CN101006149A - Water-repellent/oil-repellent composition - Google Patents

Water-repellent/oil-repellent composition Download PDF

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CN101006149A
CN101006149A CN 200580027829 CN200580027829A CN101006149A CN 101006149 A CN101006149 A CN 101006149A CN 200580027829 CN200580027829 CN 200580027829 CN 200580027829 A CN200580027829 A CN 200580027829A CN 101006149 A CN101006149 A CN 101006149A
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water
active agent
weight
composition
polymerizable monomer
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柏木正人
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Daikin Industries Ltd
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Daikin Industries Ltd
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Abstract

Disclosed is an aqueous water-repellent/oil-repellent composition containing the following components (A), (B) and (C). Fluorine-containing copolymer (A): a copolymer containing a polymerizable monomer (a1) having a perfluoroalkyl group with 1-6 carbon atoms or a perfluoroalkenyl group wherein the amount of (a1) is not less than 20% by weight relative to the copolymer. Surfactant (B): a surfactant essentially containing a sorbitan ester or an alkylene oxide addition product thereof. Aqueous medium (C): a medium substantially containing water only or water and a water-soluble organic solvent.

Description

Composition of waterproofing and oil-proof agent
Technical field
The present invention relates to a kind of composition of waterproofing and oil-proof agent, more particularly, relate to a kind of composition of waterproofing and oil-proof agent of water tolerance excellence.
Background technology
Comprise the unitary polymkeric substance of the polymerizable monomer with multi-fluorinated alkyl in the past and be widely used as water and oil repellent agent.In order to obtain containing the multipolymer of multi-fluorinated alkyl, can use polymerization processs such as mass polymerization, solution polymerization, suspension polymerization, letex polymerization, wherein solution polymerization, letex polymerization are more commonly used.This wherein the problem from the operating environment, considers the problems such as influence of environment, by the aqueous dispersion of emulsion polymerization prepared than with better by the solvent dispersion of solution polymerization.
The fibre product of handling through water and oil repellent agent is widely used in daily dress material, motion dress material, indoor article, outdoor goods, medical non woven fabric etc., expansion along with its purposes, expectation further improves the flexibility, didirtresistance, water tolerance of these fibre products etc., and the weather resistance of improving these character.
In recent years, in order to address these problems, open 2000-212549 the spy, the spy opens and discloses the monomeric validity of specific bridging property (reactivity) etc. among the 2000-282016.
Te Kaiping 6-10271, the flat 10-501306 of special table, spy open and disclose share of isocyanate compound, blocked isocyanate compounds among the 2000-136337.
The polymkeric substance of fluorine-containing (methyl) acrylate/vinylchlorid (VCl), vinylidene chloride (VdCl) or alkyl acrylate etc. is disclosed in the document of some patents etc.
The Rf base of used (methyl) acrylate that contains Rf base long-chain fluoro-alkyl (containing 8 carbon atoms) normally in the middle of these.
Result's [EPA reports " PRELIMINARY RISKASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATEDWITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITSSALTS " (http://www.epa.gov/opptintr/pfoa/pfoara.pdf)] etc. in the light of recent researches, the load that the PFOA (Perfluorocaprylic Acid, perfluorooctanoic acid) of one of clear and definite gradually long-chain fluorinated alkyl compound may bring environment; EPA (the U.S. environment protection Room) need to strengthen in declaration on April 14th, 2003 science of PFOA is investigated.On the other hand, federal register (Federal Register) (FR Vol.68, No.73/2003 April 16, [FRL-2303-8], http://www.epa.gov/opptintr/pfoa/pfoafr.pdf), the EPA Enviromental News FOR RELEASE:EPAINTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICALPROCESSING AID (http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf) of issue on April 16th, 2003 (Monday), the EPA OPPT FACT SHEET (http://www.epa.gov/opptintr/pfoa/pfoafacts.pdf) on April 14th, 2003 has announced that long-chain fluoro-alkyl (telomer) has the possibility that generates PFOA by decomposition or metabolism.
