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.
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.