CN103184690A - Surface treating agent and manufacturing method thereof - Google Patents
Surface treating agent and manufacturing method thereof Download PDFInfo
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- CN103184690A CN103184690A CN2012105860043A CN201210586004A CN103184690A CN 103184690 A CN103184690 A CN 103184690A CN 2012105860043 A CN2012105860043 A CN 2012105860043A CN 201210586004 A CN201210586004 A CN 201210586004A CN 103184690 A CN103184690 A CN 103184690A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/395—Isocyanates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/02—Moisture-responsive characteristics
- D10B2401/021—Moisture-responsive characteristics hydrophobic
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
The utility model provides a surface treating agent. By using the surface treating agent, fiber substrate can have good waterproof performance. The surface treating agent includes (1) fluorine-containing polymer provided with (a) a repetitive unit sourced from a fluorine-containing monomer acting as Alpha-chlorin acrylate of perfluoroalkyl and (b) a repetitive unit sourced from a non-fluorine-containing monomer; and (2) cationic surfactant added after the polymerization of fluorine-containing polymer.
Description
Technical field
The present invention relates to a kind of excellent in stability when having high water-repellancy and in treatment fluid, having field trash to contain with the α-Lv Bingxisuan ester be the fluoro-containing composition (surface conditioning agent) that constitutes the fluoropolymer of monomer.
Background technology
Known have have perfluoroalkyl or perfluor and have acrylic or the polymer of the polymerizable compound of methacrylic acid group can be used as water extraction oil extracticn agents such as fiber textile, the aqueous liquid dispersion that particularly utilizes surfactant that this polymer dispersed is obtained in aqueous medium is widely used industrial.
In addition, also known in above-mentioned fluoropolymer compound, making vinyl chloride or the so chloride polymerizable compound of vinylidene chloride carry out copolymerization usually, can give excellent durability.And, also proposed to contain seizure by the water extraction oil extracticn agent of the compound of the hydrochloric acid of this copolymer generation.
The carbon number of the fluoroalkyl that is positioned at side chain of fluorine-containing (methyl) acrylic polymer that uses in these practicalities is generally more than 8, is commonly called " telomer ".
Worry that " telomer " may be 8 the PFOA(perfluoro caprylic acid that contains carboxylic acid fluoride by decomposition or metabolism generation as carbon number), in addition, also publish " telomer " at the agent of foam quench, care article and cleaning article, comprise that the water-repellent oil-repellent that is arranged in carpet, textiles, paper, the leather coats and the many goods of antifouling processing in being coated in use (EPAOPPT FACT SHEET April 14,2003) (http://www.epa.gov/opptintr/pfoa/pfoafacts.pdf).
In recent years, more and more obvious for the worry of the load of the environment of this PFOA, in EPA(Environmental Protection Agency USA on April 14th, 2003) delivered the accent Check that strengthens for the science of PFOA.
In this case, (methyl) acrylate of developing to have carbon number and being 6 perfluoroalkyl is the water extraction oil extracticn agent of monomer component, but be that (methyl) acrylate more than 8 is that the water extraction oil extracticn agent of monomer component is compared with carbon number, not only water-repellent oil-repellent reduction, and mechanical stability is insufficient, in addition, owing in processing is handled, be attached to the sneaking into of field trash of processing cloth etc. from pretreatment procedure, the dispersed variation of aqueous liquid dispersion and produce cohesion, the precipitation of emulsion particle sometimes.Therefore, the reduction of the performance of handled thing, polymer adheres to (gum up) and produces the processing inequality in mangle and at processing cloth, up to now, fails to solve this problem (gumup) in the water-repellent oil-repellent processing.
At present, as the technology of the surface being given simultaneously water-repellancy and group oiliness, carry out to use and to comprise low molecular compound that molecule contains the copolymer of the polymer of polymerized unit of polymerizable monomer of perfluoroalkyl (below, the perfluoroalkyl note is made the Rf yl) or this polymer and other monomer or have a Rf base and make the product of organic solvent solution or aqueous liquid dispersion and handle article.The performance of this water-repellent oil-repellent is owing to cause at surface formation critical surface tension low " surface of low-surface-energy " by the surface orientation of the Rf base in the coated film.In order to make water-repellancy and group oiliness and to deposit, the orientation of the Rf base on surface is considered to very important.This contains Rf base monomer and is achieving the goal aspect the performance of water-repellent oil-repellent, but the function in other practicality is still improved.For example, improve in order to make the durability to washing, dry-cleaning, friction etc., carried out following improvement: with containing the monomer that Rf base monomer uses the monomer of giving high rigidity or has the cross-linking reaction group; Maybe polymer blending that the copolymer that obtains and coverlay intensity is high; Admix etc. with blocked isocyanate.On the other hand, the copolymer about the polymerized unit that contains Rf base monomer has carried out making the limpen research of hard quality, reduces the research etc. of the fusing point of Rf base in order to show the water-repellancy under the low-temperature setting condition.For example, known have the monomer that makes the Rf base that contains wide chain length scope and the example that contains the alkyl monomer copolymerization.In addition, known have organosilyl method, the use of using the Rf base that contains same wide chain length scope to contain the organosilyl method of sulfydryl.
As known example, for example can enumerate: Japan's No. 3624615 communiques of special permission are (with Rf base (methyl) acrylate, (methyl) acrylic acid stearyl and other 2 kinds of monomers are 4 membered copolymers of essential composition), No. 3433024 communiques of Japan special permission (fluorine class water extraction oil extracticn agent and contain the alcohol of Rf base of certain chain lengths or the complex of perfluoro-polyether base alcohol), Japanese kokai publication hei 8-109580 communique (containing amido organosilicon and the reactant that contains Rf base ester compounds), WO2009/122919(is with Rf base (methyl) acrylate monomer, hydrocarbon (methyl) acrylate monomer and contain the copolymer that the sulfydryl organosilicon is constituent), WO2009/113589(contains and does not have perfluoroalkyl, has carbon number and is (methyl) acrylate of 20～30 alkyl, alkenyl halide and to have carbon number be the fluorinated copolymer that the monomer of 1～6 fluoroalkyl forms) etc.
WO2011/122442 discloses the agent composition that contains fluoropolymer, and this fluoropolymer has the repetitive that is derived from the α-Lv Bingxisuan ester and has (methyl) acrylate monomer of alkyl.In this communique, to not research at length of emulsifying agent (surfactant).
The prior art document
Patent documentation
Patent documentation 1: No. 3624615 communiques of Japan's special permission
Patent documentation 2: No. No. 3433024 communiques of Japan's special permission
Patent documentation 3: Japanese kokai publication hei 8-109580 communique
Patent documentation 4:WO2009/122919
Patent documentation 5:WO2009/113589
Patent documentation 6:WO2011/122442
Summary of the invention
Invent problem to be solved
The objective of the invention is to, provide a kind of base materials such as fibre are given excellent water-repellancy, processed the surface conditioning agent of the dispersion stabilization excellence of sneaking into the aqueous liquid dispersion that causes of field trash in the processing at it.
Be used for solving the method for problem
Inventors of the present invention are that purpose is concentrated on studies in order to address the above problem a little to provide the surface conditioning agent of the water-repellancy excellence that comprises the copolymer compositions that contains fluorine monomer by adding additive after finishing in the emulsion polymerization.It found that, by adding cationic emulsifier, can achieve the above object, thereby finish the present invention.
The invention provides a kind of surface conditioning agent, it contains:
(1) fluoropolymer, this fluoropolymer has:
(a) be derived from as have fluoroalkyl the α-Lv Bingxisuan ester fluorochemical monomer repetitive and
(b) be derived from the repetitive of non-fluorine monomer; And
(2) cationic surface active agent that after the polymerization of fluoropolymer, adds.
The effect of invention
According to the manufacture method of surface conditioning agent of the present invention, can make base materials such as fibre are given excellent water-repellancy, processed the surface conditioning agent of the dispersion stabilization excellence of sneaking into the aqueous liquid dispersion that causes of field trash in the processing at it.
The specific embodiment
In the present invention, as monomer, use (a) fluorochemical monomer and (b) non-fluorine monomer.
In the present invention, fluoropolymer has:
(a) be derived from the repetitive of fluorochemical monomer (α-chlorine substituted acrylate) and the repetitive that (b) is derived from non-fluorine monomer.
Fluoropolymer of the present invention can only comprise be derived from monomer (a) and monomer (b) ((b1) have carbon number be the acrylate of 12～30 straight chain shape or a chain alkyl and/or (b2) glass transition temperature (Tg) or fusing point (Tm) are (methyl) acrylate monomer more than 50 ℃) repetitive, perhaps also can on the basis of the repetitive that is derived from monomer (a) and monomer (b), have the repetitive that is derived from other monomer.
(a) fluorochemical monomer (α-chlorine replaces fluorochemical monomer)
Fluorochemical monomer is to replace fluorochemical monomer by the α shown in the following formula-chlorine,
CH
2=C(-Cl)-C(=O)-Y-Z-Rf
[in the formula, Y is-O-or-NH-,
Z is the organic group of directly combination or divalence,
Rf is the fluoroalkyl of carbon number 1～20.]。
Fluorochemical monomer (a) preferably Y base is-acrylate of O-.
