetoacetyl, can list such as: acetoacetic acid vinyl esters, allyl acetoacetate Base ester, diacetic acid allyl ester, (methyl) acrylic acid acetoacetoxyethyl .beta.-methylacrylic acid acetoacetoxyethyl, (methyl) acrylic acid acetoacetoxy groups propyl ester .beta.-methylacrylic acid acetoacetoxy groups propyl ester, (methyl) acrylic acid 2-cyano-acetamide second Acyloxy ethyl ester etc..

As the monomer of above-mentioned hydroxyl, can list such as: (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid hydroxyl (methyl) acrylate etc. such as propyl ester, (methyl) acrylic acid 4-hydroxy butyl ester, the effect of the protecting colloid when emulsion is polymerized and quilt From the viewpoint of washing performance, preferably acrylic acid 2-hydroxyl ethyl ester, HEMA.

As above-mentioned carboxylic monomer, can list such as: (methyl) acrylic acid, acrylic acid dimer .beta.-methylacrylic acid, horse Come sour, maleic anhydride, fumaric acid, citraconic acid, glutaconate, itaconic acid, acrylamide N-glycolic, cinnamic acid etc., wherein, from From the viewpoint of the effect of protecting colloid during emulsion polymerization and being washed property, preferably acrylic acid, methacrylic acid.

As the content ratio of above-mentioned (methyl) acrylic monomer (I-1), overall relative to monomer composition [I], excellent Elect 80～100 weight %, particularly preferably 85～99.99 weight %, more preferably 90～99.9 weight % as.

When the content ratio of above-mentioned (methyl) acrylic monomer (I-1) is very few, has and cannot play performance of sufficiently haircuting Tendency.During it should be noted that comprise monomer of more than two kinds as (methyl) acrylic monomer (I-1), preferably these lists The total content ratio of body is above-mentioned scope.

As the above-mentioned content ratio containing monomer (I-2), overall relative to monomer composition [I], preferably 0～ 20 weight %, particularly preferably 0.01～15 weight %, more preferably 0.1～10 weight %.

When above-mentioned content ratio is too much, acrylic resin becomes really up to the mark, it is impossible to produce sufficient bonding force, haircuting property The tendency reduced, when above-mentioned content ratio is very few, has the tendency of the effect being difficult to play being washed property.It should be noted that bag Containing monomer of more than two kinds as during containing monomer (I-2), the preferably total content ratio of these monomers is above-mentioned scope.

During it addition, (I-2) Han monomer comprises the monomer in molecular structure with more than 2 vinyls, this molecule The content ratio of the monomer in structure with more than 2 vinyls is overall relative to monomer composition [I] is preferably 0.01～10 Weight %, particularly preferably 0.05～5 weight %, more preferably 0.1～3 weight %.

During it addition, (I-2) Han monomer comprises the monomer containing hydrolysis of silyl, this contains the list of hydrolysis of silyl The content ratio of body is overall relative to monomer composition [I] is preferably 0.01～5 weight %, particularly preferably 0.02～3 weights Amount %, more preferably 0.05～2 weight %.

It addition, in the range of this external effect not destroying the present invention, it is possible to use a small amount of styrene, Alpha-Methyl benzene The styrenic monomers such as ethylene, vinyl formate, vinyl acetate, propionate, vinyl valerate, vinyl butyrate, different Vinyl butyrate, trimethylacetic acid vinyl acetate, caprate, vinyl laurate, stearic acid vinyl ester, vinyl benzoate, uncle The vinyl esters system monomers such as ethylene carbonate, 2 ethyl hexanoic acid vinyl acetate.

＜ monomer composition [II] ＞

Monomer composition [II] is specifically described.

As monomer composition [II], such as, can enumerate: (methyl) acrylic monomer (II-1), containing monomer (II-2) etc..Monomer composition [II] can be only made up of, also one kind or two or more (methyl) acrylic monomer (II-1) Can be only made up of one kind or two or more (II-2) containing monomer, it is also possible to comprise one kind or two or more (methyl) third Alkene acrylic monomer (II-1) and one kind or two or more containing monomer (II-2).Wherein, preferably with (methyl) acrylic compounds Monomer (II-1) is main component.

As above-mentioned (methyl) acrylic monomer (II-1), in the same manner as above-mentioned (methyl) acrylic monomer (I-1), Such as can enumerate: (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) propylene Acid isobutyl ester, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) Fat family (methyl) the esters of acrylic acid list such as lauryl acrylate, (methyl) 1-Octyl acrylate, (methyl) stearyl acrylate ester Body；Fragrance family (methyl) acrylic ester monomer such as (methyl) acrylic acid benzene oxygen ester；(methyl) acrylic acid trifluoro ethyl ester etc..Need It is noted that they can be used alone or be applied in combination two or more.

Wherein, from the fatty family that the carbon number of the aspect of topknot sense, again haircuting property, preferably alkyl is 1～18 (methyl) acrylic ester monomer, the carbon number of particularly preferred alkyl is fatty family (methyl) esters of acrylic acid of 1～12 Monomer, the carbon number of further preferred alkyl is fatty family (methyl) acrylic ester monomer of 1～4, particularly preferred first Base acrylic acid methyl ester., ethyl methacrylate, propyl methacrylate, n-BMA.

Furthermore it is also possible to be suitable for using with methyl methacrylate as main component, be applied in combination other (methyl) propylene Acid esters.

As containing monomer (II-2), with above-mentioned containing in the same manner as monomer (I-2), such as, can enumerate: point Minor structure has the monomer of more than 2 vinyls, the monomer containing glycidyl, the monomer containing pi-allyl, containing water-disintegrable first The monomer of silylation, the monomer containing acetoacetyl, the monomer of hydroxyl, carboxylic monomer etc..

Wherein, never reduce from the viewpoint of haircuting property and being washed property improve, preferably by molecular structure has 2 with The monomer of upper vinyl or the monomer copolymerization containing hydrolyzable silyl group.

As above-mentioned molecular structure has the monomer of more than 2 vinyls, can list such as: divinylbenzene, benzene Dioctyl phthalate diallyl, triallyl cyanurate, triallyl isocyanurate, ethylene glycol bisthioglycolate (methyl) acrylate, 1,2-third Glycol two (methyl) acrylate, 1,3-propylene glycol two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1, 6-hexanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylic acid Ester, (methyl) allyl acrylate etc..

Wherein, from (methyl) acrylate contained with (methyl) acrylic monomer (II-1), monomer composition [I] From the viewpoint of the copolymerizable excellence of class monomer, preferably ethylene glycol bisthioglycolate (methyl) acrylate, 1,2-PD two (methyl) third Olefin(e) acid ester, 1,3-propylene glycol two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,6-HD two (first Base) acrylate, neopentyl glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate.

As the above-mentioned monomer containing glycidyl, can list such as: (methyl) glycidyl acrylate, (first Base) glycidyl base ether, (methyl) acrylic acid 3,4-epoxycyclohexyethylSiOi ester etc..

