CN101952386A - Aqueous polymer dispersion composition and water-repellent oil-repellent agent - Google Patents
Aqueous polymer dispersion composition and water-repellent oil-repellent agent Download PDFInfo
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- CN101952386A CN101952386A CN2009801059442A CN200980105944A CN101952386A CN 101952386 A CN101952386 A CN 101952386A CN 2009801059442 A CN2009801059442 A CN 2009801059442A CN 200980105944 A CN200980105944 A CN 200980105944A CN 101952386 A CN101952386 A CN 101952386A
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Abstract
Disclosed is a water-dispersed water-repellent oil-repellent composition which can exhibit high water/oil repellency and durability thereof even when the amount of an Rf-containing resin used therein is significantly reduced. The water-repellent oil-repellent composition is characterized by containing a polymer (A) and a polymer (B) which are not present in a same one particle. The polymer (A) is an addition polymer containing a polymerization unit of a polymerizable monomer (a) described below and a polymerization unit of a polymerizable monomer (b) or (c) described below. The polymer (B) is an addition polymer not containing a polymerization unit of the polymerizable monomer (a) but containing a polymerization unit of the polymerizable monomer (c) or a polymerizable monomer (y). The polymerizable monomer (a) is a (meth)acrylate having a polyfluoroalkyl group or an acrylate halogen-substituted at the a-position. The polymerizable monomers (b) and (c) are acrylates having an alkyl group but not having a polyfluoroalkyl group, which may be halogen-substituted at the a-position. The polymerizable monomer (y) is a polymerizable monomer wherein a halogen atom is bonded to a carbon atom constituting an unsaturated double bond.
Description
Technical field
Also can pay the excellent water-repellent oil-repellent (particularly water-repellancy) and the water extraction oil extracticn agent composition (particularly dryingagent composition) of weather resistance thereof even the object of the present invention is to provide a kind of usage quantity of reduction fluorochemical monomer to article such as fibers.
Background technology
In the prior art, the polymkeric substance or the multipolymer of the known polymerizable monomer that will contain fluoro-alkyl or the compound that contains fluoro-alkyl are as organic solvent solution or aqueous dispersion, fibre product etc. is handled, thus the technology of their surface being paid water-repellent oil-repellent.
With the weather resistance that improves the water-repellent oil-repellent of washing or dry-cleaning etc. is purpose, has attempted making the polymerizable monomer that contains fluoro-alkyl and has had the method that the monomer of cementability group carries out copolymerization.In addition, also attempt not contain the polymkeric substance and the mixed with polymers that contains fluoro-alkyl of fluoro-alkyl, createed the water-repellent oil-repellent composition (patent documentation 1～2) of economy excellence.
In addition, as can not making antifouling property and endurance quality etc. reduce polymkeric substance, multipolymer that ground adds, advocate the polymerizable monomer (patent documentation 3) that use has ad hoc structure.
In recent years, a kind of resin combination is disclosed, contain two kinds of different polymkeric substance of the content of polymkeric substance of fluoro-alkyl by mixing and do not contain the polymkeric substance of fluoro-alkyl, thereby obtain having the resin combination (patent documentation 4) on the surface that surface property such as water-repellent oil-repellent and maintenance thereof be improved.
In addition, disclosing by at least a homopolymer in the hydrocarbon mixture polymerizable compound or multipolymer and glass transition point is polymkeric substance more than 50 ℃, thereby improve the scheme (patent documentation 5) of slip resistance, a kind of carpet is also disclosed with dialling liquor, it is characterized in that, mix the polymkeric substance that contains the polymkeric substance of fluoro-alkyl and do not contain fluoro-alkyl, any glass transition point or fusing point are all at (patent documentation 6) more than 45 ℃.
Patent documentation 1: Japanese Patent Publication 38-22487
Patent documentation 2: Japanese Patent Publication 41-8579
Patent documentation 3: Japanese Patent Publication 49-42878
Patent documentation 4: Japanese kokai publication hei 06-228241
Patent documentation 5: Japanese kokai publication sho 61-264081
Patent documentation 6:US4043964
Summary of the invention
In existing water extraction oil extracticn agent, with the weather resistance that improves the water-repellent oil-repellent of washing or dry-cleaning etc. is purpose, the monomer of having attempted making the polymerizable monomer that contains fluoro-alkyl and having had a cementability group carries out copolymerization, perhaps mixes the scheme of the high polymkeric substance of the polymkeric substance that contains fluoro-alkyl and film toughness.But,, cause the insufficient result of weather resistance though can realize higher water-repellent oil-repellent by a large amount of importing fluorinated monomers.On the contrary, though the monomer that has a cementability group by a large amount of importings can be paid sufficient weather resistance, lack water-repellent oil-repellent.In addition, in order to show sufficient water-repellent oil-repellent, must import a large amount of fluoromonomers, because fluoromonomers is very expensive, thereby cost improves.
Even expectation obtains the also excellent machining agent of weather resistance that a kind of usage quantity of reduction fluoromonomers also can be brought into play high water-repellent oil-repellent and water-repellent oil-repellent.
The present inventor is purpose in order to address the above problem even also can bring into play the also excellent water extraction oil extracticn agent composition of high water-repellent oil-repellent and weather resistance with the usage quantity that a kind of reduction fluoromonomers is provided, and furthers investigate.Found that, by mixing have the polymerized unit with particular chemical structure polymkeric substance, have the polymkeric substance and the aqueous liquid dispersion that are derived from the monomeric polymerized unit that contains fluoro-alkyl, can have significant water-repellent oil-repellent and weather resistance, realize above-mentioned purpose, thereby finish the present invention.
That is, the invention provides a kind of aqueous dispersion type water extraction oil extracticn agent composition that contains water-medium, following polymkeric substance (A) and following polymkeric substance (B).
Polymkeric substance (A) is the polymkeric substance that contains fluoro-alkyl,
Polymkeric substance (B) is the polymkeric substance that contains halogen atom on the main chain.
" contain halogen atom on the main chain " and be meant on the carbon atom of the main chain that constitutes polymkeric substance and directly be combined with halogen atom.
The invention effect
According to the present invention, have the polymkeric substance (B) of polymerized unit and have the aqueous dispersion type water-repellent oil-repellent composition that the polymkeric substance (A) that is derived from the monomeric polymerized unit that contains fluoro-alkyl obtains by mixing and have significant water-repellent oil-repellent and weather resistance with particular chemical structure.Therefore, the present invention can provide by the usage quantity that reduces fluoromonomers and reduce cost, high water-repellent oil-repellent and the also excellent water extraction oil extracticn agent of weather resistance of performance.
Embodiment
Below, describe the present invention in detail.
The invention provides a kind of water extraction oil extracticn agent composition, it is characterized in that, contain following polymkeric substance (A) and following polymkeric substance (B), and polymkeric substance (A) and polymkeric substance (B) are not present in the same particle.Usually, the particle that forms by polymkeric substance (A) and in aqueous liquid dispersion, exist respectively by the particle that polymkeric substance (B) forms.
Polymkeric substance (A) is the polymkeric substance of the polymerized unit (more than the preferred 50 weight %) that contains following polymerizable monomer (a) and at least a polymerized unit in following polymerizable monomer (b) or the polymerizable monomer (c) (preferred 50 weight % following (also be included as the situation of 0 weight %, but more than the preferred 1 weight %)).