Particularly, the Z base can for: carbon number 1～20(for example, carbon number 1～10, be in particular 1～4, be in particular 1 or 2) straight chain shape or chain aliphatic group (for example, alkylidene), for example formula-(CH
2)
x-(in the formula, x is 1～10.) shown in group,
The aromatic group of carbon number 6～18 or cyclic aliphatic group,
Formula-R
2(R
1) N-SO
2-or formula-R
2(R
1) group shown in the N-CO-(in the formula, R
1Be the alkyl of carbon number 1～10, R
2Straight-chain alkyl-sub-or a chain alkylidene for carbon number 1～10.), for example-CH
2CH
2N (R
1) SO
2-Ji (wherein, R
1Alkyl for carbon number 1～4.）、
Formula-CH
2CH (OR
3) CH
2-[Ar-(O)
q]
p-(in the formula, R
3Be the acyl group (for example formoxyl or acetyl group etc.) of hydrogen atom or carbon number 1～10, Ar is for having substituent arlydene (for example, phenylene) as required, p be 0 or 1, q be 0 or 1.) shown in group,
Formula-(CH
2)
n-Ar-(O)
q-(in the formula, Ar is for having substituent arlydene (for example, phenylene) as required, and n is that 0～10, q is 0 or 1.) shown in group or
-(CH
2)
m-SO
2-(CH
2)
n-Ji or-(CH
2)
m-S-(CH
2)
n-Ji (wherein, m is that 1～10, n is 0～10).
Aromatic group or cyclic aliphatic group can be for replacing or non-replacement.S base or SO
2Base can with the directly combination of Rf base.
The Rf base is preferably perfluoroalkyl.The carbon number of Rf base is preferably 1～12, for example is 1～6, is preferably 4～6 especially.The example of Rf base is-CF
3,-CF
2CF
3,-CF
2CF
2CF
3,-CF (CF
3)
2,-CF
2CF
2CF
2CF
3,-CF
2CF (CF
3)
2,-C (CF
3)
3,-(CF
2)
4CF
3,-(CF
2)
2CF (CF
3)
2,-CF
2C (CF
3)
3,-CF (CF
3) CF
2CF
2CF
3,-(CF
2)
5CF
3,-(CF
2)
3CF (CF
3)
2,-(CF
2)
4CF (CF
3)
2,-C
8F
17Deng.
As the concrete example of fluorochemical monomer (a), can illustration following compound for example, but be not limited to these compounds.
CH
2=C(-Cl)-C(=O)-O-(CH
2)
2-Rf
CH
2=C(-Cl)-C(=O)-O-(CH
2)
4-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(-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(-Cl)-C(=O)-O-CH
2CH
2N(CH
3)SO
2-Rf
CH
2=C(-Cl)-C(=O)-O-CH
2CH(OCOCH
3)CH
2-Rf
CH
2=C (Cl)-C (=O)-O-CH
2-Ph-O-Rf(wherein, Ph is 1,4-phenylene.）
CH
2=C(-Cl)-C(=O)-O-CH
2CH(OH)CH
2-Ph-O-Rf
CH
2=C(-Cl)-C(=O)-O-CH
2-Ph-Rf
CH
2=C(-Cl)-C(=O)-O-CH
2CH(OCOCH
3)CH
2-Ph-Rf
[in the above-mentioned formula, Rf is the fluoroalkyl of carbon number 1～20.]
(b) non-fluorine monomer
Non-fluorine monomer (b) is the monomer of contain fluorine atoms not.Non-fluorine monomer (b) can be the acrylate compounds of carbon number 4～32.Non-fluorine monomer (b) can be for by the acrylate compounds shown in the following formula,
CH=CR
1-C(=O)O-R
2
[in the formula, R
1Be H, C
1～C
4Alkyl or halogen,
R
2Be C
1～C
30Alkyl (for example, aliphatic group, aromatic group, aromatic-aliphatic group).]。
Non-fluorine monomer (b) can be non-fluorine non-crosslinked monomer (for example (methyl) acrylate, alkenyl halide) or the non-fluorine cross-linkable monomer that uses as required.
Non-fluorine monomer (b) can to have carbon number be the acrylate of 12～30 straight chain shape or a chain alkyl and (b2) glass transition temperature (Tg) or fusing point (Tm) are at least a kind of compound in (methyl) acrylate more than 50 ℃ in order to be selected from (b1).
(b1) having carbon number is 12～30 straight chain shape or the acrylate that props up the chain alkyl
Acrylate (b1) with alkyl of straight chain shape or a chain does not have cyclic hydrocarbon group.The alkyl of straight chain shape or a chain can be the alkyl of straight chain shape especially.The carbon number of the alkyl of straight chain shape or a chain is 12～30, generally is preferably saturated aliphatic alkyl.
Acrylate (b1) with straight chain shape or chain alkyl can be alkyl acrylate.The number of the carbon atom of alkyl can be 12～30, for example is 12～22, can be 14～20 especially.For example, the acrylate (b1) with alkyl of straight chain shape or chain can be for by the acrylate shown in the following formula,
CH
2＝CHCOOA
1
[in the formula,
A
1For by C
nH
2n+1Alkyl shown in (n=12～30, be in particular 12～22).]。
As the concrete example of the acrylate (b1) of the alkyl with straight chain shape or chain, can illustration following compound for example, but be not limited to these compounds.
CH
2=C(-H)-C(=O)-O-(CH
2)
11-CH
3
CH
2=C(-H)-C(=O)-O-(CH
2)
13-CH
3
CH
2=C(-H)-C(=O)-O-(CH
2)
15-CH
3
CH
2=C(-H)-C(=O)-O-(CH
2)
17-CH
3
CH
2=C(-H)-C(=O)-O-(CH
2)
21-CH
3
(that is, lauryl acrylate, acrylic acid myristyl ester, acrylic acid cetyl ester, acrylic acid stearyl, acrylic acid docosyl ester)
(b2) glass transition temperature (Tg) or fusing point (Tm) are (methyl) more than 50 ℃
Acrylate monomer
(methyl) acrylate monomer (b2) is (methyl) acrylate monomer more than 50 ℃ for the glass transition temperature of homopolymers (Tg) or fusing point (Tm).(methyl) acrylate monomer (b2) is monomer (b1) monomer in addition.
Glass transition temperature, fusing point are respectively the extrapolation glass transition final temperature (T of regulation among the JIS K7121-1987 " the transition temperature assay methods of plastics "
Eg), fusion peak temperature (T
Pm).
The upper limit of glass transition temperature (Tg) or fusing point (Tm) can be 300 ℃, for example can be 200 ℃.
(methyl) acrylate monomer (b2) is preferably by the acrylate compounds shown in the following formula,
CH=CR
11-C(=O)O-R
12
[in the formula, R
11Be H, C
1～C
4Alkyl or halogen,
R
12Be C
1～C
30Aliphatic group, the C of straight chain shape, chain or ring-type
6～C
20Aromatic group, C
7～C
25The aromatic-aliphatic group.]。
R
11Example be hydrogen atom, methyl, chlorine atom, bromine atoms, iodine atom.R
11Be preferably methyl.
R
12Example be aliphatic group (for example norborny, bornyl, isobornyl, adamantyl), phenyl, naphthyl, the benzyl of (for example carbon number 1～6) alkyl (for example methyl, ethyl, propyl group, butyl), (for example carbon number 5～10) cycloalkyl (for example cyclohexyl), (for example carbon number 7～20) polycycle.
R
12The group that preferably has ring-type is preferably aliphatic group, aromatic group or the aromatic-aliphatic group of cycloalkyl, polycycle.Particularly at R
11Under the situation for hydrogen atom, R
12The group that preferably has ring-type is generally aliphatic group, aromatic group or the aromatic-aliphatic group of cycloalkyl, polycycle.
As the concrete example of (methyl) acrylate monomer (b2), can illustration:
Acrylate such as cyclohexyl acrylate, isobornyl acrylate, acrylic acid norbornene ester, acrylic acid adamantane esters, acrylic acid two ring pentyl esters, acrylic acid two cyclopentene esters, acrylic acid three ring esters in the last of the ten Heavenly stems, phenyl acrylate, acrylic acid naphthalene ester, benzyl acrylate, acrylic acid 2-tert-butyl group phenyl ester, acrylic acid naphthalene ester;
Methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, the metering system tert-butyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate, the methacrylic acid norbornene ester, the methacrylic acid adamantane esters, methacrylic acid two ring pentyl esters, methacrylic acid two cyclopentene esters, methacrylic acid three ring esters in the last of the ten Heavenly stems, phenyl methacrylate, methacrylic acid naphthalene ester, benzyl methacrylate, methacrylic acid (2-dimethylamino) ethyl ester, methacrylic acid aziridine ester, methacrylic acid '-aziridino ethyl ester, methacrylates such as methacrylic acid two cyclopentene esters;
Chloropropene acid esters such as methylallyl chloride acid esters, but be not limited to these compounds.
(c) other monomer
Can use non-fluorine monomer (b) other monomer (c) of (particularly monomer (b1) and (b2) in addition) in addition, be non-fluorine monomer especially, for example other non-fluorine non-crosslinked monomer.
In the example of other monomer (c), for example comprise: ethene, vinyl acetate, acrylonitrile, polyethylene glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate and vinyl alkyl ethers.Other monomer is not limited to these examples.
Other monomer (c) can be alkenyl halide.
It is 2～20 alkene that alkenyl halide is preferably the carbon number that replaces with 1～10 chlorine atom, bromine atoms or iodine atom.Alkenyl halide is preferably the chloro-alkenes of carbon number 2～20, is preferably the carbon number with 1～5 chlorine atom especially and is 2～5 alkene.The preferred concrete example of alkenyl halide is vinyl halides, for example is vinyl chloride, bromine ethene, iodoethylene, vinylidene halide, for example be vinylidene chloride, dibromoethane, inclined to one side acetylene diiodide partially.