As the above-mentioned monomer containing pi-allyl, can list such as: triolefin propoxy, diallyl maleate, cyanogen Uric acid triallyl, triallyl isocyanurate, tetraallyloxyethane etc. have the monomer of more than 2 pi-allyls, pi-allyl Glycidyl ether, allyl acetate etc..

As the above-mentioned monomer containing hydrolyzable silyl group, can list such as: vinyltrimethoxy silane, vinyl Triethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) the ethylene base system such as silane, vinyl methyl dimethoxysilane contain The monomer of silicyl；γ-(methyl) acryloxypropyl trimethoxy silane, γ-(methyl) acryloxypropyl first Base dimethoxysilane, γ-(methyl) acryloxypropyl triethoxysilane, γ-(methyl) acryloxypropyl first (methyl) the acryloyl-oxy base systems such as the base diethoxy silane monomer containing silicyl.

Wherein, from (methyl) acrylate contained with (methyl) acrylic monomer (II-1), monomer composition [I] From the viewpoint of the copolymerizable excellence of class monomer, preferably (methyl) the acryloyl-oxy base system monomer containing silicyl.

As the above-mentioned monomer containing acetoacetyl, can list such as: acetoacetic acid vinyl esters, allyl acetoacetate Base ester, diacetic acid allyl ester, (methyl) acrylic acid acetoacetoxyethyl .beta.-methylacrylic acid acetoacetoxyethyl, (methyl) acrylic acid acetoacetoxy groups propyl ester .beta.-methylacrylic acid acetoacetoxy groups propyl ester, (methyl) acrylic acid 2-cyano-acetamide second Acyloxy ethyl ester etc..

As the monomer of above-mentioned hydroxyl, can list such as: (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid hydroxyl (methyl) acrylate etc. such as propyl ester, (methyl) acrylic acid 4-hydroxy butyl ester, the effect of the protecting colloid when emulsion is polymerized and quilt From the viewpoint of washing performance, preferably acrylic acid 2-hydroxyl ethyl ester, HEMA.

As above-mentioned carboxylic monomer, can list such as: (methyl) acrylic acid, acrylic acid dimer .beta.-methylacrylic acid, horse Come sour, maleic anhydride, fumaric acid, citraconic acid, glutaconate, itaconic acid, acrylamide N-glycolic, cinnamic acid etc., wherein, from From the viewpoint of the effect of protecting colloid during emulsion polymerization and being washed property, preferably acrylic acid, methacrylic acid.

It is as the content ratio of above-mentioned (methyl) acrylic monomer (II-1), overall relative to monomer composition [II], It is preferably 80～100 weight %, particularly preferably 85～99.99 weight %, more preferably 90～99.9 weight %.

When the content ratio of above-mentioned (methyl) acrylic monomer (II-1) is above-mentioned lower limit, have cannot play the most whole The tendency of volatility.During it should be noted that comprise monomer of more than two kinds as (methyl) acrylic monomer (II-1), excellent The total content ratio selecting these monomers is above-mentioned scope.

As the above-mentioned content ratio containing monomer (II-2), overall relative to monomer composition [II], preferably 0 ～20 weight %, particularly preferably 0.01～15 weight %, more preferably 0.1～10 weight %.

When above-mentioned content ratio is too much, there is the tendency that polymerization stability reduces, have time very few and be difficult to learn being washed property The tendency of effect.It should be noted that comprise monomer of more than two kinds as during containing monomer (II-2), preferably these are single The total content ratio of body is above-mentioned scope.

During it addition, (II-2) Han monomer comprises the monomer in molecular structure with more than 2 vinyls, this molecule The content ratio of the monomer in structure with more than 2 vinyls is overall relative to monomer composition [II] is preferably 0.01～10 Weight %, particularly preferably 0.05～5 weight %, more preferably 0.1～3 weight %.

During it addition, (II-2) Han monomer comprises the monomer containing hydrolysis of silyl, this contains hydrolysis of silyl The content ratio of monomer is overall relative to monomer composition [II] is preferably 0.01～5 weight %, particularly preferably 0.02～3 weights Amount %, more preferably 0.05～2 weight %.

It addition, in the range of this external effect not destroying the present invention, it is possible to use a small amount of styrene, Alpha-Methyl benzene The styrenic monomers such as ethylene；Vinyl formate, vinyl acetate, propionate, vinyl valerate, vinyl butyrate, different Vinyl butyrate, trimethylacetic acid vinyl acetate, caprate, vinyl laurate, stearic acid vinyl ester, vinyl benzoate, uncle The vinyl esters system monomers such as ethylene carbonate, 2 ethyl hexanoic acid vinyl acetate.

＜ other compositions ＞

In the acrylic resin emulsion of the present invention, in addition to above-mentioned monomer composition [I] and monomer composition [II], Can also the most suitably use other compositions.As other compositions such, such as, can enumerate: emulsifying agent, polymerization are drawn Send out agent, polymerization regulator, plasticizer etc., wherein, emulsifying agent is preferably used.As mentioned emulsifier, preferably water solublity high score Son, particularly preferably polyvinyl alcohol resin (following, to be sometimes denoted as " PVA system resin ").

And then, in the present invention, become good aspect, the preferably propylene in acrylic resin emulsion from being washed property Acid resin granule passes through polyvinyl alcohol resin by decentralized stabilization.

Referred to by the state of decentralized stabilization it should be noted that above-mentioned, emulsion is stood 1 month with 23 DEG C and also keeps all Even state and there is not settlement separate dispersity.

As above-mentioned PVA system resin, it is preferably as follows the shown PVA with specific mean saponification degree and average degree of polymerization It it is resin.

As the mean saponification degree of PVA system resin, preferably 70～99.9 moles %, particularly preferably 80～99.5 rub You are %, more preferably 85～99 moles of %.

When above-mentioned mean saponification degree is too low, polymerization is difficult to stably carry out, even if polymerization terminates, it is possible to see the guarantor having emulsion Depositing the tendency that stability reduces, when above-mentioned mean saponification degree is too high, emulsion stability reduces, it is seen that have emulsion manufacture to become difficulty Tendency.

It should be noted that in this specification, mean saponification degree can be according to the soap described in JIS K 6726 (1994) The calculation method of change degree is obtained.

It addition, as the average degree of polymerization of PVA system resin, preferably 50～3000, particularly preferably 100～2000, enter One step is preferably 200～1000, especially preferably 200～500.

When above-mentioned average degree of polymerization is too low, protecting colloid ability during emulsion polymerization becomes insufficient, it is seen that have polymerization difficulty With the tendency stably carried out, when above-mentioned average degree of polymerization is too high, occurs thickening and reaction system to become unstable during polymerization, have The tendency that dispersion stabilization reduces.

It should be noted that in this specification, average degree of polymerization can be according to putting down described in JIS K 6726 (1994) All calculation methods of the degree of polymerization are obtained.

In the present invention, PVA system resin refers to, PVA itself or such as by the material of various modified material modifications, its Modification degree is usually 20 moles of below %, preferably 15 moles below %, more preferably 10 moles of below %.