Polymkeric substance (B) is not contain the polymerized unit of polymerizable monomer (a) and contain at least a polymkeric substance in polymerizable monomer (y) or the polymerizable monomer (c).
Polymerizable monomer (a) is to have (methyl) acrylate of multi-fluorinated alkyl or the esters of acrylic acid that the α position is replaced by halogen.
Polymerizable monomer (b) is to have alkyl and (methyl) acrylate of not having multi-fluorinated alkyl.
Polymerizable monomer (c) is to have alkyl and do not have acrylate multi-fluorinated alkyl, that the α position is replaced by halogen.
Polymerizable monomer (y) is the polymerizable monomer except that polymerizable monomer (a) and (b), (c), is combined with halogen atom on the carbon atom that forms unsaturated double-bond.
In addition, the invention provides and use this water extraction oil extracticn agent composition to handle and the article that obtain.
In this manual, vinylformic acid and methacrylic acid are referred to as (methyl) vinylformic acid.The souvenir of (methyl) acrylate etc. is also identical.In addition, multi-fluorinated alkyl is designated as the Rf base.
Polymkeric substance (A) is preferably more than the polymerized unit 50 weight % that contain polymerizable monomer (a), at least a polymerized unit 50 weight % in polymerizable monomer (b) or the polymerizable monomer (c) following (situation that comprises 0 weight %), as required, contain polymerizable monomer (a), (b) polymerizable monomer in addition (x) (for example, forming the polymerizable monomer (z) that is combined with (y) of halogen atom on the carbon atom of unsaturated double-bond or has reactive group) polymerized unit, and, the polymerized unit of polymerizable monomer (a), the polymerized unit of polymerizable monomer (b) and polymerizable monomer (c) add up to the above addition polymer of 50 weight %.That is, can not contain polymerizable monomer (b) or polymerized unit (c) in the polymkeric substance (A).
Polymerizable monomer (a) is to have (methyl) acrylate of Rf base or the esters of acrylic acid that the α position is replaced by halogen [below, be designated as monomer (a) or contain the monomer of Rf base].Have (methyl) acrylate of Rf base or esters of acrylic acid that the α position is replaced by halogen and be meant that the Rf base is present in the compound of the pure residue part of (methyl) vinylformic acid or α substituted acrylate.
The Rf base is two groups that above hydrogen atom is replaced by fluorine atom of alkyl.The carbonatoms of Rf base is preferably 2～20, and more preferably 4～16, be preferably 4～6 especially.There was the tendency of water-repellancy decline in carbonatoms less than 2 o'clock; Surpass at 20 o'clock, exist monomer (a) to become solid at normal temperatures, sublimability also increases, operate the tendency that becomes difficult.
In addition, the Rf base also can contain other the halogen atom except that fluorine atom.As other halogen atom, preferred chlorine atom.In addition, can also between the C-C in the Rf base, insert the Sauerstoffatom of ether type or the sulphur atom of thioether type.As the structure of the terminal portions of Rf base, can enumerate CF
3CF
2-, (CF
3)
2CF-, CHF
2-, CH
2F-, CClF
2-etc., preferred CF
3CF
2-.
The Rf base is the group that the plural hydrogen atom of saturated alkyl is replaced by fluorine atom.The ratio of the fluorine atom in the Rf base (number of fluorine atoms in the Rf base)/(number of hydrogen atoms in the number of fluorine atoms in the Rf base+Rf base) is preferably more than 40%, and be preferred especially more than 60%.In addition, part or all of the hydrogen atom of Rf base can be replaced by the chlorine atom.
The structure of preferred straight chain of Rf base or side chain, the structure of preferred especially straight chain.When being branched structure, preferred component is present near the end of Rf base.In addition, preferred component is that carbonatoms is about 1～4 short chain.In addition, the preferred carbonatoms of Rf base is 1～12.
As the Rf base, the ratio of preferred especially above-mentioned fluorine atom is essentially 100% perfluoroalkyl or contains the Rf base of perfluoroalkyl moieties.Perfluoroalkyl is the structure of preferred straight chain also.As the perfluoroalkyl of straight chain, preferably with C
mF
2m+1The situation of-(wherein, m is 2～20 integer) expression.
The concrete example of Rf is listed below.Wherein, in following example, comprise the different group of structure, promptly comprise the isomerism group with same molecular formula.C
4F
9-[F (CF
2)
4-, (CF
3)
2CFCF
2-, (CF
3)
3C-], C
5F
11-[F (CF
2)
5-, (CF
3)
3CCF
2-etc.], C
6F
13-[F (CF
2)
6-etc.], C
7F
15-, C
8H
17-, C
9F
19-, C
10F
21-, Cl (CF
2)
t-, H (CF
2)
t(t is 2～20 integer), (CF
3)
2CF (CF
2)
y-(y is 1～17 integer) etc.
Contain in the monomer of Rf base, Rf base and polymerizability unsaturated group directly in conjunction with or by the indirect combination of conjugated group, preferred indirect bonded situation.As conjugated group, be the conjugated group more than the divalent, preferred alkylidene group, ester group, amide group, amino, urethane groups, ether, inferior phenoxy group, alkylsulfonyl or contain the conjugated group of these structures.These contain the monomer of Rf, can adopt known or known compound, can by the alcohol that contains the Rf base, contain the carboxylic acid of Rf base or contain the sulfonic acid etc. of Rf base easily synthetic.
Wherein, as the monomer that contains the Rf base of the present invention, the compound of one of preferred Rf base structure that is connected with the polymerizability unsaturated group by the conjugated group of divalent.For example preferably contain the Rf base acrylate, contain the Rf base methacrylic ester, contain the Rf base vinylbenzene, contain the vinyl acetate of Rf base and contain fumarate of Rf base etc.
In addition, as the monomer that contains the Rf base of the present invention,, especially preferably contain (methyl) acrylate of Rf base or the acrylate that the α position is chlorinated from the viewpoint of versatility.
The monomer that preferably contains the Rf base is by general formula R f-Q
1-X
1Expression,
[in the formula, Rf represents fluoro-alkyl, Q
1The organic group of expression divalence, X
1Expression contains any monovalent organic radical group of polymerizability unsaturated group.]
Q
1Expression divalent organic group, preferred-(CH
2)
N+p-,-(CH
2)
nC (O) ONH (CH
2)
p-,-(CH
2)
nCONH (CH
2)
p-,-(CH
2)
nSO
2NH (CH
2)
p-,-(CH
2)
nNHC (O) NH (CH
2)
p-etc.Wherein, n and p represent the integer more than 0 or 1, and n+p is 2～22 integer.Wherein, as Q
1, preferred-(CH
2)
N+p-,-(CH
2)
nC (O) ONH (CH
2)
p-,-(CH
2)
nSO
2NH (CH
2)
p-, and p is the integer more than 2, n+p is 2～6 situation.Preferred especially n+p be 2～6 o'clock-(CH
2)
N+p-, promptly preferred dimethylene～hexa-methylene.