Other monomer (c) can be non-fluorine cross-linkable monomer.Non-fluorine cross-linkable monomer is the monomer of contain fluorine atoms not.Non-fluorine cross-linkable monomer can be for having compound at least 2 reactive groups and/or carbon-to-carbon double bond, not fluorine-containing.Non-fluorine cross-linkable monomer can be the compound with at least 2 carbon-to-carbon double bonds or the compound with at least 1 carbon-to-carbon double bond and at least 1 reactive group.The example of reactive group is hydroxyl, epoxy radicals, chloromethyl, blocked isocyanate base, amino, carboxyl etc.
Non-fluorine cross-linkable monomer can be list (methyl) acrylate, two (methyl) acrylate or single (methyl) acrylamide with reactive group.Perhaps, non-fluorine cross-linkable monomer can be two (methyl) acrylate.
1 example of non-fluorine cross-linkable monomer is the vinyl monomer with hydroxyl.
As non-fluorine cross-linkable monomer, but illustration for example: two acetone (methyl) acrylamide, N-methylol (methyl) acrylamide, (methyl) acrylic acid hydroxyl methyl esters, (methyl) hydroxy-ethyl acrylate, 3-chloro-2-hydroxypropyl (methyl) acrylate, 2-acetoacetoxy groups ethyl (methyl) acrylate, butadiene, isoprene, chlorobutadiene, the monochloro vinyl acetate, the metering system vinyl acetate, (methyl) glycidyl acrylate, 1,6-hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate etc., but be not limited to these materials.
In this manual, " (methyl) acrylate " refers to acrylate or methacrylate, and " (methyl) acrylamide " refers to acrylamide or Methacrylamide.
In fluoropolymer, the amount of fluorochemical monomer (a) can for example be 10～90 weight % for 5～95 weight % of fluoropolymer, is in particular 20～70 weight %.
The mol ratio of the repetitive of the repetitive of fluorochemical monomer (a)/non-fluorine monomer (b) can be 0.01/1～10/1, for example is 0.1/1～5/1.
With respect to fluorochemical monomer (a) 100 weight portions,
Amount with acrylate (b1) of straight chain shape or a chain alkyl is 1～1500 weight portion, is 4～800 weight portions for example, is in particular 10～400 weight portions,
The amount of (methyl) acrylate monomer (b2) is 0～1500 weight portion, is 4～800 weight portions for example, is in particular 10～400 weight portions,
The amount of other monomer (c) can be 0～100 weight portion, is 1～70 weight portion for example, is in particular 3～50 weight portions.
The number-average molecular weight of fluoropolymer (Mn) generally can be 1000～1000000, is 5000～500000 for example, is in particular 3000～200000.The number-average molecular weight of fluoropolymer (Mn) general using GPC(gel permeation chromatography) measures.
In the present invention, generally by in the presence of surfactant (polymerization surfactant), making monomer (a) and (b) after the copolymerization, add cationic surface active agent (back interpolation surfactant), obtain in medium, being dispersed with the fluoro-containing composition (surface conditioning agent) of fluoropolymer.
The polymerization surfactant is nonionic surface active agent, cationic surface active agent, anionic surfactant, amphoteric surfactant or their combination.
Nonionic surface active agent (nonionic emulsifier) be generally have polyoxyethylene (POE) base compound.Problem (Biodegradable, environmental hormone etc.) from environment considers that nonionic surface active agent does not preferably contain the structure of aromatic group.
Nonionic surface active agent can be polyoxyethylene fatty acid ester, polyoxyethylene sorbitan acid anhydride fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene alkyl ether, polyxyethylated allyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl amine or polyoxyethylene alkyl amine fatty acid ester.
Nonionic surface active agent is preferably by the surfactant shown in the following formula,
R
61O-(CH
2CH
2O)
r-(R
62O)
s-R
63
[in the formula, R
61Be the alkyl of carbon number 1～22 or the thiazolinyl of carbon number 2～22, R
62Be the alkylidene of carbon number more than 3 (for example 3～10), R
63Be the alkyl of hydrogen atom, carbon number 1～22 or the thiazolinyl of carbon number 2～22, r is the number more than 2, and s is the number more than 0 or 1.]。
R
62Example be propylidene, butylidene.R
63Be preferably hydrogen atom.S can be 0.
The concrete example of nonionic surface active agent is:
C
10H
21O-(CH
2CH
2O)
r-(C
3H
6O)
s-H
C
12H
25O-(CH
2CH
2O)
r-(C
3H
6O)
s-H
C
16H
31O-(CH
2CH
2O)
r-(C
3H
6O)
s-H
C
16H
33O-(CH
2CH
2O)
r-(C
3H
6O)
s-H
C
18H
35O-(CH
2CH
2O)
r-(C
3H
6O)
s-H
C
18H
37O-(CH
2CH
2O)
r-(C
3H
6O)
s-H
C
12H
25O-(CH
2CH
2O)
r-(C
3H
6O)
s-C
12H
25
C
16H
31O-(CH
2CH
2O)
r-(C
3H
6O)
s-C
16H
31
C
16H
33O-(CH
2CH
2O)
r-(C
3H
6O)
s-C
12H
25
iso-C
13H
27O-(CH
2CH
2O)
r-(C
3H
6O)
s-H
[in the formula, r is identical with above-mentioned meaning with s.] etc.
Nonionic surface active agent can be only a kind, or also can be the mixture more than 2 kinds.Nonionic surface active agent can be that r is more than 10, s is 0 nonionic surface active agent and r is lower than 10, s is 0 nonionic surface active agent, and (for example mol ratio is 0.5:1～20:1, be 1:1～10:1 for example, be in particular 1.5:1～7:1's) mixture.
Cationic surface active agent (cationic emulsifier) is generally ammonium salt.Cationic surface active agent can be for by the ammonium salt shown in the following formula,
(R
51)
pN
＋(R
52)
4-pX
-
[in the formula, R
51Be aliphatic (the saturated and/or unsaturated) group of the straight chain shape more than the C12 and/or a chain,
R
52Be alkyl, benzyl, the polyoxyethylene groups (quantity of oxyethylene group is 1～50 for example, is in particular 2～50, is in particular 3～50) of H or C1～4,
X is the group of formation anion,
P is 1 or 2.]。
R
51Can be C
12～C
50, for example be C
18～C
40, be in particular C
20～C
35, be in particular C
22～C
30R
52Be preferably CH
3Or C
2H
5The concrete example of X is halogen, the CH of F, Cl, Br, I and so on
3COO
-And so on C
1～4Carboxylic acid ester, HSO
4 -And so on sulfuric ester, H
2PO
4 -And so on phosphate.
As the concrete example of cationic surface active agent, can enumerate: alkyl trimethyl ammonium halides such as octyl group trimethylammonium bromide, octyl group trimethyl ammonium chloride, DTAB, Dodecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, tetradecyl trimethyl ammonium chloride, softex kw, hexadecyltrimethylammonium chloride, octadecyl trimethyl ammonium chloride;
The lauryl pyridinium chloride;
Dialkyl dimethyl ammonium halides such as dioctyl dimethyl ammonium bromide, Quaternium 24, didodecyldimethylammbromide bromide, two dodecyl dimethyl ammonium chloride, two myristyl dimethyl ammonium bromide, two myristyl alkyl dimethyl ammonium chloride, double hexadecyl dimethyl ammonium bromide, Varisoft 432PPG, dioctadecyl dimethyl ammonium chloride etc.
Cationic surface active agent can be only a kind, maybe can be the mixture more than 2 kinds.Cationic surface active agent can be that p is 1 cationic surface active agent [(R
51) N
+(R
52)
3X
-] and p be 2 cationic surface active agent [(R
51)
2N
+(R
52)
2X
-] (for example mol ratio 0.5:1～20:1 is 1:1～10:1 for example, is in particular 1.5:1～7:1's) mixture.
As the concrete example of anionic surfactant, can enumerate: NaLS; triethanolamine lauryl sulfate; polyoxyethylene lauryl ether sodium sulphate; polyoxyethylene nonylplenyl ether sodium sulphate; polyoxyethylene lauryl ether sulfuric acid triethanolamine; the cocoyl sodium sarcosinate; N cocoyl N-methyltaurine sodium; polyoxyethylene cocounut oil sodium alkylether sulphate; diether hexyl sodium sulfosuccinate; the alpha-olefin sodium sulfonate; the lauryl sodium phosphate; the polyoxyethylene lauryl ether sodium phosphate; perfluoroalkyl carboxylate (trade name Unidyne DS-101; 102(Daikin Ind Ltd system)) etc.
Amphoteric surfactant can be alanine class, imidazoles betaines, amide betaine class or acetic acid betaine etc.As the concrete example of amphoteric surfactant, can enumerate: empgen BB, octadecyl betaine, dodecyl carboxyl methyl hydroxyethyl imidazoles betaine, dodecyl dimethyl amion acetic acid betaine, fatty amide propyl dimethylaminoethyl acid betaine etc.
Polymerization is preferably the mixture of cationic surface active agent and nonionic surface active agent with surfactant.With in the surfactant, the weight ratio of cationic surface active agent and nonionic surface active agent can be 10～99:90～1, is 20～95:80～5 for example, is in particular 50～90:50～10, is in particular 55～80:45～20 in polymerization.With respect to monomer 100 weight portions, polymerization can be the scope of 0.5～30 weight portion with the amount of surfactant, for example is the scope of 1～20 weight portion.