As modified PVA system resin, can list such as: be the anion of representative in order to carboxylic acid group, sulfonic group, phosphate The anion-modified PVA system resin that property is group modified；Change by the cation of the cationic groups modifications such as quaternary ammonium group Property PVA system resin；It is the various functional groups etc. of representative in order to acetoacetyl, diacetone acrylamide base, sulfydryl, silanol group The modified PVA system resin of modification；The PVA system resin etc. of 1,2-diol structure unit is contained at side chain.

The PVA system resin of 1,2-diol structure unit is contained to acrylate list at side chain from as above-mentioned PVA system resin It is preferred from the viewpoint of disperseing excellent in stability when body is polymerized, particularly preferably containing 1 shown in following formula (1), The PVA system resin of 2-diol structure unit.

(in formula (1), R¹～R⁶Separately representing hydrogen atom or organic group, X represents singly-bound or bonding chain.)

In above-mentioned formula (1), R¹～R⁶Separately represent hydrogen atom or organic group.R¹～R⁶The most all hydrogen is former Son, so long as not significantly damaging the amount of resin properties, then can also be organic group.For this organic group, the most particularly Limit, be preferably the alkane of the carbon numbers 1～4 such as such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group Base；Can also have the substituent groups such as halogen, hydroxyl, ester group, carboxylic acid group, sulfonic group as required.

In formula (1), X is singly-bound or bonding chain, from sizing retentivity, without sticking the viewpoints such as the affinity of greasy and hair, It is preferably singly-bound.For above-mentioned bonding chain, there is no particular limitation, can list: alkylidene, alkenylene, alkynylene, sub-benzene The hydrocarbon such as base, naphthylene (these hydrocarbon are optionally replaced by the halogens such as fluorine, chlorine, bromine etc.), in addition, can list-O-,- (CH₂O)_m-、-(OCH₂)_m-、-(CH₂O)_mCH₂-、-CO-、-COCO-、-CO(CH₂)_mCO-、-CO(C₆H₄)CO-、-S-、-CS-、- SO-、-SO₂-、-NR-、-CONR-、-NRCO-、-CSNR-、-NRCS-、-NRNR-、-HPO₄-、-Si(OR)₂-、-OSi (OR)₂-、-OSi(OR)₂O-、-Ti(OR)₂-、-OTi(OR)₂-、-OTi(OR)₂O-、-Al(OR)-、-OAl(OR)-、-OAl(OR) O-etc..Wherein, R each stands alone as arbitrary substituent group, preferably hydrogen atom, alkyl；It addition, m is natural number.Wherein, from system The viewpoints such as viscosity stability when making, thermostability are set out, preferably the alkylidene of carbon number less than 6 or-CH₂OCH₂-, more excellent Elect methylene ,-CH as₂OCH₂-。

Described containing 1 shown in formula (1), the PVA system resin of 2-diol structure unit obtains, such as by the following method: A () makes the method that the copolymer of vinyl acetate and 3,4-diacetoxy-1-butylene carries out saponification；B () makes vinyl acetate The method carrying out saponification and decarboxylation with the copolymer of vinylethylene carbonate；C () makes vinyl acetate and 2,2-dialkyl group-4- The copolymer of vinyl-1,3-dioxa penta ring carries out saponification and de-ketalization method；D () makes vinyl acetate and glycerol list The copolymer of allyl ether carries out the method etc. of saponification.

Containing containing of the 1,2-diol structure unit in the PVA system resin of the 1,2-diol structure unit shown in formula (1) Rate is preferably 1～15 mole of %, particularly preferably 1～12 mole %, and then preferably 2～10 moles %, particularly preferably 2～ 9 moles of %.

When the containing ratio of described 1,2-diol structure unit is too low, there is the tendency that the mechanical stability of emulsion reduces；Contain When rate is too high, stability during polymerization is had to reduce and be difficult to obtain the tendency of the high stable emulsion of nonvolatile component.

It should be noted that for the side chain 1 in PVA system resin, the containing ratio of 2-diol units, can be by complete by PVA The material of full saponification¹H-NMR spectrum (solvent: DMSO-d₆, internal standard substance: tetramethylsilane) and obtain, specifically, can With by the hydroxyl proton come from 1,2 glycol unit, methine protons, methene proton, the methene proton of main chain or It is connected to the peak area of the proton etc. of the hydroxyl of main chain and calculates.

It addition, containing 1 shown in formula (1), the mean saponification degree preferably 85 of the PVA system resin of 2-diol structure unit rubs You are more than %, more preferably 86.5～99.8 moles %, particularly preferably 95～99 moles %.

If described saponification degree is too small, then stability when having emulsion to be polymerized reduces and is difficult to obtain inclining of target emulsion To.

And then, containing 1 shown in formula (1), the average degree of polymerization of the PVA system resin of 2-diol structure unit be preferably 50～ 3000, and then preferably 100～2500, more preferably 200～2000, particularly preferably 200～500.

When described average degree of polymerization is too small, there is the tendency being difficult to manufacture PVA system resin industrially；Average degree of polymerization is excessive Time, there is the viscosity of emulsion to become the tendency that too high or emulsion polymerization stability reduces.

It addition, PVA system resin generally uses aqueous medium to make aqueous solution, it uses during emulsion is polymerized. Herein, aqueous medium refers to water or the alcohol solvent based on water, preferably water.

For the amount (nonvolatile component) of the PVA system resin in this aqueous solution, there is no particular limitation, from processing easiness From the viewpoint of, preferably 5～30 weight %.

The consumption of above-mentioned PVA system resin is relative to total 100 weight portion of monomer composition [I] and monomer composition [II] It is preferably 0.01～40 weight portions, particularly preferably 0.1～30 weight portions, more preferably 0.5～20 weight portion.

When the consumption of described PVA system resin is very few, protecting colloid quantitative change when having emulsion to be polymerized obtains not enough and polymerization-stable Property the tendency that reduces and preferably, when consumption is too much, have the viscosity of acrylic resin emulsion to raise and tendency that stability reduces.

As the emulsifying agent in addition to above-mentioned PVA system resin, such as, can enumerate: anionic property, cationic and non- The water soluble polymer with protecting colloid ability and water solublity beyond ionic surfactant, PVA system resin are low Polymers etc..

As above-mentioned surfactant, such as, can enumerate: the such the moon of sodium lauryl sulfate, dodecylbenzene sodium sulfonate Ionic surfactant, and have the material of Pluronic type structure, the material with polyoxyethylene-type structure etc. non-from Sub-property surfactant.It addition, as surfactant, it is possible to use structure has free-radical polymerised unsaturated bond Reactive surfactant.They can be used alone or be applied in combination two or more.

The use of above-mentioned surfactant has makes emulsion polymerization successfully carry out, be easily controlled (the effect as emulsifying agent The coarse granule that really) or produces in suppression polymerization, the effect of generation of block-wise thing.But, if by these surfactants When more using as emulsifying agent, there is the tendency that percent grafting reduces.Therefore, when using surfactant, its usage amount is relative It is the amount of auxiliary in PVA system resin, the fewest amount.