X
1Expression contains 1 valency organic group of polymerizability unsaturated group, preferred alkenes class residue, ethene ethers residue, vinyl esters residue, (methyl) esters of acrylic acid residue, styrenic residue etc.As the olefines residue, preferred-CR
1=CH
2Or-OCH
2-
-CR
1=CH
2As (methyl) esters of acrylic acid residue, preferred-OC (O) CR
1=CH
2As ethene ethers residue, preferred-OCR
1=CH
2As the vinyl esters residue, preferred-C (O) OCR
1=CH
2As the styrenic residue, preferred-
-CH=CH
2Or-O-
-CH=CH
2Wherein, R
1Be that hydrogen atom, carbonatoms are 1～21 straight chain shape or prop up catenate alkyl, fluorine atom, chlorine atom, bromine atoms, iodine atom, CFX
1X
2Base (wherein, X
1And X
2Be hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom), cyano group, carbonatoms is the phenyl of benzyl, replacement or the non-replacement of 1～21 straight chain shape or catenate fluoro-alkyl, replacement or non-replacement,
It is phenylene.Wherein, as X
1, the residue of preferred (methyl) esters of acrylic acid, preferred especially R
1Be hydrogen atom, methyl or chlorine atomic time-OC (O) CR
1=CH
2, that is, and preferred acryloxy, methacryloxy or alpha-chloro acryloxy.As containing the Rf monomer, from the flexibility of the film that forms with other monomeric polymerizability and at fiber, to the cementability of base material, to the viewpoint of the solvability of solvent, the easiness of emulsion polymerization etc., preferred especially (methyl) esters of acrylic acid.
The monomer that contains the Rf base can use a kind of or use two or more.
As the monomeric example that contains the Rf base, can be the material of following general formula.
General formula: CH
2=C (X)-C (=O)-Y-Z-Rf
[in the formula, X is that hydrogen atom, carbonatoms are 1～21 straight chain shape or prop up catenate alkyl, fluorine atom, chlorine atom, bromine atoms, iodine atom, CFX
1X
2Base (wherein, X
1And X
2Be hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom), cyano group, carbonatoms is the phenyl of benzyl, replacement or the non-replacement of 1～21 straight chain shape or catenate fluoro-alkyl, replacement or non-replacement; Y is-O-or-NH-; Z is that carbonatoms is that 1～10 fatty group, carbonatoms are 6～18 aromatic series base or annular aliphatic base, CH (R
1) SO
2-Ji (wherein, R
1Be that carbonatoms is 1～4 alkyl) ,-CH
2CCH (OZ
1) CH
2-Ji (wherein, Z
1Be hydrogen atom or ethanoyl) ,-(CH
2)
m-SO
2-(CH
2)
n-Ji or-(CH
2)
m-S-(CH
2)
n-Ji (wherein, m is 1～10, n be 0～10), Rf is that carbonatoms is 1～21 a straight chain shape or a catenate fluoro-alkyl.]
As the monomeric concrete example that contains the Rf base, can illustration following material, but be not subjected to the qualification of these materials.
CH
2＝C(-H)-C(＝O)-O-(CH
2)
2-Rf
CH
2＝C(-H)-C(＝O)-O-C
6H
4-Rf
CH
2＝C(-Cl)-C(＝O)-O-(CH
2)
2-Rf
CH
2＝C(-H)-C(＝O)-O-(CH
2)
2N(-CH
3)SO
2-Rf
CH
2＝C(-H)-C(＝O)-O-(CH
2)
2N(-C
2H
5)SO
2-Rf
CH
2＝C(-H)-C(＝O)-O-CH
2CH(-OH)CH
2-Rf
CH
2＝C(-H)-C(＝O)-O-CH
2CH(-OCOCH
3)CH
2-Rf
CH
2＝C(-H)-C(＝O)-O-(CH
2)
2-S-Rf
CH
2＝C(-H)-C(＝O)-O-(CH
2)
2-S-(CH
2)
2-Rf
CH
2＝C(-H)-C(＝O)-O-(CH
2)
3-SO
2-Rf
CH
2＝C(-H)-C(＝O)-O-(CH
2)
2-SO
2-(CH
2)
2-Rf
CH
2＝C(-H)-C(＝O)-NH-(CH
2)
2-Rf
CH
2＝C(-CH
3)-C(＝O)-O-(CH
2)
2-S-Rf
CH
2＝C(-CH
3)-C(＝O)-O-(CH
2)
2-S-(CH
2)
2-Rf
CH
2＝C(-CH
3)-C(＝O)-O-(CH
2)
3-SO
2-Rf
CH
2＝C(-CH
3)-C(＝O)-O-(CH
2)
2-SO
2-(CH
2)
2-Rf
CH
2＝C(-CH
3)-C(＝O)-NH-(CH
2)
2-Rf
CH
2＝C(-F)-C(＝O)-O-(CH
2)
2-S-Rf
CH
2＝C(-F)-C(＝O)-O-(CH
2)
2-S-(CH
2)
2-Rf
CH
2＝C(-F)-C(＝O)-O-(CH
2)
2-SO
2-Rf
CH
2＝C(-F)-C(＝O)-O-(CH
2)
2-SO
2-(CH
2)
2-Rf
CH
2＝C(-F)-C(＝O)-NH-(CH
2)
2-Rf
CH
2＝C(-Cl)-C(＝O)-O-(CH
2)
2-S-Rf
CH
2＝C(-Cl)-C(＝O)-O-(CH
2)
2-S-(CH
2)
2-Rf
CH
2＝C(-Cl)-C(＝O)-O-(CH
2)
2-SO
2-Rf
CH
2＝C(-Cl)-C(＝O)-O-(CH
2)
2-SO
2-(CH
2)
2-Rf
CH
2＝C(-Cl)-C(＝O)-NH-(CH
2)
2-Rf
CH
2＝C(-CF
3)-C(＝O)-O-(CH
2)
2-S-Rf
CH
2＝C(-CF
3)-C(＝O)-O-(CH
2)
2-S-(CH
2)
2-Rf
CH
2＝C(-CF
3)-C(＝O)-O-(CH
2)
2-SO
2-Rf
CH
2＝C(-CF
3)-C(＝O)-O-(CH
2)
2-SO
2-(CH
2)
2-Rf
CH
2＝C(-CF
3)-C(＝O)-NH-(CH
2)
2-Rf
CH
2＝C(-CF
2H)-C(＝O)-O-(CH
2)
2-S-Rf
CH
2＝C(-CF
2H)-C(＝O)-O-(CH
2)
2-S-(CH
2)
2-Rf
CH
2＝C(-CF
2H)-C(＝O)-O-(CH
2)
2-SO
2-Rf
CH
2＝C(-CF
2H)-C(＝O)-O-(CH
2)
2-SO
2-(CH
2)
2-Rf
CH
2＝C(-CF
2H)-C(＝O)-NH-(CH
2)
2-Rf
CH
2＝C(-CN)-C(＝O)-O-(CH
2)
2-S-Rf
CH
2＝C(-CN)-C(＝O)-O-(CH
2)
2-S-(CH
2)
2-Rf
CH
2＝C(-CN)-C(＝O)-O-(CH
2)
2-SO
2-Rf
CH
2＝C(-CN)-C(＝O)-O-(CH
2)
2-SO
2-(CH
2)
2-Rf
CH
2＝C(-CN)-C(＝O)-NH-(CH
2)
2-Rf
CH
2＝C(-CF
2CF
3)-C(＝O)-O-(CH
2)
2-S-Rf
CH
2＝C(-CF
2CF
3)-C(＝O)-O-(CH
2)
2-S-(CH
2)
2-Rf
CH
2＝C(-CF
2CF
3)-C(＝O)-O-(CH
2)
2-SO
2-Rf
CH
2＝C(-CF
2CF
3)-C(＝O)-O-(CH
2)
2-SO
2-(CH
2)
2-Rf
CH
2＝C(-CF
2CF
3)-C(＝O)-NH-(CH
2)
2-Rf
CH
2＝C(-F)-C(＝O)-O-(CH
2)
3-S-Rf
CH
2＝C(-F)-C(＝O)-O-(CH
2)
3-S-(CH
2)
2-Rf
CH
2＝C(-F)-C(＝O)-O-(CH
2)
3-SO
2-Rf
CH
2＝C(-F)-C(＝O)-O-(CH
2)
3-SO
2-(CH
2)
2-Rf
CH
2＝C(-F)-C(＝O)-NH-(CH
2)
3-Rf
CH
2＝C(-Cl)-C(＝O)-O-(CH
2)
3-S-Rf
CH
2＝C(-Cl)-C(＝O)-O-(CH
2)
3-S-(CH
2)
2-Rf
CH
2＝C(-Cl)-C(＝O)-O-(CH
2)
3-SO
2-Rf
CH
2＝C(-Cl)-C(＝O)-O-(CH
2)
3-SO
2-(CH
2)
2-Rf
CH
2＝C(-CF
3)-C(＝O)-O-(CH
2)
3-S-Rf
CH
2＝C(-CF
3)-C(＝O)-O-(CH
2)
3-S-(CH
2)
2-Rf
CH
2＝C(-CF
3)-C(＝O)-O-(CH
2)
3-SO
2-Rf
CH
2＝C(-CF
3)-C(＝O)-O-(CH
2)
3-SO
2-(CH
2)
2-Rf
CH
2＝C(-CF
2H)-C(＝O)-O-(CH
2)
3-S-Rf
CH
2＝C(-CF
2H)-C(＝O)-O-(CH
2)
3-S-(CH
2)
2-Rf
CH