Add with surfactant the back is cationic surface active agent.As cationic surface active agent, can enumerate with polymerization with the same above-claimed cpd of surfactant.With respect to monomer (or fluoropolymer) 100 weight portions, the amount that add with surfactant the back can be 0.05～20 weight portion, is 0.1～10 weight portion for example, is in particular 0.3～5 weight portion, is in particular the scope of 2～5 weight portions.
Can will carry out polymerization in the presence of at least a kind of compound of monomer in being selected from blocked isocyanate compound and organopolysiloxane compound.With respect to monomer 100 weight portions, the amount of blocked isocyanate compound (or organopolysiloxane compound) can be 0～100 weight portion, for example is 1～50 weight portion.
By monomer is carried out polymerization in the presence of the blocked isocyanate compound, can obtain having the fluoropolymer of blocked isocyanate base.The blocked isocyanate compound is the isocyanates that utilizes at least a sealer to seal.As the example of sealer, can enumerate: oximes, phenols, alcohols, thio-alcohol, amide-type, acid imide, imidazoles, ureas, amine, imines class, pyrazoles and activity methene compound class.In other example of sealer, can enumerate: pyridone class, benzenethiol class, two ketones and ester class.The blocked isocyanate compound can utilize the compound of possess hydrophilic property group to carry out modification.
By monomer is carried out polymerization in the presence of organopolysiloxane compound (for example Mercaptofunctional organopolysiloxane, vinyl functional organopolysiloxane), can obtain having the fluoropolymer of siloxy group.In 1 embodiment, the Mercaptofunctional organopolysiloxane contains the first siloxy group unit with following average formula:
(R
2SiO)
a(RR
NSiO)
b(RR
SSiO)
c
[in the formula, a is 0～4000, or is 0～1000, or is 0～400,
B is 1～1000, or is 1～100, or is 1～50,
C is 1～1000, or is 1～100, or is 1～50;
R is the organic group of monovalence independently,
Perhaps, R is the hydrocarbon of carbon number 1～30,
Perhaps, R is the univalent alkyl of carbon number 1～12,
Perhaps, R is methyl;
R
NBe the organic group of the amino functional of monovalence,
R
SOrganic group for the Mercaptofunctional of monovalence.]
Organic group R as the amino functional of organic functional group
NBy having formula :-R
1NHR
2, formula :-R
1NR
2 2Or formula :-R
1NHR
1NHR
2(in the formula, each R
1Independent, be the alkyl of the divalence of carbon number more than 2, R
2Alkyl for hydrogen or carbon number 1～20.) the group illustration.The typical case, each R
1Alkylidene for carbon number 2～20.
Several examples of preferred amino functional alkyl have:
-CH
2CH
2NH
2、-CH
2CH
2CH
2NH
2、
-CH
2CHCH
3NH
2、-CH
2CH
2CH
2CH
2NH
2、
-CH
2CH
2CH
2CH
2CH
2NH
2、
-CH
2CH
2CH
2CH
2CH
2CH
2NH
2、
-CH
2CH
2NHCH
3、-CH
2CH
2CH
2NHCH
3、
-CH
2(CH
3)CHCH
2NHCH
3、-CH
2CH
2CH
2CH
2NHCH
3、
-CH
2CH
2NHCH
2CH
2NH
2、
-CH
2CH
2CH
2NHCH
2CH
2CH
2NH
2、
-CH
2CH
2CH
2CH
2NHCH
2CH
2CH
2CH
2NH
2、
-CH
2CH
2NHCH
2CH
2NHCH
3、
-CH
2CH
2CH
2NHCH
2CH
2CH
2NHCH
3、
-CH
2CH
2CH
2CH
2NHCH
2CH
2CH
2CH
2NHCH
3, and
-CH
2CH
2NHCH
2CH
2NHCH
2CH
2CH
2CH
3。The typical case, the amino functional group is-CH
2CH
2CH
2NH
2
R
SBy formula :-R
1SR
2(in the formula, each R
1Independent, be the alkyl of the divalence of carbon number more than 2, R
2Alkyl for hydrogen or carbon number 1～20.In the formula, each R
1And R
2As mentioned above.) shown in the group illustration.The typical case, each R
1Alkylidene for carbon number 2～20.The example of Mercaptofunctional group is as shown in the formula described:
For-CH
2CH
2CH
2SH ,-CH
2CHCH
3SH ,-CH
2CH
2CH
2CH
2SH,
-CH
2CH
2CH
2CH
2CH
2SH、-CH
2CH
2CH
2CH
2CH
2CH
2SH、
-CH
2CH
2SCH
3。The typical case, the Mercaptofunctional group is-CH
2CH
2CH
2SH.
Fluoropolymer among the present invention is generally made by the emulsion polymerization.
In the emulsion polymerization, adopt and in the presence of polymerization initiator and emulsifying agent, to make monomer emulsification and carry out nitrogen displacement back, stir the method that made its copolymerization in 1～10 hour 50～80 ℃ scopes in water.Polymerization initiator can use benzoyl peroxide; lauroyl peroxide; tert butyl peroxy benzoate; 1-hydroxy-cyclohexyl hydrogen peroxide; 3-carboxypropanoyl peroxide; acetyl peroxide; two isobutyl amidine-the dihydrochlorides of azo; azodiisobutyronitrile; sodium peroxide; potassium peroxydisulfate; water miscible polymerization initiator such as ammonium persulfate or azodiisobutyronitrile; benzoyl peroxide; two-tert-butyl peroxide; lauryl peroxide; isopropyl benzene hydroperoxide; the peroxidating pivalic acid tert-butyl ester; oil-soluble polymerization initiator such as di-isopropyl peroxydicarbonate.With respect to monomer 100 weight portions, use polymerization initiator with the scope of 0.01～10 weight portion.
In order to obtain the copolymer aqueous dispersions of shelf-stability excellence, preferably use the emulsifier unit that can give powerful broken energy of high pressure homogenizer or Soniprep and so on, monomer is carried out micronize and carries out polymerization in water.In addition, as emulsifying agent, can use the various emulsifying agents of anionic, cationic or nonionic.With respect to monomer 100 weight portions, the amount of emulsifying agent can be the scope of 0.5～30 weight portion, for example is the scope of 1～20 weight portion.The situation that monomer not exclusively mixes, the preferred phase solvation that these monomers are mixed fully that adds for example adds water-miscible organic solvent or low-molecular-weight monomer.By adding the phase solvation, can make emulsibility and copolymerization raising.
As water-miscible organic solvent, can enumerate: acetone, MEK, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol etc., with respect to water 100 weight portions, can be with the scope of 1～50 weight portion, for example use with the scope of 10～40 weight portions.In addition, as low-molecular-weight monomer, can enumerate: methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate etc., with respect to total amount 100 weight portions of monomer, can be with the scope of 1～50 weight portion, for example use with the scope of 10～40 weight portions.
Fluoro-containing composition of the present invention is preferably emulsion (particularly aqueous liquid dispersion) or aerocolloidal form.Fluoro-containing composition contains fluoropolymer (active component of surface conditioning agent) and medium (particularly liquid medium, for example organic solvent and/or water).For example, with respect to fluoro-containing composition, the amount of medium can be 5～99.9 weight %, is in particular 10～90 weight %.
In fluoro-containing composition, the concentration of fluoropolymer can be 0.01～95 weight %, for example is 5～50 weight %.
Fluoro-containing composition of the present invention can utilize at present, and known method is applied to object being treated.Usually employing is scattered in organic solvent or water with this fluoro-containing composition and dilutes, utilizes known methods such as dip coated, spraying, foam coating to make it be attached to the surface of object being treated and carry out dry method.In addition, if desired, then can use jointly and be cured with suitable crosslinking agent.And, also can in fluoro-containing composition of the present invention, add insect-proof agent, softener, antiseptic, fire retardant, antistatic additive, coating fixative, anti-creasing agent etc. and and use.Can be 0.01～10 weight %(situation of dip coated particularly with the concentration of fluoropolymer in the treatment fluid that base material contacts), for example be 0.05～10 weight %.
As with the handled object being treated of fluoro-containing composition of the present invention (for example water extraction oil extracticn agent), can enumerate: the parts of fibre, stone material, filter (for example electrostatic filter), dust cover, fuel cell (for example gas-diffusion electrode and gas diffusion supporter), glass, paper, wood, leather, fur, asbestos, brick, cement, metal and oxide, ceramic industry goods, plastics, painted surface and calcimine etc.As fibre, can enumerate various examples.For example can enumerate: inorfil or their blended fiber such as semisynthetic fibres such as synthetic fiber such as of animal or plant nature natural fabric, polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, artificial silk, acetate fiber, glass fibre, carbon fiber, asbestos fibre such as cotton, fiber crops, wool, silk.
Fibre can be any of forms such as fiber, cloth.
Fluoro-containing composition of the present invention also can use as internal mold release or external release agent.
Fluoropolymer can utilize the method known for fibre is handled in liquid any be applied to fibrous substrate (for example fibre etc.).When fibre is cloth, cloth can be soaked in the solution, or can adheres to or spray solution at cloth.In order to make the fibre performance of handling dial oiliness, it is carried out drying, preferably heat at for example 100 ℃～200 ℃.
Perhaps, fluoropolymer can utilize washing method to be applied to fibre, for example can use washing or be applied to fibre in dry cleaning process etc.