As the water soluble polymer with protecting colloid ability beyond above-mentioned PVA system resin, can list such as: hydroxyl Ethyl cellulose, polyvinyl pyrrolidone, methylcellulose etc..They can be used alone or be applied in combination two or more. They make the aspect of viscosity change at thickening, the particle diameter of change emulsion of emulsion is effective.

As above-mentioned water-soluble oligomer, can list such as: preferably there is sulfonic group, carboxyl, hydroxyl, aklylene glycol The polymer of the hydrophilic radicals such as base, the most preferably can list polymer or copolymer that the degree of polymerization is 10～about 500.Make For the concrete example of water-soluble oligomer, can list such as: the amide such as 2-Methacrylamide-2-methyl propane sulfonic acid copolymer Based copolymer, Sodium methacrylate .-4-styrene sulfonic acid ester copolymer, styrene/maleic acid, melamine sulfonic acid and formaldehyde contract Compound, poly-(methyl) acrylates etc..And then, as concrete example, it is also possible to list: will have sulfonic group, carboxyl, hydroxyl, The monomer of aklylene glycol base etc. or free-radical polymerised reactive emulsifier is polymerized alone in advance or with other monomer altogether Poly-water-soluble oligomer etc..They can be used alone or be applied in combination two or more.

As above-mentioned polymerization initiator, it is possible to use common emulsion is polymerized the material that can use, and can list example As: the inorganic peroxides such as potassium peroxydisulfate, sodium peroxydisulfate, Ammonium persulfate.；Organic peroxide, azo series initiators, peroxidating The peroxide such as hydrogen, butylperoxide；And they combine with the reducing agent such as sodium acid sulfite, L-AA Redox polymerization initiator etc..They can be used alone or be applied in combination two or more.

Wherein, from the viewpoint of easily polymerization, preferably Ammonium persulfate., potassium peroxydisulfate.

As above-mentioned polymerization regulator, suitably can select from known material.As such polymerization regulator, can List such as: chain-transferring agent, buffer agent etc..

As above-mentioned chain-transferring agent, can list such as: the alcohol such as methanol, ethanol, propanol, butanol；Acetaldehyde, propionic aldehyde, positive fourth The aldehydes such as aldehyde, furfural, benzaldehyde；And dodecyl mercaptans, lauryl mercaptan, positive mercaptan, thioglycolic acid, thioglycolic are misery The thio-alcohol such as ester, thioglycerol etc..They can be used alone or be applied in combination two or more.The use of chain-transferring agent is from stable Ground is effective from the viewpoint of being polymerized, and is preferably used to regulate the degree of polymerization of acrylic resin.

As above-mentioned buffer agent, can list such as: sodium acetate, ammonium acetate, sodium phosphite, sodium citrate etc..They can Two or more to be used singly or in combination.

As above-mentioned plasticizer, it is possible to use adipate ester system plasticizer, phthalic acid system plasticizer, phosphoric acid system plasticizer Deng.

For the consumption of other composition, in the range of the effect not damaging the present invention, can be suitable according to purpose Select.

Manufacture method ＞ of ＜ acrylic resin emulsion

For monomer composition [I] and monomer composition [II] are obtained so that 2 stages carried out emulsion polymerization successively third The manufacture method of olefin(e) acid resin emulsion illustrates.

The acrylic resin emulsion of the present invention such as can be enumerated: use PVA system resin is as dispersion stabilizer, first Monomer composition [I] is carried out emulsion polymerization obtain the 1st emulsion after, then monomer composition [II] is carried out in the 1st emulsion The method of emulsion polymerization.

Generally emulsion is polymerized in addition to PVA system resin and aforementioned monomer composition, uses polymerization initiator as required, gathers Close other compositions aforementioned of regulator, coemulsifier or the like and implement.It addition, the reaction condition of polymerization can basis The kind of monomer, purpose etc. suitably select.

As the method for emulsion polymerization, can list such as: in retort, add water, PVA system resin, heat up and drip The monomer dropping formula emulsion polymerization of monomer component and polymerization initiator；The mix monomer of the monomer component of dropping is used in advance The water soluble polymer with protecting colloid ability beyond PVA system resin and/or PVA system resin and water carry out dispersion and emulsion it After, drip the emulsified monomer dropping formula emulsion polymerization etc. of this dispersion and emulsion monomer；Reactivity when aqueous monomers uses, The aspects such as the management of polymerization process, controlling are set out, and emulsified monomer dropping formula polymerization is favourable.

It addition, in order to emulsion being given stability, giving water solublity and/or the redispersibility to water, it is also possible in polymerization After the water soluble polymer with protecting colloid ability beyond PVA system resin and/or PVA system resin being carried out at the end of reaction Add.

Emulsion polymerization process is the most specifically illustrated, as described below.

In the polymerization of above-mentioned monomer dropping formula emulsion, first, in retort, water, PVA system resin, as required are added Coemulsifier, after heated up (usual 40～90 DEG C), by a part of monomer composition [I] (relative to monomer group Compound [I] total amount, usually 0.1～50 weight %, preferably 1～30 weight %) and polymerization initiator add to this retort In, implement initial polymerization.Then, monomer composition [I] remaining monomer composition is disposably added to retort or Dropping limit, limit is added to retort, and interpolation polymerization initiator limit in limit is polymerized further as required.Then, while by monomer Compositions [II] is disposably added to retort or dropping limit, limit is added to retort, and limit is added further as required Polymerization initiator limit is polymerized.At the end of judging polyreaction, retort can be cooled down, take out target acrylic acid Resin emulsion.

It addition, in above-mentioned emulsified monomer dropping formula emulsion polymerization, such as, first, add water in retort, according to need The PVA system resin wanted, coemulsifier, after heated up (usual 40～90 DEG C), by PVA system resin and/or PVA system resin The water soluble polymer with protecting colloid ability in addition, as required carry out emulsion dispersion with coemulsifier and water and Become monomer composition [I] a part (relative to monomer composition [I] total amount, usually 0.1～50 weight %, preferably 1 ～30 weight %) and polymerization initiator add to this retort, implement initial polymerization.Then, monomer composition [I] is remained Monomer composition disposably add to retort or dropping limit, limit is added in retort, limit adds further as required Polyaddition initiator limit is polymerized.Then, the water with protecting colloid ability beyond PVA system resin and/or PVA system resin Soluble macromolecular, as required carry out the monomer composition [II] of emulsion dispersion disposably with co-emulsifier and water Adding to retort or dropping limit, limit is added to retort, interpolation polymerization initiator limit in limit is gathered further as required Close.At the end of judging polyreaction, retort can be cooled down, take out target acrylic resin emulsion.

Alternatively, it is also possible to do not implement above-mentioned initial polymerization and implement dropping limit, limit and add monomer composition in retort The total amount of [I] and polymerization initiator, then limit dropping limit add the total amount of monomer composition [II] in retort and polymerization is drawn The method sending out agent.During it addition, above-mentioned reaction temperature is less than 70 DEG C, from the redox polymerization reactant being applied in combination reducing agent System successfully react from the viewpoint of and preferred.