For the alternative compounds of using with telomer has different chemical skeleton structures reduces load to environment, the use of the polymerizable monomer that contains short chain Rf base is also studied.
The prior art that contains the polymerizable monomer of short chain Rf base as use, a kind of composition of waterproofing and oil-proof agent is disclosed among the WO03/062521, said composition contains the multipolymer of (methyl) acrylate with short chain Rf base and VCl or VdCl to improve water tolerance, but the water and oil-resistant of said composition and water tolerance are also insufficient, its prolonged preservation stability and also insufficient to the stability of inclusion.In addition, also put down in writing the example that uses the polymerizable monomer that contains short chain Rf base among WO02/083809, the WO04/035708, but its water and oil-resistant and water tolerance are insufficient.
According to above-mentioned document, known in the polymkeric substance of the polymerized unit with the acrylate that contains the Rf base, if the chain length of Rf base shortens, then the waterproof and oilproof performance descends.Also find in contriver's the research in addition, if the simple chain length that shortens the Rf base then in such as the such rainfall endurance test of this test (Bundesmanntest) of Bandaid, flows out the phenomenon that the water yield has remarkable increase (water tolerance decline).
That is to say, in the prior art, adopt alternative compounds can not obtain when satisfied reduction is to the purpose of carrying capacity of environment, also satisfying highly water-proof aqueous liquid dispersion of water and oil repellent with the chemical skeleton structure that is different from telomer.
Summary of the invention
The object of the present invention is to provide and a kind ofly can give highly water-proof composition to fiber base material, use the compound with the chemical skeleton structure that is different from telomer in the described composition, the problem that this compound is caused aspect environment is less.
The invention provides a kind of aqueous water-and-oil repellant composition, said composition comprises following fluorinated copolymer (A), tensio-active agent (B) and aqueous medium (C).
Wherein, described fluorinated copolymer (A) comprises following polymerizable monomer (a1) and polymerizable monomer (a2), and also comprises following polymerizable monomer (a3) as required, and the amount of described polymerizable monomer (a1) is more than the 20 weight % with respect to this multipolymer;
Described (a1) is 1～6 the perfluoroalkyl or the polymerizable monomer of perfluoro alkenyl for having carbonatoms;
Described (a2) be can with the polymerizable monomer of (a1) copolymerization, the glass transition temperature Tg of its homopolymer be more than 50 ℃ and/or fusing point Tm be more than 30 ℃;
Described (a3) is for containing the polymerizable monomer of polar group or reactive group.
Described tensio-active agent (B) is nonionic surface active agent (b1), and this nonionic surface active agent (b1) is Isosorbide Dinitrate and/or its epoxide affixture.
Described aqueous medium (C) is the medium that only contains water, or is the medium that contains the mixture of water and organic solvent.
The present invention also provides a kind of aqueous water-and-oil repellant mixture, and described mixture contains above-mentioned aqueous water-and-oil repellant composition and linking agent.
By the present invention, can give excellent water and oil-resistant to fiber base material, particularly can give the water tolerance of its height, and the stability of described fiber base material (mechanical stability, chemical stability, prolonged preservation) is good.
Embodiment
Be used for polymerizable monomer of the present invention (a1) for having the compound of perfluoroalkyl or perfluoro alkenyl and polymerizability unsaturated group.
Being limited to 6 on the carbonatoms of perfluoroalkyl or perfluoro alkenyl, is 5 for example, in particular for 4.The example of perfluoroalkyl 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) 2Deng.The example of perfluoro alkenyl is-CF=CF (CF 3) ,-CF=C (CF 3) 2,-C (CF 3)=CF (CF (CF 3) 2) ,-C (CF 2CF 3)=C (CF 3) 2Deng.