2＝C(-CF
2H)-C(＝O)-O-(CH
2)
3-SO
2-Rf
CH
2＝C(-CF
2H)-C(＝O)-O-(CH
2)
3-SO
2-(CH
2)
2-Rf
CH
2＝C(-CN)-C(＝O)-O-(CH
2)
3-S-Rf
CH
2＝C(-CN)-C(＝O)-O-(CH
2)
3-S-(CH
2)
2-Rf
CH
2＝C(-CN)-C(＝O)-O-(CH
2)
3-SO
2-Rf
CH
2＝C(-CN)-C(＝O)-O-(CH
2)
3-SO
2-(CH
2)
2-Rf
CH
2＝C(-CF
2CF
3)-C(＝O)-O-(CH
2)
3-S-Rf
CH
2＝C(-CF
2CF
3)-C(＝O)-O-(CH
2)
3-S-(CH
2)
2-Rf
CH
2＝C(-CF
2CF
3)-C(＝O)-O-(CH
2)
3-SO
2-Rf
CH
2＝C(-CF
2CF
3)-C(＝O)-O-(CH
2)
2-SO
2-(CH
2)
2-Rf
[in the above-mentioned formula, Rf is that carbonatoms is 1～21 fluoro-alkyl, and preferred especially carbonatoms is 1～6 fluoro-alkyl.]
The monomer that contains the Rf base can be two or more mixture.With respect to polymkeric substance (A), the monomeric amount that contains the Rf base is 50～100 weight %, for example is 50～90 weight %.
Polymerizable monomer (b) is to have alkyl and (methyl) acrylate (below, be designated as monomer (b)) of not having the Rf base.(methyl) acrylate with alkyl is meant that alkyl is present in the compound of the pure residue part of (methyl) acrylate.As alkyl, preferred carbonatoms is 2 or more, for example 2～30 alkyl (ring-type and catenate alkyl), the especially preferably alkyl of linear chain structure.
As the concrete example of monomer (b), can enumerate (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) ethyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid cetyl, (methyl) stearyl acrylate ester, (methyl) vinylformic acid mountain Yu ester, (methyl) lauryl acrylate, (methyl) cyclohexyl acrylate etc.Monomer (b) can be to have alkyl and polymerizable monomer two or more that do not have the Rf base.
Polymerizable monomer (c) is to have alkyl and do not have the acrylate Rf base, that the α position is replaced by halogen (below, be designated as monomer (c)).Having α position that acrylate that alkyl and α position replaced by halogen is meant acrylate by the acrylate that halogen replaces, is the compound that alkyl is present in pure residue part.As alkyl, preferred carbonatoms is 2 or more, for example 2～30 alkyl (ring-type and catenate alkyl), the especially preferably alkyl of linear chain structure.
As the concrete example of monomer (c), preferably enumerate α-Lv Daibingxisuan ethyl ester, the positive butyl ester of α-Lv Daibingxisuan, α-Lv Daibingxisuan isobutyl ester, the α-Lv Daibingxisuan tert-butyl ester, α-Lv Daibingxisuan-2-ethylhexyl, α-Lv Daibingxisuan isodecyl ester, α-Lv Daibingxisuan cetyl, α-Lv Daibingxisuan stearyl ester, α-Lv Daibingxisuan mountain Yu ester, α-Lv Daibingxisuan lauryl, α-Lv Daibingxisuan cyclohexyl etc.Monomer (c) can be to have alkyl and polymerizable monomer two or more that do not have the Rf base.
In the polymkeric substance (A), when containing the polymerized unit of monomer (b) or monomer (c), the weight ratio of the polymerized unit of the polymerized unit of preferred monomers (a)/(monomer (b)+monomer (c)) is more than 1.
The total that polymkeric substance (A) is preferably the polymerized unit of the polymerized unit of the polymerized unit of the polymerizable monomer (x) that contains as required except that polymerizable monomer (a) and (b), (c) (for example, be combined with (y) of chlorine atom on the carbon atom that forms unsaturated double-bond or have the polymerizable monomer (z) of reactive group) and polymerizable monomer (a) and polymerizable monomer (b) and polymerizable monomer (c) is the addition polymer more than the 70 weight % with respect to polymkeric substance.
With respect to polymkeric substance, the ratio of the polymerized unit of monomer (a) is more than the 50 weight % in the polymkeric substance (A), for example is preferably 50～90 weight %, is preferably 60～80 weight % especially.With respect to polymkeric substance, the ratio of the polymerized unit of monomer (b) is below the 50 weight % in the polymkeric substance (A), for example is preferably 1～40 weight %, is preferably 3～30 weight % especially.With respect to polymkeric substance, the ratio of the polymerized unit of monomer (c) is below the 50 weight % in the polymkeric substance (A), for example is preferably 0～40 weight %, and more preferably 0～30 weight % is preferably 1～10 weight % especially.
With respect to polymkeric substance (A), adding up to more than the 90 weight % of the polymerized unit of the polymerized unit of the polymerized unit of monomer (a), monomer (b), the polymerized unit of monomer (c) and monomer (x) for example is preferably 95～100 weight %.
With respect to polymkeric substance (A), the ratio of the polymerized unit of monomer (x) is below the 70 weight %, for example is preferably 0～40 weight %, is preferably 1～30 weight % especially.
Monomer (x), particularly monomer (y) can be the compounds of contain fluorine atoms not.As monomer (x), can be co-polymerized monomer with phenyl ring.At this moment, (methyl) acrylate that preferably has phenyl ring.Phenyl ring can have substituting group (for example, carbonatoms is 1～10 alkyl or alkoxyl group or halogen atom).As (methyl) esters of acrylic acid with phenyl ring, preferred (methyl) phenyl acrylate, (methyl) vinylformic acid benzene methyl perhaps are combined with the compound of methyl, methoxyl group, chlorine atom etc. on their phenyl ring.