The emulsion polymerization of monomer composition [I] can continue after the moment that the total amount adding monomer composition [I] terminates Be polymerized usual 5 minutes～1 hour (preferably 10 minutes～30 minutes), monomer composition [I] aggregate rate more than 90% (preferably 95%) moment terminates polymerization, obtains the 1st emulsion, can then carry out the emulsion polymerization of monomer composition [II].

In the present invention, it is polymerized by emulsion and the acrylic resin emulsion that obtains is typically uniform milky, third The mean diameter of the acrylic resin in olefin(e) acid resin emulsion is preferably 0.2～2 μm, more preferably 0.3～1.5 μm.

It should be noted that herein, mean diameter can be divided by conventional method such as laser desorption/scattering formula granularity Cloth determinator " LA-950S2 " (Horiba Seisakusho K.k.'s system) and be measured.

And then, in the present invention, from obtain be dried before acrylic resin emulsion self storage-stable, bonding by force The viewpoints such as the deviation of the measured value in degree mensuration tails off are set out, at least some of and foregoing acrylic of preferably PVA system resin Resin is grafted.

In the case of PVA system resin is grafted with foregoing acrylic resin, the value (W) that following formula (2) represents is preferably 90 Below weight %, below more preferably 85 weight %, and then below preferably 80 weight %.It should be noted that as lower limit, Usually 1 weight %, preferably 5 weight %, and then preferably 10 weight %.Described value is the standard of grafting degree, if This value is too low, then the degree having a grafting is low, emulsion polymerization time protective colloid action reduction, polymerization stability reduction etc. inclines To, if this value is too high, then has and be difficult to generate high concentration and the tendency of stable emulsion.

The value (W) of formula (2) calculates as follows.

That is, the emulsion as object etc. is carried out drying at room temperature and make overlay film, by this overlay film in boiling water and in acetone Extract 8 hours respectively, remove the resin etc. not having grafting.By in the case of this, extract before overlay film absolute dry weight be set to w₁ G the overlay film absolute dry weight after (), extraction is set to w₂G (), is obtained by following formula (2).

W (weight %)=(w₂)/(w₁)×100…(2)

As the method for the value (W) regulating above-mentioned formula (2), can list: change emulsion polymerization temperature or by denier Reducing agent and the method etc. being applied in combination as the persulfate etc. of catalyst for polymerization.Such as, by improving emulsion polymerization Temperature can improve value (W), can be with decreasing value (W) by reducing emulsion polymerization temperature.It addition, use sodium acid sulfite etc. to make During for reducing agent, value (W) uprises.

In the present invention, in the acrylic resin emulsion after emulsion is polymerized, various adding can be added as required further Add agent.As such additive, can list such as: organic pigment, inorganic pigment, water-soluble additives, pH adjusting agent, anti- Rotten agent, antioxidant etc..

So, obtaining the acrylic resin emulsion of the present invention, it generally regulates preferably as nonvolatile component when using It is 0.1～65 weight %.

It addition, using described acrylic resin emulsion as hair mousse use time, with resin described later, additive etc In the case of other compounding ingredients is applied in combination, the viewpoint being not easily susceptible to limit from the use of other resin, additive goes out Sending out, preferably nonvolatile component is typically set to 30～60 weight %.

It should be noted that using described acrylic resin emulsion as hair mousse be used alone time, send out from easily correct Equably from the viewpoint of coating, preferably nonvolatile component is typically set to 1～10 weight %.

By above method, obtain the acrylic resin emulsion of the present invention.Described acrylic resin emulsion is applied In hair mousse purposes, employ the hair mousse of this emulsion given play to formative nature, again haircut performance, touch sensitivity, be washed performance this The desired performance of sample.

As long as the hair mousse of the present invention contains aforesaid propylene acid resin emulsion, can be used alone acrylic compounds tree Fat liquor, it is also possible to acrylic resin emulsion is applied in combination with various compounding agent.

In the hair mousse of the present invention, the hair mousse of the present invention preferably contains 1 in hair mousse with acrylic resin emulsion More than weight % (solid constituent conversion), more preferably contains more than 3 weight % (solid constituent conversion), and then preferably comprises 5 weights Amount more than % (solid constituent conversion).It should be noted that as the upper limit, preferably 70 weight % (solid constituent conversion), more It is preferably 60 weight % (solid constituent conversion), and then preferably 50 weight % (solid constituent conversion).The hair mousse of the present invention With acrylic resin emulsion very few time, have haircut power reduce tendency；The tendency that washing performance is easily reduced is had time additionally too much.

In the hair mousse of the present invention, suitably can be compounded known logical in above-mentioned acrylic resin emulsion according to purpose Various compounding ingredients used in normal hair mousse, such as: oil preparation, polyhydric alcohol, lower alcohol, surfactant, ultraviolet are inhaled Receive agent, spice, antioxidant, wetting agent, clear agent, vitamins, plant extract etc., thus manufacture.

As above-mentioned oil preparation, can list such as: Oleum Helianthi, Oleum Gossypii semen, soybean oil, olive oil, Oleum Cocois, Semen Ricini The oils and fatss such as oil, Jojoba oil, Camellia oil, ermine oil；Cera Flava, Brazil wax, candelilla wax, rice bran wax, shellac wax, spermaceti, sheep The wax classes such as hair fat；Ceresine, hard paraffin, liquid paraffin, liquid isoparaffin, microwax, polyethylene end, Tissuemat E, Fischer-Tropsch The hydrocarbon ils such as wax, vaseline, squalane；Lauric acid, myristic acid, Palmic acid, stearic acid, oleic acid, behenic acid, 2 Ethylbutanoic acid, The higher fatty acids such as isovaleric acid, 2 methyl valeric acid, 2-ethylpentanoic, isostearic acid, 12-hydroxy stearic acid；Lauryl alcohol, Semen Myristicae The higher alcohols such as alcohol, spermol, stearyl alcohol, oleyl alcohol, lanolin alcohol, mountain alcohol, 18 hexadecanol；Ethyl oleate, myristic acid are different Propyl ester, isopropyl palmitate, myristyl myristate, cetin, oleic acid oil base ester, myristic acid octyl dodecanol Ester, oleic acid octyl dodecanol ester, isostearic acid ethyl ester, isopropyl isostearate, 2 ethyl hexanoic acid cetyl, 2 ethyl hexanoic acid ten Six octadecyl, glycerol three 2-ethylhexanoate, the different cetylate of glycerol three, four 2 ethyl hexanoic acid pentaerythritol esters, octanoic acid are different Cetyl, sad different stearyl ester, the different cetyl of isostearic acid, isostearic acid octyl dodecanol ester, the misery base of dimethyl-octa 12 The fatty acid ester oils such as alcohol ester；Methyl polysiloxane, high polymeric MAO polysiloxanes, methyl phenyl silicone, prestox three silicon Oxygen alkane, decamethyl tetrasiloxane, octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane, ten diformazan basic ring six siloxanes, methyl The organic silicone oils etc. such as cyclopolysiloxane, alcohol modified silicone, alkyl-modified silicone, amino modified silicone, epoxy-modified silicone.It May be used alone, can also be used in combination two or more.