The polymerizability unsaturated group can be acrylate-based (OC (=O)-CH=CH 2), methacrylate based (OC (=O)-C (CH 3)=CH 2), vinyl (CH=CH 2), vinylidene (CH=CH-), vinylidene base (=C=CH 2), α substitutional crylic acid ester group (OC (=O)-CX=CH 2[X is halogen atom (for example fluorine atom, chlorine atom, bromine atoms, iodine atom), CFX 1X 2Base (X 1And X 2Be hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom) (CF for example 3), cyano group, carbon atom is 1～21 a straight chain shape or a catenate fluoro-alkyl, the benzyl that replaces or do not have replacement, replace or do not have the phenyl of replacement]) etc.
Polymerizable monomer (a1) for example is the compound of following formula (11).
(Rf-A) n-B formula (11)
Rf: carbonatoms is 1～6 perfluoroalkyl or perfluoro alkenyl;
A: the organic radical of divalence or singly-bound;
B: polymerizability unsaturated group;
N:1 or 2.
In the formula (11), the organic group of divalence (A yl) can be ester group (C (=O) O-), amide group, alkylidene group (carbonatoms 1～10), ether (O-) ,-CH 2CH (OX) CH 2The combination of-(X is that hydrogen or carbonatoms are 1～5 acyl group) and above-mentioned group etc.
Polymerizable monomer (a1) can be the compound of following formula (11-1)～(11-7).
Rf-SO 2-N (R 1)-R 2-OCOCR 3=CH 2Formula (11-1)
Rf-R 2-OCOCR 3=CH 2Formula (11-2)
Rf-CO-N (R 1)-R 2-OCOCR 3=CH 2Formula (11-3)
RfCH 2CH (OR 4) CH 2-OCOCR 3=CH 2Formula (11-4)
Rf-O-Ar-CH 2-OCOCR 3=CH 2Formula (11-5)
Rf-R 5-SO 2-R 2-OCOCR 3=CH 2Formula (11-6)
Rf-R 2-O-CON (R 1)-R 6-OCOCR 3=CH 2Formula (11-7)
Rf: carbonatoms is 1～6 perfluoroalkyl or perfluoro alkenyl;
R 1: H or carbonatoms are 1～4 alkyl;
R 2: carbonatoms is 1～10 alkylidene group;
R 3: H, carbonatoms are 1～4 alkyl or halogen;
R 4: H or carbonatoms are 1～4 acyl group;
Ar: aromatic series base, particularly phenylene;
R 5: carbonatoms is 1～10 alkylidene group or singly-bound;
R 6: carbonatoms be 1～10 alkylidene group or-R 7-N (R 1) CO-O-R 2-;
R 7: carbonatoms be 1～10 alkylidene group, ring alkylidene group, phenylene, methylene phenyl or
Figure A20058002782900081
Polymerizable monomer (a1) is preferably acrylate, and its α position can be substituted.
The specific examples of polymerizable monomer (a1) is as follows.
C 2F 5CH 2OCOCH＝CH 2、C 2F 5CH 2OCOC(CH 3)＝CH 2、
C 2F 5CH 2OCOCF＝CH 2、C 2F 5CH 2OCOCCl＝CH 2、
C 2F 5CH 2CH 2OCOCH＝CH 2、C 2F 5CH 2CH 2OCOC(CH 3)＝CH 2、
C 2F 5CH 2CH 2OCOCCF＝CH 2、C 2F 5CH 2CH 2OCOCCl＝CH 2、
C 4F 9CH 2CH 2OCOCH＝CH 2、C 4F 9CH 2CH 2OCOC(CH 3)＝CH 2、