In addition, can also be ethene, styrenic etc.
Monomer (y) as be combined with halogen atom in the monomer (x) on the carbon atom that forms unsaturated double-bond exists in the repeating unit that directly is combined with halogen atom on the carbon atom that constitutes main chain.Such repeating unit can be derived from the monomer (being called " backbone monomers with halogen atom " in this specification sheets) that directly is combined with halogen atom on the carbon atom that forms carbon-to-carbon double bond.The example of halogen atom is fluorine, chlorine, bromine and iodine.
As the example of the backbone monomers with halogen atom (being monomer (y)), can enumerate vinylidene halides such as ethylene halides such as vinylchlorid and vinyl fluoride, vinylidene chloride or vinylidene fluoride, trifluorochloroethylene, have alpha-chloro (methyl) acrylate of alkyl etc.Be included in the monomer (c) owing to have alpha-chloro (methyl) esters of acrylic acid of alkyl, therefore do not belong to monomer (y).As monomer (y), preferred vinylchlorid, vinylidene chloride.Backbone monomers with halogen atom can be one or more kinds of combinations.
With respect to polymkeric substance (A), the amount of the polymerized unit of monomer (y) is below the 40 weight %, for example is preferably 0～30 weight %, is preferably 1～25 weight % especially.
As the polymerizable monomer with reactive group (z), can contain the reactive group beyond the polymerizability unsaturated link(age) of isocyanate group etc. of oxyethyl group, halogen atom, hydroxyl, amide group, amino, imino-, alkoxysilyl, N-methylol, N-alkoxyalkyl, blockization.As the polymerizable monomer that contains reactive group (z), for example, preferably (methyl) vinylformic acid-3-chloro-2-hydroxy propyl ester, (methyl) 2-Hydroxy ethyl acrylate, (methyl) acrylamide, N-methylol (methyl) acrylamide, diacetone (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N, N-di-isopropyl (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, γ-trimethoxy-silylpropyl (methyl) acrylate, Racemic glycidol (methyl) acrylate etc.
As (methyl) acrylate that contains hydroxyl, for example, preferred (methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid-2-hydroxy propyl ester, list (methyl) vinylformic acid binaryglycol ester, polypropylene glycol list (methyl) acrylate, poly-(ethylene glycol/propylene glycol) single (methyl) acrylate, list (methyl) vinylformic acid glyceryl ester, TriMethylolPropane(TMP) list (methyl) acrylate etc.
As the co-polymerized monomer of isocyanate group with blockization, preferably make the resultant of reaction that (methyl) acrylate that contains hydroxyl and polyisocyanates obtain with the ratio reaction that remains an isocyanate group at least the block thing, make (methyl) acrylate that contains hydroxyl and isocyanate group and at least one cyanate ester based freely polyisocyanates derivatives reaction and the resultant of reaction that obtains etc. with at least one blockization.
As polyisocyanates, can enumerate aliphatic polyisocyantes such as hexamethylene diisocyanate, lysinediisocyanate, or isophorone diisocyanate, 4, the alicyclic polyisocyanates of 4 '-dicyclohexyl methane diisocyanate, cyclohexylidene vulcabond, two (isocyanic ester methyl) hexanaphthene etc., and their uric acid modifier, prepolymer modifier, biuret modified thing etc., preferred fat (cyclo) aliphatic diisocyanates or alicyclic diisocyanate.
As the block agent of the isocyanate group that is used to obtain blockization, can enumerate oximes, alkyl ketone oximes, phenols, beta-diketon class, malonic ester class, lactams, alkanols etc.The object lesson of block agent can be enumerated hexamethylene oxime, methyl ethyl ketoxime, phenol, cresols, methyl ethyl diketone, diethyl malonate, Virahol, the trimethyl carbinol, ε-Ji Neixianan, maleimide, sodium bisulfite etc., preferred hexamethylene oxime, methyl ethyl ketoxime etc.
With respect to polymkeric substance (A), the amount of the polymerized unit of monomer (z) is below the 10 weight % in the polymkeric substance (A), for example is preferably 0.1～8 weight %.
With respect to polymkeric substance (A), the amount of the polymerized unit of demonomerization (y) and monomer (z) monomer (x) in addition is below the 30 weight %, for example is preferably 0～10 weight %.
As the polymerization process that obtains polymkeric substance (A), when utilizing emulsion polymerization method or dispersion copolymerization method to carry out polymerization, can be illustrated under the existence of emulsifying agent and polymerisation medium, above-mentioned polymerizable monomer is added polymerization starter and carries out the polymeric method.Be not particularly limited as emulsifying agent, can use more than one of known or known emulsifying agent of non-ionic type, cationic, anionic, amphoteric.With respect to 100 weight part polymerizable monomers, the amount of emulsifying agent is preferably 0.5～20 weight part, from the viewpoint of the stability of water-repellent oil-repellent and dispersion liquid, about preferred especially 1～10 weight part.
Polymerisation medium is the medium that contains water, also can contain organic solvent according to expectation.As organic solvent, preferred water miscible organic solvent, the organic solvent of preferred ester class, ketone, ethers (alcohols) etc.As the organic solvent of ester class, ethyl acetate, butylacetate, ethyl succinate etc.As the organic solvent of ketone, preferred methylethylketone, methyl iso-butyl ketone (MIBK), acetone etc.As the organic solvent of ethers (alcohols), preferred glycol ether, dipropylene glycol, tripropylene glycol, triethylene glycol, ethylene glycol and their monomethyl ether or dme, diethyl ether etc.Wherein, as organic solvent, from viewpoints such as ignition quality are low, the organic solvent of preferred ethers (alcohols).The ratio of water and organic solvent is not particularly limited, and can be arbitrary proportion.With respect to 100 weight parts waters, the amount of organic solvent is below 100 weight parts, for example can be 1～10 weight part.With respect to 1 weight part polymerizable monomer, the amount of polymerisation medium is 0.5～100 weight part, for example is 1～20 weight part.
As polymerization starter, preferably water dissolubility or oil-soluble polymerization starter can use the general initiator of persulfuric acid salt, azo class, peroxide, redox class according to polymerization temperature.Polymerization temperature is not particularly limited, and is preferably 20 ℃～150 ℃.
In addition, in the polyreaction of first polymkeric substance, be purpose with the control molecular weight, can contain chain-transfer agent.As chain-transfer agent, preferably use thio-alcohol.
As the beginning polymeric last stage in the polyreaction, can utilize homogenizer or high-pressure emulsification machine etc. that the mixture that is made of polymerizable monomer, water and emulsifying agent is handled, perhaps carry out preceding dispersion in advance.
By aforesaid method synthetic polymkeric substance (A) (first polymkeric substance), preferably in medium, exist with graininess.The particle diameter of the particulate of polymkeric substance (A) is preferably 0.001～1 μ m, for example is preferably 0.01～0.5 μ m.If be in this scope, can access stable dispersion liquid, thereby the amount of emulsifying agent can reduce, the water-repellent oil-repellent height, polymer particles is stable existence in medium.When surpassing 0.5 μ m, under the situation of prolonged preservation, sedimentation can take place.This particle diameter can utilize dynamic light scattering device, electron microscope etc. to measure.When implementing polymerization in the method for utilizing common emulsion polymerization, in the presence of emulsifying agent, median size is in the above-mentioned preferred range usually.