Generally from the viewpoint of emulsifying, the content of described oil preparation is preferably 0.5～50 weight % in hair mousse total amount, Particularly preferably 1～40 weight %.It addition, from the viewpoint of greasy, the glutinous soapy feeling reducing hair mousse, be preferably set to as far as possible Few content；But the acrylic resin emulsion of the application of the invention, can reduce the consumption of oil preparation or not use.

As above-mentioned polyhydric alcohol, can exemplify such as: ethylene glycol, dipropylene glycol, propylene glycol, i-butylene glycol, glycerol, Two glycerol, 1,3 butylene glycol, 1,2-pentanediol, 1,2-hexanediol, 1,2-ethohexadiol, Decane-1,2-diol etc..They can be independent Use, it is also possible to be applied in combination two or more.

From the viewpoint of using sense, the content of described polyhydric alcohol is preferably 0.1～20 weight % in hair mousse total amount, Particularly preferably 0.5～15 weight %.

For the hair mousse acrylic resin emulsion of the present invention, such as, by acrylic resin emulsion water, polynary Alcohol, lower alcohol etc. dilute, and make the hair mousse of liquid-type and use；Or it is compounded above-mentioned oil in acrylic resin emulsion Demultiplexing surfactant and the material of water emulsification dispersion, make viscous solution type or the hair mousse of frost shape type and use.

＜ haircuts method ＞

As the method for haircuting of the hair mousse using the hair mousse acrylic resin emulsion containing the present invention, such as may be used Following operation (A) and the method for haircuting of operation (B) is included to enumerate.

Operation (A), the hair mousse that monomer composition [I] and monomer composition [II] are carried out emulsion polymerization and obtained is with third The effectively amount of haircuting of olefin(e) acid resin emulsion coats hair；

Operation (B), before foregoing sequence (A), simultaneously and afterwards at least any one time inscribe hair adjusted For desired shape.

Wherein, aforementioned monomer compositions [I] and aforementioned monomer compositions [II] meet following condition (i)～(iii).

In (i) aforementioned monomer compositions [I] and aforementioned monomer compositions [II] at least any one comprises (methyl) third Olefin(e) acid esters monomer.

(ii) aforementioned monomer compositions [II] polymerization is used and the vitrification obtained by Fox formula of the polymer that obtains is turned Temperature (Tg2) is than using aforementioned monomer compositions [I] polymerization and the vitrification obtained by Fox formula of the polymer that obtains is turned Temperature (Tg1) is high more than 30 DEG C.

(iii) aforementioned monomer compositions [I] is monomer group with the compounding ratio (weight ratio) of aforementioned monomer compositions [II] Compound [I]: monomer composition [II]=50:50～99:1.

By haircuting in this wise, it is possible to be readily formed desired hair style.And, the hair mousse of the present invention water-soluble Property and/or water in redispersibility excellent, therefore can easily rinse.

It should be noted that from can effectively carry out the aspect haircuted, aforementioned hair mousse acrylic resin The effectively amount of haircuting of emulsion refers to, is preferably 0.01～1g relative to the topknot of length 20cm × weight 1.2g.

Embodiment

Hereinafter, list embodiment and the present invention is illustrated in more detail, but the present invention is without departing from its main idea Scope, is not limited by these embodiments.It should be noted that " part ", " % " represent weight basis in example.

First, as described below, modulate various acrylic resin emulsion.It should be noted that for acrylic resin The nonvolatile component of emulsion, viscosity utilize following method to be measured, for the mensuration of glass transition temperature according to aforementioned Method be measured.

＜ nonvolatile component ＞

It is being shaped to flat type weighing botle 50mm × 30mm of specifying with JIS R 3503 (1994) aluminium foil with floor space Ware container is smeared expansion sample 1g, correctly weighs.Container is placed in the center of temperature chamber, at 105 DEG C ± 2 DEG C, carries out 60 After ± 5 minutes are dried, cool down in exsiccator, weigh its weight.

Afterwards, calculated by following formula.

N=(Wd/Ws) × 100

(herein, N be nonvolatile component (%), Wd be the weight (g) of dried sample, Ws be dried before sample Weight (g).)

＜ viscosity ＞

It is measured with Brookfield viscometer (such as, Tokyo Keiki Inc.'s system, BL type viscometer).Not to be mixed into bubble Mode in sample container, add sample about 500ml, keep sample container so that liquid level the leading less than thermostatic bath of sample The liquid level of thermal medium.Can mix with Glass rod as required, specimen temperature is measured at 23 ± 1 DEG C.

Viscosity calculates (significant digits 2) by following formula.

η=Kn × θ

(herein, η be viscosity (mPa s), Kn be the conversion multiplier attached by viscometer, θ be that the viscometer measured for 2 times refers to Indicating value average.)

＜ embodiment 1: acrylic resin emulsion (a) ＞

Use following monomer composition [I] and monomer composition [II] in advance, prepare following shown emulsion X, emulsifying Liquid Y, solution Z.

Monomer composition [I]: 2-EHA 75 parts, methyl methacrylate 16 parts, ethylene glycol dimethyl (Mitsubishi Rayon Co., Ltd. manufacture acrylate；Trade name " Acryl ester ED ") 0.9 part, Tg1=-52 ℃

Monomer composition [II]: methyl methacrylate 9 parts, ethylene glycol dimethacrylate (Mitsubishi Rayon Co., Ltd. manufacture；Trade name " Acryl ester ED ") 0.1 part, Tg2=105 DEG C

Emulsion X: use turbo blade with 1200rpm by deionized water 64 parts, unmodified PVA system resin (average soap 88 moles of % of change degree, average degree of polymerization 500/ the Nippon Synthetic Chemical Industry Co., Ltd manufacture) 4.5 parts, monomer composition [I] breast The material changed 20 minutes and obtain.

Emulsion Y: use turbo blade with 1200rpm by deionized water 7 parts, resin (the average saponification of unmodified PVA system Spend 88 moles of %, average degree of polymerization 500/ the Nippon Synthetic Chemical Industry Co., Ltd manufactures) 0.5 part, monomer composition [II] breast The material changed 20 minutes and obtain.

Solution Z:10%APS (Ammonium persulfate .) aqueous solution 2.7 parts

In rustless steel (SUS) retort processed possessing cooling tube and stirring vane, side chain is contained 1,2-diol structure (99 moles of % of mean saponification degree, average degree of polymerization 300, the containing ratio 8 of 1,2-diol structure unit of side chain rub for the PVA of unit Your %/the Nippon Synthetic Chemical Industry Co., Ltd manufactures) 10 parts, sodium sulfite 0.2 part and sodium carbonate trihydrate 0.4 part It is dissolved completely in deionized water (72 parts), is warming up to 75 DEG C.

In retort, the most disposably add the 11% and the 30% of solution Z of emulsion X, stir 45 minutes, then use 3.1 hours dropping emulsion X remaining 89% and the 53% of solution Z, after completion of dropwise addition continuously stirred 10 minutes, obtain the 1st breast Liquid.