C 4F 9CH 2CH 2OCOCF＝CH 2、C 4F 9CH 2CH 2OCOCCl＝CH 2、
C 6F 13CH 2CH 2OCOCH＝CH 2、C 6F 13CH 2CH 2OCOC(CH 3)＝CH 2、
C 6F 13CH 2CH 2OCOCF＝CH 2、C 6F 13CH 2CH 2OCOCCl＝CH 2、
(CF 3) 2CFCF 2CF 2CH 2CH 2OCOCH＝CH 2、
(CF 3) 2CFCF 2CF 2CH 2CH 2OCOC(CH 3)＝CH 2、
(CF 3) 2CFCF 2CF 2CH 2CH 2OCOCF＝CH 2、
(CF 3) 2CFCF 2CF 2CH 2CH 2OCOCCl＝CH 2、
(CF 3) 2CFCH 2CH 2OCOCH＝CH 2、
(CF 3) 2CFCH 2CH 2OCOC(CH 3)＝CH 2、
(CF 3) 2CFCH 2CH 2OCOCF＝CH 2、(CF 3) 2CFCH 2CH 2OCOCCl＝CH 2、
C 4F 9SO 2N(CH 3)CH 2CH 2OCOCH＝CH 2、
(CF 3) 2CFCF 2CF 2CH 2CH(OCOCH 3)CH 2OCOCH＝CH 2、
C 6F 11O-C 6H 4-CH 2OCOCH＝CH 2、
C 2F 5-SO 3-CH 2CH 2OCOCH＝CH 2、C 2F 5-SO 2-CH 2CH 2OCOC(CH 3)＝CH 2
C 2F 5CH 2CH 3-SO 2-CH 2CH 3OCOCH＝CH 2、C 2F 5CH 2CH 2-SO 2-CH 2CH 2OCOC(CH 3)＝CH 2
C 4F 9-SO 2-CH 3CH 2OCOCH＝CH 2、C 4F 9-SO 2-CH 2CH 3OCOC(CH 3)＝CH 2
C 4F 9CH 2CH 2-SO 2-CH 2CH 3OCOCH＝CH 2、C 4F 3CH 2CH 2-SO 2-CH 2CHOCOC(CH 3)＝CH 2
C 4F 9CH 2CH 2-O-CONH-CH 2CH 2OCOCH＝CH 2、C 4F 9CH 2CH 2-O-CONH-CH 2CH 2OCOC(CH 3)＝CH 2
C 4F 9CH 2CH 2-O-CONH-R 7-NHCO-O-CH 2CH 2OCOCH=CH 2(R 7: the methylene phenyl)
C 4F 9CH 2CH 2-O-CONH-R 7-NHCO-O-CH 2CH 2OCOOC (CH 3)=CH 2(R 7: the methylene phenyl)
Be used for polymerizable monomer (a2) that can copolymerization of the present invention and be not particularly limited, generally can be the compound of following formula (12).
(R-A) n-B formula (12)
R: carbonatoms is 1～30 alkyl, cycloalkyl, alkenyl or cycloalkenyl;
A: the organic radical of divalence or singly-bound;
B: polymerizability unsaturated group;
N:1 or 2.
In the formula (12), the organic radical of divalence (A yl) can be ester group (C (=O) O-or-OC (=O)-), amide group, ether are (O-) etc.Polymerizability unsaturated group (B yl) can be acrylate-based (OC (=O)-CH=CH 2), methacrylate based (OC (=O)-C (CH 3)=CH 2), vinyl (CH=CH 2), vinylidene (CH=CH-), vinylidene base (=C=CH 2), α substitutional crylic acid ester group (OC (=O)-CX=CH 2(X is halogen (for example fluorine, chlorine or bromine), CF 3Or CN)) etc.
Further, polymerizable monomer (a2) can be the compound of following formula (12-1)～(12-5).
R-OCOCR 3=CH 2Formula (12-1)
R-OCOCH=CHCOO-R formula (12-2)
R 1-COOCH=CH 2Formula (12-3)
R 2-CR 3=CH 2Formula (12-4)
Formula (12-5)
R: carbonatoms is 1～30 alkyl, cycloalkyl, alkenyl or cycloalkenyl;
R 1: carbonatoms is 1～20 alkyl or alkenyl;
R 2: carbonatoms is 1～30 alkyl, cycloalkyl, aromatic series base or halogen;
R 3: H, carbonatoms are 1～4 alkyl or halogen;
R 4: H, carbonatoms are 1～10 alkyl or cycloalkyl.