Polymkeric substance (B) is preferably the polymerized unit that does not contain polymerizable monomer (a) and at least a polymerized unit that contains polymerizable monomer (c) and polymerizable monomer (y) adds up to more than the 10 weight %, contains the polymerizable monomer except that single thing (y) in polymerizable monomer (b) or the polymerizable monomer (x) or has the addition polymer of polymerized unit of the polymerizable monomer (z) of reactive group.
Polymkeric substance (B) also can be the polymkeric substance of contain fluorine atoms not.
Monomer (a) and (b), (c), (x), (y), (z) same meaning in monomer (a) and (b) in the polymkeric substance (B), (c), (x), (y), (z) and the polymkeric substance (A).There is not monomer (a) in the polymkeric substance (B).
Monomer (b) in the polymkeric substance (B), (c), (x), (y), (z) can be identical with monomer (b), (c), (x), (y), (z) in the polymkeric substance (A), also can be different.In addition, monomer (b), (c), (x), (y), (z) can use two or more respectively.
There is at least a of monomer (c) or monomer (y) in the polymkeric substance (B).
The amount of (with respect to polymkeric substance) monomer (b) is below the 90 weight % in the polymkeric substance (B), for example is preferably 5～80 weight %, and more preferably 10～70 weight % are preferably 30～65 weight % especially.The amount of monomer (c) for example is preferably 0～8 weight %, is preferably 0.5～5 weight % especially.The amount of monomer (y) is more than the 20 weight %, for example is preferably 25～85 weight %, is preferably 30～80 weight % especially.The total amount of monomer (c) and monomer (y) is more than the 10 weight %, for example is preferably 20～90 weight %, is preferably 30～80 weight % especially.The amount of the monomer (x) that demonomerization (y) and monomer (z) are outer is below the 40 weight %, for example is preferably 0～30 weight %, is preferably 0～20 weight % especially.The amount of monomer (z) is below the 10 weight %, for example is preferably 0.1～8 weight %.
As the polymerization process that obtains polymkeric substance (B), same with the polymerization process that obtains polymkeric substance (A), preferred emulsion polymerization, outstanding turbid polymerization etc., preferred especially emulsion polymerization.By emulsion polymerization etc., can obtain as the state (being also referred to as dispersion) of particles dispersed with polymkeric substance (B) at water solvent.
Emulsion polymerization preferably uses polymerization starter to carry out.As polymerization starter, preferred superoxide or azo compound, preferred especially azo compound.Example as azo compound, preferably be set forth in explanation oil-soluble polymerization initiator, 2 in the polymkeric substance (A), 2 '-two (the 2-methyl-prop amidine) hydrochlorides, 2 of azo, 2 '-two [2-(2-tetrahydroglyoxaline-2-yl) propane] hydrochlorides, 2,2 of azo '-water-soluble polymerization initiator of two [2-(2-tetrahydroglyoxaline-2-yl) propane] sulfate hydrates of azo etc.
In addition, the molecular weight of the polymkeric substance (B) that obtains with control is a purpose, can add chain-transfer agent when polyreaction.As chain-transfer agent, preferably use the chain-transfer agent of enumerating in the explanation of polymkeric substance (A).
Can there be emulsifying agent in the dispersion of polymkeric substance (B), as emulsifying agent, nonionic emulsifier, cationic emulsifier, anionic emulsifier or the amphoteric emulsifier of explanation in the preferred polymers (A).
Emulsifying agent can use a kind of or two or more.And during with ionic different emulsifying agent, preferred nonionic emulsifier and the combination of cationic emulsifier or the combination of nonionic emulsifier and amphoteric emulsifier.In addition, with respect to 100 parts by weight polymer (B), the amount of emulsifying agent is preferably 1～20 weight part.
The median size of polymkeric substance (B) is 0.001～1 μ m, is preferably 0.03～0.5 μ m especially.Median size in order to obtain stable dispersion, needs a large amount of emulsifying agents or has self emulsifiable polymerizable monomer during less than 0.03 μ m, may cause water-repellancy to reduce.In addition, when surpassing 0.5 μ m, may cause particles settling.
In the water extraction oil extracticn agent composition of the present invention, polymkeric substance (A) and polymkeric substance (B) are not present in the same particle, form particle separately respectively.Water extraction oil extracticn agent composition of the present invention in order to obtain polymkeric substance (A) and polymkeric substance (B), preferably carries out polyreaction respectively separately, forms particle separately, obtains dispersion, mixes each dispersion afterwards and modulates.
In the water extraction oil extracticn agent composition, polymkeric substance (A) and preferred (A)/(B)=40/60～90/10 of the weight ratio of polymkeric substance (B), preferred especially 50/50～80/20.When the ratio of polymkeric substance (A) or polymkeric substance (B) was in the above-mentioned scope, water-repellent oil-repellent excellence, the weather resistance of water-repellent oil-repellent were also excellent.In addition, the polymer concentration (solid component concentration) in the water extraction oil extracticn agent composition is preferably 0.1～50 weight %.
Polymkeric substance (A) and polymkeric substance (B) can use two or more polymkeric substance respectively.
In order to make article such as fibre product show various rerum naturas, can in water extraction oil extracticn agent composition of the present invention, cooperate the crosslinked catalyzer of polymkeric substance (A) or polymkeric substance (B) other polymkeric substance, dryingagent, oil extracticn agent, promotion in addition as required, regulate hand feeling agent, static inhibitor, penetrant, insect-proof agent, fire retardant, wrinkle resistant sanforzing agent, dye stability, pH regulator agent etc.
Water extraction oil extracticn agent composition of the present invention can be according to purpose and purposes, is diluted to any concentration and is applicable to article.To the drying working method of article, can adopt arbitrary method according to the kind of article and the modulation form of composition etc.For example, can adopt, make it attached to the surface of article and carry out the exsiccant method by dipping or lining such as coating working method.In addition, can use suitable linking agent simultaneously if desired, heat-treat.
As drying working method, preferably article are immersed in the method in the water extraction oil extracticn agent composition that contains polymkeric substance (A) and polymkeric substance (B) to article.In addition, article are immersed in contain polymkeric substance (B) and after not containing in the composition of polymkeric substance (A), being immersed in the drying working method that contains polymkeric substance (A) and do not contain in the composition of polymkeric substance (B) also can access equal effect again, thus preferred.
As the article (base material or processed article) that use water extraction oil extracticn agent composition of the present invention (treatment agent) to handle, be not particularly limited, except fibre product, can also enumerate stone material, strainer (for example electrostatic filter), dw, glass, paper, timber, leather, fur, asbestos, brick, cement, metal and oxide compound, ceramic, plastics, coatingsurface and plaster etc.Optimum fiber, fabric, fiber are compiled thing etc.As fiber, can enumerate of animal or plant nature natural fibers such as cotton, fiber crops, wool, silk, synthon such as polymeric amide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, semi-synthetic fibre such as regenerated fiber, acetic ester, inorganic fibre such as glass fibre, carbon fiber, perhaps their blend fiber.The article that use water extraction oil extracticn agent compositions-treated of the present invention to cross have excellent water-repellancy, and its weather resistance is also excellent.
In the present invention, utilize treatment agent that processed article are handled." processing " is meant by dipping, spraying, coating etc. treatment agent is used for object being treated.By handling, soak into the inside of object being treated and/or be attached to the surface of object being treated as the fluoropolymer of treatment agent effective constituent.