The typical case, processed fibre is cloth, comprising cloth and the carpet of textiles, knitting, nonwoven fabric, dress material product form, but also can be fiber, yarn or median fiber goods (for example sliver or rove etc.).The fibre material can be natural fabric (for example cotton or wool etc.), chemical fibre (for example viscose or Lyocell(レ オ セ Le) etc.), synthetic fiber (for example polyester, polyamide or acrylic fiber etc.), maybe can be the mixture (for example mixture of natural fabric and synthetic fiber etc.) of fiber.Manufacturing polymer of the present invention cellulosic fibre (for example cotton or artificial silk etc.) is made oleophobic property and dial oiliness aspect effective especially.In addition, method of the present invention is generally made fibre hydrophobicity and water-repellancy.
Perhaps, fibrous substrate can be leather.Be hydrophobicity and oleophobic property in order to make leather, can be in each stage of leather processing, for example the wetting processing of leather during in or during leather accurately machined in, will make polymer and be applied to leather from the aqueous solution or aqueous emulsifying thing.
Perhaps, fibrous substrate can be paper.Can make polymer applications in preformed paper, or application in can be between the dry period of various stages of papermaking, for example paper.
" processing " refers to finishing agent utilization dipping, spraying, coating etc. are applied to object being treated.By handling, soak in the inside of object being treated and/or be attached to the surface of object being treated as the fluoropolymer of the active ingredient of finishing agent.
[embodiment]
Below, enumerate embodiment, explain the present invention, but the present invention is not limited to these embodiment.
Below, short of specified otherwise, part, % or ratio expression weight portion, weight % or weight ratio.
Test procedure is as described below.
The test of spray water-repellancy
Spray the water-repellancy test according to JIS-L-1092.The test of spray water-repellancy utilizes (shown in the table 1 of following record) water-repellancy No.(numbering) expression.
Use volume to be the nozzle of the glass funnel of 250ml at least and can the enough 20 seconds～water of 250ml was sprayed in 30 seconds.The framework of fixation test cloth is that diameter is the metal system of 15cm.Prepare 3 test cloth that size is about 20cm * 20cm, will test cloth and be fixed in framework, make test cloth not have fold.The center of spraying is placed the center of test cloth.In glass funnel, add the water (250mL) of room temperature, test cloth (through 25 seconds～30 seconds time) is sprayed.Take off framework from platform, catch an end of framework to make the face that has sprayed water be in downside, locate to collide with lightly framework at experimental bench etc., excessive water droplet is fallen.Then, make framework Rotate 180 °, repeat identical step, thereafter, viewing test cloth surface is estimated according to the water-repellancy No. of table 1.On average obtain the result from what measure for 3 times.
[table 1]
| The water-repellancy numbering | State |
| 5 | The surface does not have the situation of adhesional wetting |
| 4 | The surface shows the situation of adhesional wetting a little |
| 3 | The surface shows local wetting situation |
| 2 | The surface shows wetting situation |
| 1 | Whole surface shows wetting situation |
The test of infiltration water-repellancy
Be that the metallicity framework of 15cm is fixed with test cloth diameter.Prepare 3 test cloth that size is about 20cm * 20cm, will test cloth and be fixed in framework, making does not have fold on the sheet material.Put the water of 2g at the center of test film, estimate after 5 minutes the infiltration to test film.
Zero: not infiltration
△: see infiltration
*: see the infiltration around being diffused into.
The field trash stability test
It is solid component concentration 0.6 weight % that aqueous liquid dispersion is diluted with running water, to wherein adding nylon with FIX agent 0.03 weight %, fully mixes, and observes the generation of condensation product.
Zero: do not have the generation of condensation product fully
△: produce condensation product a little
*: condensation product produces in large quantities
Production Example 1
In the 1L autoclave, add CF
3CF
2-(CF
2CF
2)
n-CH
2CH
2OCOC (Cl)=CH
2(n=2.0) 37.25g, acrylic acid stearyl 64.57g, pure water 220g, dipropylene glycol monomethyl ether 37.24g, dioctadecyl dimethyl ammonium chloride (cationic surface active agent) 6.16g, octadecyl trimethyl ammonium chloride (cationic surface active agent) 1.74g, polyoxyethylene lauryl ether (EO:20.EO represents the ethylene oxide unit number) (nonionic surface active agent) 3.28g, polyoxyethylene isotridecyl ether (EO:3) (nonionic surface active agent) 1.30g, polyoxyethylene oleyl ether (EO:50) (nonionic surface active agent) 0.68g, under agitation, 60 ℃ with ultrasonic wave its emulsification was disperseed 15 minutes.Add lauryl mercaptan 1.24g, to carry out in the autoclave after the nitrogen displacement, be pressed into and fill vinyl chloride (VCM) 22.35g, add 2, below two (2-amidine propane) the 2 hydrochloride 0.62g(of 2-azo, note is made V-50) and the solution of water 18g, reacted 5 hours at 60 ℃, obtain the aqueous liquid dispersion of polymer.The composition basically identical of the composition of polymer and charging monomer.In the aqueous liquid dispersion that obtains, add octadecyl trimethyl ammonium chloride (cationic surface active agent) 1.0g.
Production Example 2
In the 1L autoclave, add CF
3CF
2-(CF
2CF
2)
n-CH
2CH
2OCOC (Cl)=CH
2(n=2.0) 37.25g, acrylic acid stearyl 64.57g, pure water 220g, dipropylene glycol monomethyl ether 37.24g, dioctadecyl dimethyl ammonium chloride (cationic surface active agent) 3.08g, octadecyl trimethyl ammonium chloride (cationic surface active agent) 0.87g, polyoxyethylene lauryl ether (EO:20.EO represents the ethylene oxide unit number) (nonionic surface active agent) 5.74g, polyoxyethylene isotridecyl ether (EO:3) (nonionic surface active agent) 2.28g, polyoxyethylene oleyl ether (EO:50) (nonionic surface active agent) 1.19g, under agitation, 60 ℃ with ultrasonic wave its emulsification was disperseed 15 minutes.Add lauryl mercaptan 1.24g, to carry out in the autoclave after the nitrogen displacement, be pressed into and fill vinyl chloride (VCM) 22.35g, add 2, below two (2-amidine propane) the 2 hydrochloride 0.62g(of 2-azo, note is made V-50) and the solution of water 18g, reacted 5 hours at 60 ℃, obtain the aqueous liquid dispersion of polymer.The composition basically identical of the composition of polymer and charging monomer.In the aqueous liquid dispersion that obtains, add octadecyl trimethyl ammonium chloride (cationic surface active agent) 2.0g.
Production Example 3
In the 500ml reaction flask, add CF
3CF
2-(CF
2CF
2)
n-CH
2CH
2OCOC (Cl)=CH
2(n=2.0) 18.63g, acrylic acid stearyl 12.42g, isobornyl methacrylate 31.04g, pure water 110g, dipropylene glycol monomethyl ether 18.62g, dioctadecyl dimethyl ammonium chloride (cationic surface active agent) 3.08g, octadecyl trimethyl ammonium chloride (cationic surface active agent) 0.87g, polyoxyethylene lauryl ether (EO:20.EO represents the ethylene oxide unit number) (nonionic surface active agent) 1.64g, polyoxyethylene isotridecyl ether (EO:3) (nonionic surface active agent) 0.65g, polyoxyethylene oleyl ether (EO:50) (nonionic surface active agent) 0.34g, under agitation, 60 ℃ with ultrasonic wave its emulsification was disperseed 15 minutes.Add lauryl mercaptan 0.62g, 2 with carrying out in the reaction flask after the nitrogen displacement, below two (2-amidine propane) the 2 hydrochloride 0.31g(of 2-azo, note is made V-50) and the solution of water 9g, reacted 5 hours at 60 ℃, obtain the aqueous liquid dispersion of polymer.The composition basically identical of the composition of polymer and charging monomer.In the aqueous liquid dispersion that obtains, add octadecyl trimethyl ammonium chloride (cationic surface active agent) 0.5g.
Production Example 4
In the 500ml reaction flask, add CF
3CF
2-(CF
2CF
2)
n-CH
2CH
2OCOC (Cl)=CH
2(n=2.0) 18.63g, acrylic acid stearyl 12.42g, isobornyl methacrylate 31.04g, pure water 110g, dipropylene glycol monomethyl ether 18.62g, dioctadecyl dimethyl ammonium chloride (cationic surface active agent) 1.54g, octadecyl trimethyl ammonium chloride (cationic surface active agent) 0.44g, polyoxyethylene lauryl ether (EO:20.EO represents the ethylene oxide unit number) (nonionic surface active agent) 2.87g, polyoxyethylene isotridecyl ether (EO:3) (nonionic surface active agent) 1.14g, polyoxyethylene oleyl ether (EO:50) (nonionic surface active agent) 0.60g, under agitation, 60 ℃ with ultrasonic wave its emulsification was disperseed 15 minutes.Add lauryl mercaptan 0.62g, to carry out in the autoclave after the nitrogen displacement, be pressed into and fill vinyl chloride (VCM) 22.35g, add 2, below two (2-amidine propane) the 2 hydrochloride 0.31g(of 2-azo, note is made V-50) and the solution of water 9g, reacted 5 hours at 60 ℃, obtain the aqueous liquid dispersion of polymer.The composition basically identical of the composition of polymer and charging monomer.In the aqueous liquid dispersion that obtains, add octadecyl trimethyl ammonium chloride (cationic surface active agent) 1.0g.