Then, by the total amount and the 7% of solution Z of 0.4 hour dropping emulsion Y, after completion of dropwise addition 10 minutes, disposably add Add the 5% of solution Z, and then after 35 minutes, disposably add the 5% of solution Z, stir 45 minutes.In above-mentioned polymerization, with polymerization The interior temperature of liquid keeps the mode of 75～80 DEG C to be polymerized.Then, interior temperature is set to 55 DEG C, disposable interpolation Perbutyl H- 10% aqueous solution 1.7 parts of 69 (Japan Oil Co's manufactures), was added batch-wise ascorbic 5% water-soluble points for 2 times every 30 minutes Liquid 3.4 parts, in limit keeps, temperature 50～55 DEG C is stirred on 1 hour limit altogether, obtains the 2nd emulsion.

Gained the 2nd emulsion is cooled down, obtains acrylic resin emulsion (a) (nonvolatile component 43%；Viscosity 420mPa S (Brookfield viscometer 12rpm, 23 DEG C)).It should be noted that acrylic resin emulsion (a) is by decentralized stabilization.

＜ embodiment 2: acrylic resin emulsion (b) ＞

In embodiment 1, monomer composition [I] is changed to 2-EHA 68 parts, methyl methacrylate 23 (Mitsubishi Rayon Co., Ltd. manufacture for part, ethylene glycol dimethacrylate；Trade name " Acryl ester ED ") 0.9 part, Tg1=-43 DEG C, in addition, obtain acrylic resin emulsion (b) (nonvolatile component similarly to Example 1 43%；Viscosity 1000mPa s (Brookfield viscometer 12rpm, 23 DEG C)).Acrylic resin emulsion (b) is by decentralized stabilization.

＜ comparative example 1: acrylic resin emulsion (a ') ＞

Use following monomer composition [I] in advance, prepare following shown emulsion X, solution Z.

Monomer composition [I]: 2-EHA 75 parts, methyl methacrylate 35 parts, ethylene glycol dimethyl (Mitsubishi Rayon Co., Ltd. manufacture acrylate；Trade name " Acryl ester ED ") 1 part, Tg1=-43 DEG C

Emulsion X: use turbo blade with 1200rpm by deionized water 71 parts, unmodified PVA system resin (average soap 88 moles of % of change degree, average degree of polymerization 500/ the Nippon Synthetic Chemical Industry Co., Ltd manufacture) 5 parts, monomer composition [I] emulsifying 20 minutes and the material that obtains.

Solution Z:10%APS (Ammonium persulfate .) aqueous solution 2.7 parts

In the SUS retort possessing cooling tube and stirring vane, side chain is contained 1, the PVA of 2-diol structure unit It is that (99 moles of % of mean saponification degree, average degree of polymerization 300, the containing ratio 8 of 1,2-diol structure unit of side chain rub resin Your %/the Nippon Synthetic Chemical Industry Co., Ltd manufactures) 10 parts, sodium sulfite 0.2 part and sodium carbonate trihydrate 0.4 part It is dissolved completely in deionized water (72 parts), is warming up to 75 DEG C.

In retort, the most disposably add the 10% and the 30% of solution Z of emulsion X, stir 45 minutes, then use 3.5 hours dropping emulsion X remaining 90% and the 60% of solution Z, make it carry out one-step polymerization at interior temperature 75～80 DEG C.Drip After adding end 10 minutes, disposable the 5% of the solution Z that adds, and then after 35 minutes, disposably add the 5% of solution Z, stir 45 points Clock.In above-mentioned polymerization, it is polymerized in the way of the interior temperature of polymer fluid keeps 75～80 DEG C.Then interior temperature is set to 55 DEG C, one Secondary property adds 10% aqueous solution 1.7 parts of PerbutylH-69 (Japan Oil Co's manufacture), divides and added every 30 minutes for 2 times in batches Adding ascorbic 5% aqueous solution 3.4 parts, in limit keeps, temperature 50～55 DEG C is stirred on 1 hour limit altogether.

Cool down afterwards, obtain acrylic resin emulsion (a ') (nonvolatile component 43%；Viscosity 490mPa s (B Type viscometer 12rpm, 23 DEG C)).The acrylic resin emulsion of comparative example 1 (a ') by decentralized stabilization.

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

In comparative example 1, monomer composition [I] is changed to 2-EHA 68 parts, methyl methacrylate 32 (Mitsubishi Rayon Co., Ltd. manufacture for part, ethylene glycol dimethacrylate；Trade name " Acryl ester ED ") 1 part, Tg1=-35 DEG C, in addition, obtain acrylic resin emulsion (b ') (nonvolatile component in the same manner as comparative example 1 43%；Viscosity 810mPa s (Brookfield viscometer 12rpm, 23 DEG C)).The acrylic resin emulsion of comparative example 2 (b ') disperseed Stabilisation.

The ＜ mouldability test manufacture ＞ of hair mousse solution

For above-described embodiment 1 and 2, respectively acrylic resin emulsion (a) and acrylic resin emulsion (b) are spent Ionized water dilution makes nonvolatile component become 3%, for comparative example 1 and 2, respectively by acrylic resin emulsion (a ') and third Olefin(e) acid resin emulsion (b ') make nonvolatile component become 3% with deionized water dilution, it is respectively prepared mouldability test and uses Hair mousse solution.

Use above-mentioned mouldability test hair mousse solution, as following to performance of haircuting (shaping force), haircut performance again (again shaping force, shape retentivity again) and touch sensitivity be evaluated.

＜ haircuts performance (shaping force) ＞

To topknot (length 20cm × weight 1.2g；Ketabaya) it is coated with the test of above-mentioned mouldability equably to use with dropper Hair mousse solution 0.5g, and then massage the most equably with the finger having put on polyethylene glove and be coated with.Arrange with finger So that the width of topknot becomes to be about 1cm, be dried with 100 DEG C × 1 minute with blowing-dryer, with the hair of constraint downwards and The angle of about 45 ° hands keeps to surface to send out the tip, and whether being fixed into row official for topknot can evaluate.Evaluation methodology is as follows.

(metewand)

Zero ... also can be haircuted into restrained state even if somewhat shaking.

△ ... if somewhat shaken, sends out the tip and somewhat launches.

× ... if not retraining or somewhat shaking, send out the tip and scatter completely.

＜ haircuts performance (shaping force again) ＞ again

Topknot finger after having carried out the above-mentioned power of haircuting evaluation is untied, so with comb comb open after, again use hands Refer to constraint topknot, sense evaluation is carried out for topknot state now.Evaluation methodology is as follows.

(metewand)

Zero ... again retrain topknot (haircuting).

△ ... and though constraint topknot somewhat launch.

× ... do not become topknot, can not haircut.

It should be noted that in above-mentioned evaluation, "○" represents excellent performance, " △ " represents that practicality is upper and allows.It addition, "×" Represent poor performance.

＜ haircuts performance (retentivity of shaping again) ＞ again

Topknot state when vibration gently has been carried out the topknot after above-mentioned performance of haircuting again (shaping force again) is evaluated is carried out Sense is evaluated.Evaluation methodology is as described below.