Embodiment
Below, expression embodiment and comparative example illustrate the present invention in further detail.
Below, unless otherwise specified, % and part expression weight % and weight part.
The following operation of characteristic is measured.
Water-repellent oil-repellent
When T/C cloth was handled, it was 30 weight % that the dilute with water polymer dispersion liquid makes solid component concentration, and it is 3.2% that dilute with water makes the concentration of 30 weight % dispersion liquids, modulation treatment liquid.With T/C cloth (drills, 200g/m
2, cloth is unstained) be immersed in the treatment solution, use plate mill with 4kg/cm
2, 4m/ minute squeezes and presses, carry out thermal treatment in 1 minute with 170 ℃ after, the water-repellent oil-repellent of Evaluation Division's removing the work.Equally, it is 4.8% that dilute with water makes the concentration of 30 weight % dispersion liquids, modulation treatment liquid.When cotton is handled, with cotton (drills, 160g/m
2, cloth is unstained) be immersed in the treatment solution, use plate mill with 4kg/cm
2, 4m/ minute squeezes and presses, carry out thermal treatment in 2 minutes with 170 ℃ after, the water-repellent oil-repellent of Evaluation Division's removing the work.Equally, it is 4.8% that dilute with water makes the concentration of 30 weight % dispersion liquids, modulation treatment liquid.When mylar was handled, (microfiber navy) was immersed in the treatment solution with mylar, used plate mill with 4kg/cm
2, 4m/ minute squeezes and presses, carry out thermal treatment in 2 minutes with 170 ℃ after, the water-repellent oil-repellent of Evaluation Division's removing the work.Water-repellancy No. (with reference to the following table 1) expression of water-repellancy to utilize the AATCC-21 spray method.About dialling oiliness, according to AATCC-118, dropping 3 is dripped and is stated the testing liquid shown in the table 2 on test cloth, observes the state that soaks into after 30 seconds, dials the butyrous vertex as dialling oiliness with what the testing liquid that does not show dipping was paid.During same levels, when water-repellent oil-repellent is higher with+expression, when lower with-expression.
[table 1]
[table 2] dials oiliness test liquid
The washing resistance of water-repellent oil-repellent
According to JIS L-0217-103 method, with 40 ℃ 25 minutes (5 minutes * HL, continuous 5 times) of washings washing, to dewater 3 minutes, rinsing 2 minutes was dewatered 3 minutes, and rinsing 2 minutes was dewatered 3 minutes, carried out roller drying, the water-repellent oil-repellent (HL-5) after estimating.
Median size
Use laser type light scattering method (Da mound electronics corporation to produce Fiber-Optics ParticleAnalyzer FPAR-1000), the median size of mensuration discrete particles.
Below, n-butyl acrylate is designated as n-BA, N hydroxymethyl acrylamide is designated as N-MAM, methacrylic acid-3-chloro-2-hydroxy propyl ester is designated as T-M, dodecyl mercaptans is designated as L-SH, n-BMA is designated as n-BMA, the methacrylic tert-butyl acrylate is designated as t-BMA, the stearyl acrylate ester is designated as StA, lauryl acrylate is designated as LA, vinylchlorid is designated as VCl, with methacrylic acid-3,3,4,4,5,5,6,6,7,7,8,8,8-ten trifluoro monooctyl esters are designated as 13FMA, with vinylformic acid-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-17 fluorine esters in the ninth of the ten Heavenly Stems are designated as 17FA.
As emulsifying agent, solidify the tallow alkyl alkyl dimethyl ammonium chloride with two and be designated as C2ABT, the Sorbitol Powder monopalmitate is designated as PP-40R, polyethylene glycol lauryl ether is designated as K220, polyoxyethylene oleyl ether is designated as BO50.
In addition, tripropylene glycol is designated as TPG, with 2,2 '-azo two (2-amidine propane) dihydrochloride is designated as NC-32W.
Synthesis example 1
In the container of 500mL, as polymerizable monomer, add n-BA (63.11g), N-MAM (1.26g), T-M (0.63g), L-SH (0.9g), emulsifying agent C2ABT (0.91g) and PP-40R (1.22g), K220 (5.25g), BO50 (1.3g), water (103.4g), TPG (18.62g), after disperseing before carrying out with homogenizer, use the ultrasonic emulsification machine, handled 5 minutes while cooling off, obtain the emulsion of monomer mixture.
This emulsion is added in the detachable flask of the 500mL that possesses cooling tube, nitrogen ingress pipe and thermometer, after carrying out nitrogen replacement, after dissolving initiator NC-32W (0.38g) also adds in water (4g), after being warming up to 60 ℃, carry out polymerization in 3 hours, obtain the non-fluorinated polymer particulate dispersion liquid (207.1g) of solid state component 35.3%, median size 0.109 μ m.
Synthesis example 2～16
According to the method identical with synthesis example 1, make the monomer mixture emulsification shown in the table 3, when using VCl as monomer, use the autoclave of the stainless steel of 500mL, other situations then add the detachable flask of the 500mL that possesses cooling tube, nitrogen ingress pipe and thermometer, make its polymerization, obtain various non-fluorinated polymer particles.
[table 3]
[table 4]
| Synthesis example 5 | Synthesis example 6 | Synthesis example 7 | Synthesis example 8 | |
| n-BA | 13.27 | 13.27 | ||
| n-BMA | ||||
| t-BMA | ||||
| LA | 38.77 | |||
| StA | 39.02 | |||
| VCI | 24.4 | 24.6 | 49.6 | 49.8 |
| N-MAM | 1.27 | 1.26 | 1.26 | 1.26 |
| T-M | 0.63 | 0.63 | 0.64 | 0.63 |
| L-SH | 0.61 | 0.52 | 0.50 | 0.56 |
| TPG | 18.18 | 18.66 | 18.88 | 18.62 |
| Pure water | 104.45 | 103.15 | 103.92 | 105.9 |
| C2ABT | 0.99 | 1 | 0.96 | 0.21 |
| PP40R | 1.36 | 1.38 | 1.42 | 0.23 |
| K220 | 6.07 | 5.89 | 5.91 | 0.89 |
| BO50 | 1.46 | 1.5 | 1.45 | 0.26 |
| NC-32W | 0.76 | 0.76 | 0.76 | 0.76 |
| Concentration after the polymerization | 36.9 | 36.9 | 34.2 | 35.2 |
| Particle diameter after the polymerization (μ m) | 0.113 | 0.115 | 0.199 | 0.284 |
| Output | 189.6 | 192.1 | 184.5 | 187.94 |
[table 5]
| Synthesis example 9 | Synthesis example 10 | Synthesis example 11 | Synthesis example 12 | |
| 13FMA | 49.98 | 42.22 | 42.36 | |
| 17FA | 42.14 | |||
| BA | ||||
| StA | 12.97 | 5.38 | 5.39 | 5.40 |
| VCI | 16.6 | 15.3 | 15.10 | |
| N-MAM | 1.39 | 1.28 | 1.31 | 1.26 |
| T-M | 0.66 | 0.63 | 0.63 | 0.61 |
| L-SH | ||||
| TPG | 18.62 | 18.68 | 18.54 | 18.30 |
| Pure water | 103.4 | 104.46 | 103.27 | 97.63 |
| C2ABT | 0.47 | 0.48 | 1.26 | 1.24 |
| PP40R | 0.63 | 0.69 | 1.07 | 1 |
| K220 | 2.74 | 2.75 | 7.36 | 7.34 |
| BO50 | 0.68 | 0.62 | 1.88 | 1.82 |
| NC-32W | 0.38 | 0.38 | 0.38 | 0.38 |
| Concentration after the polymerization | 34.4 | 33.7 | 36.96 | 36.26 |
| Particle diameter after the polymerization (μ m) | 0.134 | 0.156 | 0.056 | 0.086 |
| Output | 195.0 | 200.6 | 190.1 | 191.3 |
[table 6]
Embodiment 1～6, comparative example 1～6
The polymer beads dispersion liquid that obtains in the dilute with water synthesis example 1～16, making solid component concentration is 30 weight %, the dispersion liquid that dilution is obtained mixes with the ratio of mixture shown in table 7～10, obtains the dispersion liquid mixture.