Production Example 5
In the 500ml reaction flask, add CF
3CF
2-(CF
2CF
2)
n-CH
2CH
2OCOC (Cl)=CH
2(n=2.0) 14.9g, acrylic acid stearyl 13.47g, isobornyl methacrylate 33.71g, pure water 110g, dipropylene glycol monomethyl ether 18.62g, dioctadecyl dimethyl ammonium chloride (cationic surface active agent) 3.08g, octadecyl trimethyl ammonium chloride (cationic surface active agent) 0.87g, polyoxyethylene lauryl ether (EO:20.EO represents the ethylene oxide unit number) (nonionic surface active agent) 1.64g, polyoxyethylene isotridecyl ether (EO:3) (nonionic surface active agent) 0.65g, polyoxyethylene oleyl ether (EO:50) (nonionic surface active agent) 0.34g, under agitation, 60 ℃ with ultrasonic wave its emulsification was disperseed 15 minutes.Add lauryl mercaptan 0.62g, 2 with carrying out in the reaction flask after the nitrogen displacement, below two (2-amidine propane) the 2 hydrochloride 0.31g(of 2-azo, note is made V-50) and the solution of water 9g, reacted 5 hours at 60 ℃, obtain the aqueous liquid dispersion of polymer.The composition basically identical of the composition of polymer and charging monomer.In the aqueous liquid dispersion that obtains, add octadecyl trimethyl ammonium chloride (cationic surface active agent) 0.5g.
Production Example 6
In the 500ml reaction flask, add CF
3CF
2-(CF
2CF
2)
n-CH
2CH
2OCOC (Cl)=CH
2(n=2.0) 14.9g, acrylic acid stearyl 13.47g, isobornyl methacrylate 33.71g, pure water 110g, dipropylene glycol monomethyl ether 18.62g, dioctadecyl dimethyl ammonium chloride (cationic surface active agent) 1.54g, octadecyl trimethyl ammonium chloride (cationic surface active agent) 0.44g, polyoxyethylene lauryl ether (EO:20.EO represents the ethylene oxide unit number) (nonionic surface active agent) 2.87g, polyoxyethylene isotridecyl ether (EO:3) (nonionic surface active agent) 1.14g, polyoxyethylene oleyl ether (EO:50) (nonionic surface active agent) 0.60g, under agitation, 60 ℃ with ultrasonic wave its emulsification was disperseed 15 minutes.Add lauryl mercaptan 0.62g, to carry out in the autoclave after the nitrogen displacement, be pressed into and fill vinyl chloride (VCM) 22.35g, add 2, below two (2-amidine propane) the 2 hydrochloride 0.31g(of 2-azo, note is made V-50) and the solution of water 9g, reacted 5 hours at 60 ℃, obtain the aqueous liquid dispersion of polymer.The composition basically identical of the composition of polymer and charging monomer.In the aqueous liquid dispersion that obtains, add octadecyl trimethyl ammonium chloride (cationic surface active agent) 1.0g.
Production Example 7
In the 500ml reaction flask, add CF
3CF
2-(CF
2CF
2)
n-CH
2CH
2OCOC (Cl)=CH
2(n=2.0) 14.9g, acrylic acid stearyl 13.47g, isobornyl methacrylate 33.71g, pure water 110g, dipropylene glycol monomethyl ether 18.62g, dioctadecyl dimethyl ammonium chloride (cationic surface active agent) 3.08g, octadecyl trimethyl ammonium chloride (cationic surface active agent) 0.87g, polyoxyethylene lauryl ether (EO:20.EO represents the ethylene oxide unit number) (nonionic surface active agent) 1.64g, polyoxyethylene isotridecyl ether (EO:3) (nonionic surface active agent) 0.65g, polyoxyethylene oleyl ether (EO:50) (nonionic surface active agent) 0.34g, under agitation, 60 ℃ with ultrasonic wave its emulsification was disperseed 15 minutes.Add lauryl mercaptan 0.62g, 2 with carrying out in the reaction flask after the nitrogen displacement, below two (2-amidine propane) the 2 hydrochloride 0.31g(of 2-azo, note is made V-50) and the solution of water 9g, reacted 5 hours at 60 ℃, obtain the aqueous liquid dispersion of polymer.The composition basically identical of the composition of polymer and charging monomer.In the aqueous liquid dispersion that obtains, add two cocoyl alkyl dimethyl ammonium chloride 1.0g.
Production Example 8
In the 500ml reaction flask, add CF
3CF
2-(CF
2CF
2)
n-CH
2CH
2OCOC (Cl)=CH
2(n=2.0) 14.9g, acrylic acid stearyl 13.47g, isobornyl methacrylate 33.71g, pure water 110g, dipropylene glycol monomethyl ether 18.62g, dioctadecyl dimethyl ammonium chloride (cationic surface active agent) 3.08g, octadecyl trimethyl ammonium chloride (cationic surface active agent) 0.87g, polyoxyethylene lauryl ether (EO:20.EO represents the ethylene oxide unit number) (nonionic surface active agent) 1.64g, polyoxyethylene isotridecyl ether (EO:3) (nonionic surface active agent) 0.65g, polyoxyethylene oleyl ether (EO:50) (nonionic surface active agent) 0.34g, under agitation, 60 ℃ with ultrasonic wave its emulsification was disperseed 15 minutes.Add lauryl mercaptan 0.62g, 2 with carrying out in the reaction flask after the nitrogen displacement, below two (2-amidine propane) the 2 hydrochloride 0.31g(of 2-azo, note is made V-50) and the solution of water 9g, reacted 5 hours at 60 ℃, obtain the aqueous liquid dispersion of polymer.The composition basically identical of the composition of polymer and charging monomer.In the aqueous liquid dispersion that obtains, add DDAC (cationic surface active agent) 1.0g.
Production Example 9
In the 500ml reaction flask, add CF
3CF
2-(CF
2CF
2)
n-CH
2CH
2OCOC (Cl)=CH
2(n=2.0) 18.63g, acrylic acid stearyl 12.42g, cyclohexyl methacrylate 31.04g, pure water 110g, dipropylene glycol monomethyl ether 18.62g, dioctadecyl dimethyl ammonium chloride (cationic surface active agent) 3.08g, octadecyl trimethyl ammonium chloride (cationic surface active agent) 0.87g, polyoxyethylene lauryl ether (EO:20.EO represents the ethylene oxide unit number) (nonionic surface active agent) 1.64g, polyoxyethylene isotridecyl ether (EO:3) (nonionic surface active agent) 0.65g, polyoxyethylene oleyl ether (EO:50) (nonionic surface active agent) 0.34g, under agitation, 60 ℃ with ultrasonic wave its emulsification was disperseed 15 minutes.Add lauryl mercaptan 0.62g, 2 with carrying out in the reaction flask after the nitrogen displacement, below two (2-amidine propane) the 2 hydrochloride 0.31g(of 2-azo, note is made V-50) and the solution of water 9g, reacted 5 hours at 60 ℃, obtain the aqueous liquid dispersion of polymer.The composition basically identical of the composition of polymer and charging monomer.In the aqueous liquid dispersion that obtains, add octadecyl trimethyl ammonium chloride (cationic surface active agent) 0.5g.
Production Example 10
In the 500ml reaction flask, add CF
3CF
2-(CF
2CF
2)
n-CH
2CH
2OCOC (Cl)=CH
2(n=2.0) 16.77g, acrylic acid stearyl 12.98g, cyclohexyl methacrylate 32.34g, pure water 110g, dipropylene glycol monomethyl ether 18.62g, dioctadecyl dimethyl ammonium chloride (cationic surface active agent) 3.08g, octadecyl trimethyl ammonium chloride (cationic surface active agent) 0.87g, polyoxyethylene lauryl ether (EO:20.EO represents the ethylene oxide unit number) (nonionic surface active agent) 1.64g, polyoxyethylene isotridecyl ether (EO:3) (nonionic surface active agent) 0.65g, polyoxyethylene oleyl ether (EO:50) (nonionic surface active agent) 0.34g, under agitation, 60 ℃ with ultrasonic wave its emulsification was disperseed 15 minutes.Add lauryl mercaptan 0.62g, 2 with carrying out in the reaction flask after the nitrogen displacement, below two (2-amidine propane) the 2 hydrochloride 0.31g(of 2-azo, note is made V-50) and the solution of water 9g, reacted 5 hours at 60 ℃, obtain the aqueous liquid dispersion of polymer.The composition basically identical of the composition of polymer and charging monomer.In the aqueous liquid dispersion that obtains, add octadecyl trimethyl ammonium chloride (cationic surface active agent) 0.5g.
Compare Production Example 1
In the 1L autoclave, add CF
3CF
2-(CF
2CF
2)
n-CH
2CH
2OCOC (CH
3)=CH
2(n=2.0) 37.25g, acrylic acid stearyl 64.57g, pure water 220g, dipropylene glycol monomethyl ether 37.24g, dioctadecyl dimethyl ammonium chloride (cationic surface active agent) 3.08g, octadecyl trimethyl ammonium chloride (cationic surface active agent) 0.87g, polyoxyethylene lauryl ether (EO:20.EO represents the ethylene oxide unit number) (nonionic surface active agent) 5.74g, polyoxyethylene isotridecyl ether (EO:3) (nonionic surface active agent) 2.28g, polyoxyethylene oleyl ether (EO:50) (nonionic surface active agent) 1.19g, under agitation, 60 ℃ with ultrasonic wave its emulsification was disperseed 15 minutes.Add lauryl mercaptan 1.24g, to carry out in the autoclave after the nitrogen displacement, be pressed into and fill vinyl chloride (VCM) 22.35g, add 2, below two (2-amidine propane) the 2 hydrochloride 0.62g(of 2-azo, note is made V-50) and the solution of water 18g, reacted 5 hours at 60 ℃, obtain the aqueous liquid dispersion of polymer.The composition basically identical of the composition of polymer and charging monomer.In the aqueous liquid dispersion that obtains, add octadecyl trimethyl ammonium chloride (cationic surface active agent) 2.0g.