The specific examples of polymerizable monomer (a2) is for being (methyl) esters of acrylic acid of the alkyl more than 15 such as carbonatomss such as (methyl) vinylformic acid cetyl ester, (methyl) stearyl acrylate ester, (methyl) vinylformic acid 20 diester; Such as carbonatomss such as (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) vinylformic acid three ring decyl ester is ester ring type alkyl more than 6 or (methyl) esters of acrylic acid of ester ring type thiazolinyl; Vinylchlorid; The vinyl ester of the lipid acid of carbonatoms more than 15 of stearic acid vinyl ester etc.; Such as N-alkyl Maleimide classes such as N-methyl Maleimide, N-cyclohexyl Maleimides.
The specific examples of other of polymerizable monomer (a2) is methyl methacrylate, vinyl cyanide, vinylbenzene, alkyl vinyl ether, alpha-olefin etc.
For polymerizable monomer (a2), preferably the second-order transition temperature (Tg) of the homopolymer that is formed by this polymerizable monomer is more than 50 ℃, for example more than 60 ℃, particularly more than 70 ℃, and/or fusing point (Tm) is more than 30 ℃, for example more than 40 ℃, particularly more than 50 ℃.Under Tg and/or the Tm situation in this scope, can obtain high waterproof and oilproof performance.Be limited on the preferred Tg 200 ℃ and Tm on be limited to 200 ℃.
As required, be used for polymerizable monomer of the present invention (a3) and contain polar group and/or reactive group.
The example of polar group is hydroxyl (OH), polyoxy alkylidene, amino (NR 2(R is that hydrogen or carbonatoms are 1～4 alkyl)), N-methylol (NHCH 2OH), amide group, carboxyl (COOH), halogen group etc.
The example of reactive group is epoxy group(ing), end-blocking isocyanate group etc.
The specific examples of polymerizable monomer (a3) is (methyl) vinylformic acid 3-chloro-2-hydroxy propyl ester, N-methylol (methyl) acrylamide, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, 1-chloro-4-methyl-benzene, (methyl) glycidyl acrylate, diacetone-acryloamide(DAA), (methyl) vinylformic acid direactive glyceride, (methyl) vinylformic acid polyoxyalkylenes diol monoester, contains (methyl) acrylate of end-blocking isocyanate group etc.
For multipolymer (A), except (a1), (a2), (a3), can also contain can with the polymerizable monomer of (a1) copolymerization, this can for example be (methyl) acrylate, vinylidene chloride, divinyl, chloroprene, isoprene, vinyl acetate, alkyl vinyl ether etc. of the alkyl below 14 for carbonatomss such as (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylates with the polymerizable monomer of (a1) copolymerization.
Multipolymer (A) can be homopolymer or 2 membered copolymers, but the multipolymer more than 3 yuan preferably.
(a1) in multipolymer (A), (a2), (a3) ratio are:
(a1) being 20 weight %～100 weight %, (a2) is 0 weight %～80 weight %, (a3) is 0 weight %～20 weight %;
Preferably (a1) is 30 weight %～95 weight %, (a2) is 5 weight %～70 weight %, (a3) is 0 weight %～15 weight %;
More preferably (a1) is 35 weight %～90 weight %, (a2) is 9 weight %～60 weight %, (a3) is 1 weight %～10 weight %.
Being used for tensio-active agent of the present invention (B) must composition as it with nonionic surface active agent (b1) Isosorbide Dinitrate or its epoxy compounds affixture.
Tensio-active agent (B) can also comprise (b2) other nonionic surface active agent and/or (b3) cationic surfactant.
Isosorbide Dinitrate is the ester of carboxylic acid (carbonatoms is 1～30) and anhydro sorbitol.The mole number of the carboxylic acid in the Isosorbide Dinitrate is 1,2 or 3.Be preferably the monocarboxylate.