[table 7]
[table 8]
[table 9]
[table 10]
| Example | Comparative example 6 |
| Non-fluorine emulsion | Synthesis example 1 |
| Fluorine-containing latex | Synthesis example 10 |
| Non-fluorinated polymer/fluoropolymer | 20.0/80.0 |
| Fluorochemical monomer total content (weight %) | 56.0 |
Test example 1～6
The polymer beads dispersion liquid that obtains in the foregoing description 1～6 is estimated water-repellent oil-repellent.
Evaluation result is as shown in table 11.
[table 11]
Comparison test example 1～6
The polymer beads dispersion liquid that obtains in the above-mentioned comparative example 1～6 is estimated water-repellent oil-repellent.
Evaluation result is as shown in table 12.
[table 12]
Comparison test example 7～10
The polymer beads dispersion liquid that obtains in the above-mentioned synthesis example 13～16 is estimated water-repellent oil-repellent.
Evaluation result is as shown in table 13.
[table 13]
Test example 7～8 and comparison test example 11～12
The various blanks that obtain for handling according to method his-and-hers watches 14, the resin aqueous liquid dispersion shown in the table 15 shown in the test example 1, the washing resistance of evaluation water-repellent oil-repellent.
Evaluation result is shown in table 14～15.
Claims (16)
1. aqueous dispersion type water extraction oil extracticn agent composition is characterized in that:
Contain water-medium, following polymkeric substance (A) and following polymkeric substance (B), wherein,
Polymkeric substance (A) is the polymkeric substance that contains fluoro-alkyl,
Polymkeric substance (B) is the polymkeric substance that contains halogen atom on the main chain.
2. aqueous dispersion type water extraction oil extracticn agent composition as claimed in claim 1 is characterized in that:
Polymkeric substance (B) contains at least a as polymerized unit in the acrylate with alkyl, vinylchlorid or the vinylidene chloride that the α position replaced by halogen.
3. aqueous dispersion type water extraction oil extracticn agent composition as claimed in claim 2 is characterized in that:
Polymkeric substance (B) contains at least a polymerized unit 10～100 weight % in the acrylate with alkyl, vinylchlorid and the vinylidene chloride that the α position replaced by halogen.
4. as each described aqueous dispersion type water extraction oil extracticn agent composition in the claim 1～3, it is characterized in that:
Polymkeric substance (A) is to contain the polymkeric substance that is derived from the monomeric polymerized unit that contains fluoro-alkyl.
5. aqueous dispersion type water extraction oil extracticn agent composition as claimed in claim 4 is characterized in that:
Polymkeric substance (A) is to contain the polymkeric substance that is derived from monomeric polymerized unit 50～100 weight % that contain fluoro-alkyl.
6. as each described aqueous dispersion type water extraction oil extracticn agent composition in the claim 1～5, it is characterized in that:
Fluoro-alkyl is with general formula C
mF
2m+1-(wherein, m is 2～20 integer) or (CF
3)
2CF (CF
2CF
2)
n-(wherein, n is 0～10 integer) expression.
7. as claim 5 or 6 described aqueous dispersion type water extraction oil extracticn agent compositions, it is characterized in that:
The monomer that contains fluoro-alkyl is with general formula R f-Q
1-X
1Expression,
In the formula, Rf represents fluoro-alkyl, Q
1The organic group of expression divalence, X
1Expression contains any monovalent organic radical group of polymerizability unsaturated group.
8. as claim 5 or 6 described aqueous dispersion type water extraction oil extracticn agent compositions, it is characterized in that:
The monomer that contains fluoro-alkyl is general formula CH
2=C (X)-C (=O)-compound shown in the Y-Z-Rf,
In the formula, X is that hydrogen atom, carbonatoms are 1～21 straight chain shape or prop up catenate alkyl, fluorine atom, chlorine atom, bromine atoms, iodine atom, CFX
1X
2Base (wherein, X
1And X
2Be hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom), cyano group, carbonatoms is the phenyl of benzyl, replacement or the non-replacement of 1～21 straight chain shape or catenate fluoro-alkyl, replacement or non-replacement,
Y is-O-or-NH-,
Z be carbonatoms be 1～10 fatty group, carbonatoms be 6～18 aromatic series base or annular aliphatic base ,-CH
2CH
2N (R
1) SO
2-Ji (wherein, R
1Be that carbonatoms is 1～4 alkyl) ,-CH
2CH (OZ
1) CH
2-Ji (wherein, Z
1Be hydrogen atom or ethanoyl) ,-(CH
2)
m-SO
2-(CH
2)
n-Ji or-(CH
2)
m-S-(CH
2)
n-Ji (wherein, m is 1～10, and n is 0～10),
Rf is that carbonatoms is 1～21 a straight chain shape or a catenate fluoro-alkyl.
9. as claim 5 or 6 described aqueous dispersion type water extraction oil extracticn agent compositions, it is characterized in that:
Polymkeric substance (A) contains other monomer 10～50 weight % except that the monomer that contains fluoro-alkyl.
10. aqueous dispersion type water extraction oil extracticn agent composition as claimed in claim 9 is characterized in that:
Other monomer is at least a monomer mixture that contains in vinylchlorid or the vinylidene chloride.
11., it is characterized in that as each described aqueous dispersion type water extraction oil extracticn agent composition in the claim 1～10:
The particle diameter of polymkeric substance (A) is 0.001～1 μ m.
12., it is characterized in that as each described aqueous dispersion type water extraction oil extracticn agent composition in the claim 1～10:
The particle diameter of polymkeric substance (B) is 0.001～1 μ m.
13., it is characterized in that as each described water extraction oil extracticn agent composition in the claim 1～12:
Polymkeric substance (A) is the polymkeric substance that contains polymerized unit at least a in the polymerized unit of following polymerizable monomer (a) and following polymerizable monomer (b) or the polymerizable monomer (c).
14., it is characterized in that as each described water extraction oil extracticn agent composition in the claim 1～12:
Polymkeric substance (B) is not contain the polymerized unit of polymerizable monomer (a) and contain at least a polymkeric substance in polymerizable monomer (y) and the polymerizable monomer (c).
15. one kind is utilized the method that each described water extraction oil extracticn agent composition is handled base material in the claim 1～14.
16. processing base material that obtains by the described treatment process of claim 15.
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| TWI464249B (en) * | 2012-07-05 | 2014-12-11 | Univ Vanung | Composition of water and oil repellant |
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| JPWO2009104728A1 (en) | 2011-06-23 |
| CN104195828B (en) | 2018-05-15 |
| WO2009104728A1 (en) | 2009-08-27 |
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