Compare Production Example 2
In the 1L autoclave, add CF
3CF
2-(CF
2CF
2)
n-CH
2CH
2OCOCH=CH
2(n=3.0) 37.25g, acrylic acid stearyl 64.57g, pure water 220g, dipropylene glycol monomethyl ether 37.24g, dioctadecyl dimethyl ammonium chloride (cationic surface active agent) 3.08g, octadecyl trimethyl ammonium chloride (cationic surface active agent) 0.87g, polyoxyethylene lauryl ether (EO:20.EO represents the ethylene oxide unit number) (nonionic surface active agent) 5.74g, polyoxyethylene isotridecyl ether (EO:3) (nonionic surface active agent) 2.28g, polyoxyethylene oleyl ether (EO:50) (nonionic surface active agent) 1.19g, under agitation, 60 ℃ with ultrasonic wave its emulsification was disperseed 15 minutes.Add lauryl mercaptan 1.24g, to carry out in the autoclave after the nitrogen displacement, be pressed into and fill vinyl chloride (VCM) 22.35g, add 2, below two (2-amidine propane) the 2 hydrochloride 0.62g(of 2-azo, note is made V-50) and the solution of water 18g, reacted 5 hours at 60 ℃, obtain the aqueous liquid dispersion of polymer.The composition basically identical of the composition of polymer and charging monomer.In the aqueous liquid dispersion that obtains, add octadecyl trimethyl ammonium chloride (cationic surface active agent) 2.0g.
Compare Production Example 3
In the 1L autoclave, add CF
3CF
2-(CF
2CF
2)
n-CH
2CH
2OCOC (Cl)=CH
2(n=2.0) 37.25g, acrylic acid stearyl 64.57g, pure water 220g, dipropylene glycol monomethyl ether 37.24g, dioctadecyl dimethyl ammonium chloride (cationic surface active agent) 3.08g, octadecyl trimethyl ammonium chloride (cationic surface active agent) 0.87g, polyoxyethylene lauryl ether (EO:20.EO represents the ethylene oxide unit number) (nonionic surface active agent) 5.74g, polyoxyethylene isotridecyl ether (EO:3) (nonionic surface active agent) 2.28g, polyoxyethylene oleyl ether (EO:50) (nonionic surface active agent) 1.19g, under agitation, 60 ℃ with ultrasonic wave its emulsification was disperseed 15 minutes.Add lauryl mercaptan 1.24g, to carry out in the autoclave after the nitrogen displacement, be pressed into and fill vinyl chloride (VCM) 22.35g, add 2, below two (2-amidine propane) the 2 hydrochloride 0.62g(of 2-azo, note is made V-50) and the solution of water 18g, reacted 5 hours at 60 ℃, obtain the aqueous liquid dispersion of polymer.The composition basically identical of the composition of polymer and charging monomer.In the aqueous liquid dispersion that obtains, do not add cationic emulsifier.
Compare Production Example 4
In the 500ml reaction flask, add CF
3CF
2-(CF
2CF
2)
n-CH
2CH
2OCOC (Cl)=CH
2(n=2.0) 18.63g, acrylic acid stearyl 12.42g, isobornyl methacrylate 31.04g, pure water 110g, dipropylene glycol monomethyl ether 18.62g, dioctadecyl dimethyl ammonium chloride (cationic surface active agent) 1.54g, octadecyl trimethyl ammonium chloride (cationic surface active agent) 0.44g, polyoxyethylene lauryl ether (EO:20.EO represents the ethylene oxide unit number) (nonionic surface active agent) 2.87g, polyoxyethylene isotridecyl ether (EO:3) (nonionic surface active agent) 1.14g, polyoxyethylene oleyl ether (EO:50) (nonionic surface active agent) 0.60g, under agitation, 60 ℃ with ultrasonic wave its emulsification was disperseed 15 minutes.Add lauryl mercaptan 0.62g, to carry out in the autoclave after the nitrogen displacement, be pressed into and fill vinyl chloride (VCM) 22.35g, add 2, below two (2-amidine propane) the 2 hydrochloride 0.31g(of 2-azo, note is made V-50) and the solution of water 9g, reacted 5 hours at 60 ℃, obtain the aqueous liquid dispersion of polymer.The composition basically identical of the composition of polymer and charging monomer.In the aqueous liquid dispersion that obtains, add polyoxyethylene cocoyl amine (nonionic surface active agent) 1.0g.
Compare Production Example 5
In the 500ml reaction flask, add CF
3CF
2-(CF
2CF
2)
n-CH
2CH
2OCOC (Cl)=CH
2(n=2.0) 18.63g, acrylic acid stearyl 12.42g, isobornyl methacrylate 31.04g, pure water 110g, dipropylene glycol monomethyl ether 18.62g, dioctadecyl dimethyl ammonium chloride (cationic surface active agent) 1.54g, octadecyl trimethyl ammonium chloride (cationic surface active agent) 0.44g, polyoxyethylene lauryl ether (EO:20.EO represents the ethylene oxide unit number) (nonionic surface active agent) 2.87g, polyoxyethylene isotridecyl ether (EO:3) (nonionic surface active agent) 1.14g, polyoxyethylene oleyl ether (EO:50) (nonionic surface active agent) 0.60g, under agitation, 60 ℃ with ultrasonic wave its emulsification was disperseed 15 minutes.Add lauryl mercaptan 0.62g, to carry out in the autoclave after the nitrogen displacement, be pressed into and fill vinyl chloride (VCM) 22.35g, add 2, below two (2-amidine propane) the 2 hydrochloride 0.31g(of 2-azo, note is made V-50) and the solution of water 9g, reacted 5 hours at 60 ℃, obtain the aqueous liquid dispersion of polymer.The composition basically identical of the composition of polymer and charging monomer.In the aqueous liquid dispersion that obtains, add lauryl dimethyl amine oxide (amphoteric surfactant) 1.0g.
About the manufacturing of aqueous liquid dispersion, Table A is represented feed composition.
Embodiment 1～10 and comparative example 1～5
Use is by Production Example 1～10(Production Example 1～10) and Production Example 1～5(comparative example 1～5 relatively) aqueous liquid dispersion that obtains, make test cloth, estimate water-repellancy.
Be the mode dilute with water of 0.5 weight % with aqueous liquid dispersion with solid component concentration, the preparation treatment fluid.Mylar be impregnated in the treatment fluid, squeeze to press with mangle, be set at pick-up rate 65%, 100 ℃ of dryings 2 minutes, 160 ℃ of dryings 1 minute, make test cloth.Spray drying test and the test of infiltration water-repellancy with this test cloth.Table B represents result of the test.
In the table, the meaning of shorthand notation is as described below.
C6SFClA C
6F
13CH
2CH
2OCOC(Cl)=CH
2
C6SFMA C
6F
13CH
2CH
2OCOC(CH
3)=CH
2
C8SFA C
8F
17CH
2CH
2OCOCH=CH
2
VCM vinyl chloride
StA acrylic acid stearyl
IBMA isobornyl methacrylate (Tg＞50 ℃)
CHMA cyclohexyl methacrylate (Tg＞50 ℃)
[table 2]
[table 3]
[table 5]
Table B
| Example | The test of spray water-repellancy | The test of infiltration water-repellancy | Field trash stability |
| Embodiment 1 | 5 | ○ | ○ |
| Embodiment 2 | 5 | ○ | ○ |
| Embodiment 3 | 5 | ○ | ○ |
| Embodiment 4 | 5 | ○ | ○ |
| Embodiment 5 | 5 | ○ | ○ |
| Embodiment 6 | 5 | ○ | ○ |
| Embodiment 7 | 5 | ○ | ○ |
| Embodiment 8 | 5 | ○ | ○ |
| Embodiment 9 | 5 | ○ | ○ |
| Embodiment 10 | 5 | ○ | ○ |
| Comparative example 1 | 3 | △ | ○ |
| Comparative example 2 | 4 | △ | ○ |
| Comparative example 3 | 3 | × | × |
| Comparative example 4 | 3 | △ | × |
| Comparative example 5 | 3 | × | × |
Industrial utilizability
In order the parts of fibre, paper, nonwoven fabric, stone material, electrostatic filter, dust cover, fuel cell to be given excellent water-repellancy, to be dialled oiliness, soil resistance, can use fluoro-containing composition of the present invention.
Claims (20)
1. surface conditioning agent, it is characterized in that: it contains:
(1) fluoropolymer, this fluoropolymer has:
(a) be derived from as have fluoroalkyl the α-Lv Bingxisuan ester fluorochemical monomer repetitive and
(b) be derived from the repetitive of non-fluorine monomer; And
(2) cationic surface active agent that after the polymerization of fluoropolymer, adds.
2. surface conditioning agent as claimed in claim 1 is characterized in that:
The mol ratio of the repetitive (b) of the repetitive of the fluorochemical monomer in the fluorinated copolymer (a)/non-fluorine monomer is 0.01/1～10/1.