(metewand)

Zero ... keep the state constant the most do not scatter (haircut again and be kept) that topknot is restrained.

△ ... topknot slightly launches.

× ... topknot scatters (cannot keep haircuting) significantly again.

The touch sensitivity ＞ of ＜

The restraint feeling of hair when evaluating for above-mentioned performance of haircuting again (shaping force again), comments by finger opponent's sense of touch Valency.Evaluation methodology is as follows.

(metewand)

Zero ... the most smooth.

△ ... the most crude.

× ... the most crude.

＜ is washed the manufacture ＞ of performance test hair mousse solution

For above-described embodiment 1 and 2, the most directly use acrylic resin emulsion (a) and acrylic resin emulsion B () is formed respectively and is washed performance test hair mousse solution, for above-mentioned comparative example 1 and 2, the most directly use acrylic compounds Resin emulsion (a ') and acrylic resin emulsion (b ') are formed respectively and are washed performance test hair mousse solution.

＜ is washed performance (warm water) ＞

To be washed the PET that performance test hair mousse solution utilizes 100 μm applicators to coat 50 μ m-thick (poly-right by above-mentioned PET) thin film, 23 DEG C, carry out under 50%RH 30 minutes being dried, obtain thickness about 25 μm (when being dried) Film.On film, drip the deionized water of 1 60 DEG C with dropper, wipe 1 time lightly with finger to draw diameter about 1cm's Circle, wipes with paper pulp Cotton Pulp (Nippon Paper Crecia Co., Ltd. system, " Kimwipe " (registered trade mark)).It After, again drip the deionized water of 1 60 DEG C and with referring to wiping with dropper, repeat such operation and amount to 10 times.With the most right It is evaluated in the washing degree being coated with membranaceous hair mousse solution.Evaluation methodology is as follows.

(metewand)

Zero ... wipe 70% with up to 100%.

△ ... wipe 30% less than 70%.

× ... wipe 0 less than 30%.

＜ is washed performance (cold water) ＞

To be washed the PET that performance test hair mousse solution utilizes 100 μm applicators to coat 50 μ m-thick (poly-right by above-mentioned PET) thin film, 23 DEG C, carry out under 50%RH 30 minutes being dried, obtain thickness about 25 μm (when being dried) Film.On film, drip the deionized water of 1 15 DEG C with dropper, after 1 minute, tap lightly with finger 10 times, then use Paper pulp Cotton Pulp (Nippon Paper Crecia Co., Ltd. system, " Kimwipe " (registered trade mark)) is wiped.With the most right It is evaluated in the washing degree being coated with membranaceous hair mousse solution.Evaluation methodology is as follows.

(metewand)

Zero ... wipe 70% with up to 100%.

△ ... wipe 30% less than 70%.

× ... wipe 0 less than 30%.

By embodiment 1,2 and the knot of the test of the composition of comparative example 1,2, glass transition temperature and use hair mousse solution Fruit is shown in table 1.

[table 1]

2EHA: 2-EHA

MMA: methyl methacrylate

EGDMA: ethylene glycol dimethacrylate

Understand, for using the haircuting of acrylic resin emulsion obtained by 2 steps polymerizations of above-described embodiment 1 and 2 Agent, mouldability (performance of haircuting, again haircut performance, touch sensitivity) is good with the harmony being washed performance and excellent.

On the other hand understand, for the acrylic resin emulsion obtained by non-multistep polymerization of comparative example 1 and 2, though So haircut performance, again haircuting property, touch sensitivity well, but the performance of being washed, poor in particular with the being washed property of cold water.

It addition, the present invention is described in detail with reference to specific embodiment, can be the master without departing from the present invention Purport and scope ground apply various changes, correction, and this is apparent to those skilled in the art.The application is based on 2014 Japanese patent application (Japanese Patent Application 2014-044861) filed on March 7, herein with reference to and quote its content.

Industrial applicability

The hair mousse acrylic resin emulsion of the present invention (performance of haircuting, is haircuted performance, sense of touch in mouldability again Property) aspect of performance harmony is good and excellent, therefore, it is possible to be applied in combination with various compounding agent with being washed, it is possible to it is applied to each Plant dosage form, be useful.

Claims (7)

1. a hair mousse acrylic resin emulsion, it is characterised in that be by monomer composition [I] and monomer composition [II] carries out emulsion polymerization and obtains,

Described monomer composition [I] and described monomer composition [II] meet following condition (i)～(iii):

In (i) described monomer composition [I] and described monomer composition [II] at least any one comprises (methyl) acrylic acid Esters monomer,

(ii) glass transition temperature obtained by Fox formula of the polymer using described monomer composition [II] to be polymerized and to obtain The glass transition temperature obtained by Fox formula of the polymer that degree Tg2 obtains than using described monomer composition [I] to be polymerized Tg1 is high more than 30 DEG C,

(iii) described monomer composition [I] is monomer composition with the compounding ratio (weight ratio) of described monomer composition [II] [I]: monomer composition [II]=50:50～99:1.

Hair mousse acrylic resin emulsion the most according to claim 1, it is characterised in that described glass transition temperature Degree Tg1 is less than 0 DEG C, and described glass transition temperature Tg 2 is more than 30 DEG C.

Hair mousse acrylic resin emulsion the most according to claim 1 and 2, it is characterised in that acrylic resin Acrylic resin granule in emulsion passes through polyvinyl alcohol resin by decentralized stabilization.

Hair mousse acrylic resin emulsion the most according to claim 3, it is characterised in that described polyethenol series tree Fat contains the side chain 1 shown in following formula (1), 2-diol structure unit,

In formula (1), R¹～R⁶Separately representing hydrogen atom or organic group, X represents singly-bound or bonding chain.

5. according to the hair mousse acrylic resin emulsion according to any one of Claims 1 to 4, it is characterised in that only make With described monomer composition [I] and described monomer composition [II], first carry out the emulsion polymerization of described monomer composition [I], Then the emulsion polymerization of described monomer composition [II] is carried out.

6. a hair mousse, it is characterised in that containing the hair mousse acrylic compounds tree according to any one of Claims 1 to 5 Fat liquor.

7. haircuting a method, it includes following operation (A) and operation (B):

Operation (A), the hair mousse acrylic acid that monomer composition [I] and monomer composition [II] are carried out emulsion polymerization and obtain The effectively amount of haircuting of resin emulsion coats hair；

Operation (B), before described operation (A), simultaneously and afterwards at least any one moment hair is adjusted to expectation Shape,

Wherein, described monomer composition [I] and described monomer composition [II] meet following condition (i)～(iii):

In (i) described monomer composition [I] and described monomer composition [II] at least any one comprises (methyl) acrylic acid Esters monomer,

(ii) glass transition temperature obtained by Fox formula of the polymer using described monomer composition [II] to be polymerized and to obtain The glass transition temperature obtained by Fox formula of the polymer that degree Tg2 obtains than using described monomer composition [I] to be polymerized Tg1 is high more than 30 DEG C,

(iii) described monomer composition [I] is monomer composition with the compounding ratio (weight ratio) of described monomer composition [II] [I]: monomer composition [II]=50:50～99:1.