3. surface conditioning agent as claimed in claim 1 or 2 is characterized in that:
Fluorochemical monomer (a) is by the fluorochemical monomer shown in the following formula,
CH
2=C(-Cl)-C(=O)-Y-Z-Rf
In the formula, Y is-O-or-NH-,
Z is the organic group of directly combination or divalence,
Rf is the fluoroalkyl of carbon number 1～20.
4. as each described surface conditioning agent in the claim 1～3, it is characterized in that:
Non-fluorine monomer (b) is by the acrylate compounds shown in the following formula,
CH=CR
1-C(=O)O-R
2
In the formula, R
1Be H, C
1～C
4Alkyl or halogen,
R
2Be C
1～C
30Alkyl (for example being aliphatic group, aromatic group, aromatic-aliphatic group).
5. as each described surface conditioning agent in the claim 1～4, it is characterized in that:
Non-fluorine monomer (b) is for being selected from (b1) and having the acrylate of the straight chain shape of carbon number 12～30 or chain alkyl and (b2) glass transition temperature (Tg) or fusing point (Tm) being at least a kind of compound in (methyl) acrylate more than 50 ℃.
6. surface conditioning agent as claimed in claim 5 is characterized in that:
Acrylate (b1) with straight chain shape or chain alkyl is by the acrylate shown in the following formula,
CH
2＝CHCOOA
1
In the formula, A
1For by C
nH
2n+1Alkyl shown in (n=12～30).
7. surface conditioning agent as claimed in claim 6 is characterized in that:
Carbon number with the alkyl in the acrylate (b1) of straight chain shape or chain alkyl is 12～22.
8. surface conditioning agent as claimed in claim 5 is characterized in that:
(methyl) acrylate (b2) is by the acrylate compounds shown in the following formula,
CH=CR
11-C(=O)O-R
12
In the formula, R
11Be H, C
1～C
4Alkyl or halogen,
R
12Be C
1～C
30The aliphatic group of straight chain shape, chain or ring-type, C
6～C
20Aromatic group, C
7～C
25The aromatic-aliphatic group.
9. as each described surface conditioning agent in the claim 1～8, it is characterized in that:
Non-fluorine monomer (b) is for being selected from lauryl acrylate, acrylic acid myristyl ester, acrylic acid cetyl ester, acrylic acid stearyl, acrylic acid docosyl ester;
Cyclohexyl acrylate, isobornyl acrylate, acrylic acid norbornene ester, acrylic acid adamantane esters, acrylic acid two ring pentyl esters, acrylic acid two cyclopentene esters, acrylic acid three ring esters in the last of the ten Heavenly stems, phenyl acrylate, acrylic acid naphthalene ester, benzyl acrylate, acrylic acid 2-tert-butyl group phenyl ester, acrylic acid naphthalene ester;
Methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, the metering system tert-butyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate, the methacrylic acid norbornene ester, the methacrylic acid adamantane esters, methacrylic acid two ring pentyl esters, methacrylic acid two cyclopentene esters, methacrylic acid three ring esters in the last of the ten Heavenly stems, phenyl methacrylate, methacrylic acid naphthalene ester, benzyl methacrylate, methacrylic acid (2-dimethylamino) ethyl ester, methacrylic acid aziridine ester, methacrylic acid '-aziridino ethyl ester, methacrylic acid two cyclopentene esters; With
In the methylallyl chloride acid esters at least a kind.
10. as each described surface conditioning agent in the claim 1～9, it is characterized in that:
Fluoropolymer also comprises and contains the repetitive of the monomer of reactive group as co-polymerized monomer at molecule.
11. surface conditioning agent as claimed in claim 10 is characterized in that:
The above-mentioned reactive group that contains in the monomer of reactive group at molecule is hydroxyl.
12. as each described surface conditioning agent in the claim 1～11, it is characterized in that:
Contain the enclosed type polyisocyanate.
13. as each described surface conditioning agent in the claim 1～12, it is characterized in that:
By in the presence of surfactant (polymerization surfactant), make monomer (a) and (b) after the copolymerization, add cationic surface active agent (back interpolation surfactant), can access the surface conditioning agent that in medium, is dispersed with fluoropolymer.
14. as each described surface conditioning agent in the claim 1～13, it is characterized in that:
Cationic surface active agent (back interpolation surfactant) is by the ammonium salt shown in the following formula,
(R
51)
pN
＋(R
52)
4-pX
-
In the formula, R
51Be aliphatic (the saturated and/or unsaturated) group of the straight chain shape more than the C12 and/or a chain,
R
52Be alkyl, benzyl, the polyoxyethylene groups (quantity of oxyethylene group is 1～50 for example, is in particular 2～50, is in particular 3～50) of H or C1～4,
X is the group of formation anion,
P is 1 or 2.
15. as each described surface conditioning agent in the claim 1～14, it is characterized in that:
Also contain aqueous medium.
16. as each described surface conditioning agent in the claim 1～15, it is characterized in that:
It is aqueous liquid dispersion.
17. the manufacture method of a surface conditioning agent is characterized in that:
It is for the manufacture of following surface conditioning agent, and this surface conditioning agent contains:
(1) fluoropolymer, this fluoropolymer has:
(a) be derived from as have fluoroalkyl the α-Lv Bingxisuan ester fluorochemical monomer repetitive and
(b) be derived from the repetitive of non-fluorine monomer; And
(2) cationic surface active agent that after the polymerization of fluoropolymer, adds,
In described manufacture method, by in the presence of surfactant (polymerization surfactant), make monomer (a) and (b) add cationic surface active agent (back add use surfactant) after the copolymerization, can access the surface conditioning agent that in medium, is dispersed with fluoropolymer.
18. a water extraction oil extracticn agent composition is characterized in that:
It is each described surface conditioning agent in the claim 1～16.
19. a method of handling base material is characterized in that:
Comprise and utilize the step that each described surface conditioning agent is handled in the claim 1～16.
20. a fibre is characterized in that:
It is handled by each described surface conditioning agent in the claim 1～16 and obtains.
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|---|---|---|---|
| JP2011288659A JP2013136687A (en) | 2011-12-28 | 2011-12-28 | Surface treating agent, and method for producing the same |
| JP2011-288659 | 2011-12-28 |
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| Publication Number | Publication Date |
|---|---|
| CN103184690A true CN103184690A (en) | 2013-07-03 |
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|---|---|
| JP (1) | JP2013136687A (en) |
| KR (1) | KR20130076755A (en) |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105793487A (en) * | 2014-01-24 | 2016-07-20 | 日华化学株式会社 | Water repellent agent composition, water repellent fiber product and method for producing water repellent fiber product |
| CN107177982A (en) * | 2016-03-11 | 2017-09-19 | 大金工业株式会社 | Surface treatment composition |
| CN108699426A (en) * | 2016-02-23 | 2018-10-23 | 大金工业株式会社 | Surface conditioning agent |
| CN109923190A (en) * | 2016-12-15 | 2019-06-21 | 大金工业株式会社 | Dryingagent |
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| JP6015003B2 (en) * | 2011-12-28 | 2016-10-26 | ダイキン工業株式会社 | Method for producing fluorine-containing polymer and fluorine-containing composition |
| JP5811258B2 (en) * | 2013-11-22 | 2015-11-11 | ダイキン工業株式会社 | Surface treatment agent |
| JP6657730B2 (en) * | 2015-10-01 | 2020-03-04 | ダイキン工業株式会社 | Surface treatment agent |
| JP7397270B2 (en) * | 2018-10-10 | 2023-12-13 | ダイキン工業株式会社 | Fluoropolymers and surface treatment agents |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1149897A (en) * | 1995-03-31 | 1997-05-14 | 美国3M公司 | Aqueous oil and water repellent compositions |
| CN1292006A (en) * | 1998-02-27 | 2001-04-18 | 纳幕尔杜邦公司 | Stabilization of fluorochemical copolymer emulsions |
| CN1993443A (en) * | 2004-06-04 | 2007-07-04 | 优迈特株式会社 | Method for producing water-and-oil repellent agent |
| CN102149738A (en) * | 2008-09-15 | 2011-08-10 | 大金工业株式会社 | Water- and oil-repellent composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4655041B2 (en) * | 2004-06-25 | 2011-03-23 | ダイキン工業株式会社 | Soil release agent containing fluorine-containing copolymer and method for producing the same |
| CN102822309B (en) * | 2010-03-30 | 2015-12-09 | 大金工业株式会社 | Use the water extraction oil extracticn agent of α-chloroacrylic acid ester |
-
2011
- 2011-12-28 JP JP2011288659A patent/JP2013136687A/en active Pending
-
2012
- 2012-12-20 TW TW101148624A patent/TWI625339B/en active
- 2012-12-27 KR KR1020120154419A patent/KR20130076755A/en not_active Application Discontinuation
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1149897A (en) * | 1995-03-31 | 1997-05-14 | 美国3M公司 | Aqueous oil and water repellent compositions |
| CN1292006A (en) * | 1998-02-27 | 2001-04-18 | 纳幕尔杜邦公司 | Stabilization of fluorochemical copolymer emulsions |
| CN1993443A (en) * | 2004-06-04 | 2007-07-04 | 优迈特株式会社 | Method for producing water-and-oil repellent agent |
| CN102149738A (en) * | 2008-09-15 | 2011-08-10 | 大金工业株式会社 | Water- and oil-repellent composition |
Cited By (7)
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| Publication number | Publication date |
|---|---|
| TWI625339B (en) | 2018-06-01 |
| TW201336873A (en) | 2013-09-16 |
| JP2013136687A (en) | 2013-07-11 |
| KR20130076755A (en) | 2013-07-08 |
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