In the epoxide affixture of Isosorbide Dinitrate, epoxide is oxyethane or propylene oxide preferably.In the epoxide affixture, the addition mole number of epoxide can be 1～50, can be 1～30 especially.
(b1) Isosorbide Dinitrate in or its epoxide affixture can be the tensio-active agents of following formula (21) or formula (22) expression.
Figure A20058002782900111
Formula (21)
Formula (22)
In the above-mentioned formula, R 1Be that carbonatoms is that 1～22 alkyl or carbonatoms are 2～22 alkenyl; R 4, R 5, R 6Be H, R 1CO-,-(CH 2CH 2O) p-(R 2O) q-R 3(R 2Be that carbonatoms is the alkylidene group more than 3; R 3For hydrogen atom, carbonatoms are that 1～22 alkyl or carbonatoms are 2～22 alkenyl; P is the number more than 2; Q is the number more than 0 or 1.
Specific examples with the nonionic surface active agent (b1) of formula (21) or (22) expression is the mono laurate Isosorbide Dinitrate, the Stearinsaeure Isosorbide Dinitrate, single palmitinic acid Isosorbide Dinitrate, single oleic acid Isosorbide Dinitrate, sesquialter stearic acid Isosorbide Dinitrate, three stearic acid Isosorbide Dinitrate, the mono laurate Sorbitan ethoxylate, single palmitinic acid Sorbitan ethoxylate, the Stearinsaeure Sorbitan ethoxylate, single oleic acid Sorbitan ethoxylate and three stearic acid polyoxyethylene Isosorbide Dinitrate etc.
As other nonionic surface active agent (b2), can be polyalkylene glycol ester, the polyoxyethylene (POE)/polyoxypropylene (POP) multipolymer (random copolymers or segmented copolymer) of the saturated and/or unsaturated fatty acids of straight chain shape and/or catenate epoxide affixture, straight chain shape and/or a chain saturated and/or the unsaturated aliphatic base, the epoxide affixture of acetylenediol etc.Wherein, the structure of preferred epoxide addition part and polyalkylene glycol moiety is polyoxyethylene (POE) or polyoxypropylene (POP) or POE/POP multipolymer (random copolymers or segmented copolymer).
In addition, problem (biological degradability, the environmental hormone etc.) aspect from environment is considered, does not contain the aromatic series base on other nonionic surface active agent (b2) preferred structure.
Other nonionic surface active agent (b2) can be the tensio-active agents of formula (23) expression.
R 1O-(CH 2CH 2O) p-(R 2O) q-R 3Formula (23)
In the above-mentioned formula, R 1Be that carbonatoms is that 1～22 alkyl or carbonatoms are 2～22 alkenyl; R 2Be that carbonatoms is the alkylidene group of (for example 3～10) more than 3; R 3For hydrogen atom, carbonatoms are that 1～22 alkyl or carbonatoms are 2～22 alkenyl; P is the number more than 2; Q is the number more than 0 or 1.
R 2Be exemplified as propylidene and butylidene.
The object lesson of the nonionic surface active agent (b2) shown in the formula (23) is:
C 10H 21O-(CH 2CH 2O) p-(C 3H 6O) q-H、
C 12H 25O-(CH 2CH 2O) p-(C 3H 6O) q-H、
C 16H 31O-(CH 2CH 2O) p-(C 3H 6O) q-H、
C 16H 33O-(CH 2CH 2O) p-(C 3H 6O) q-H、
C 18H 35O-(CH 2CH 2O) p-(C 3H 6O) q-H、
C 18H 37O-(CH 2CH 2O) p-(C 3H 6O) q-H、
C 12H 25O-(CH 2CH 2O) p-(C 3H 6O) q-C 12H 25、
C 16H 31O-(CH 2CH 2O) p-(C 3H 6O) q-C 16H 31、
C 16H 33O-(CH 2CH 2O) p-(C 3H 6O) q-C 12H 25、
Iso-C 13H 27O-(CH 2CH 2O) p-(C 3H 6O) q-H etc.
In the above-mentioned formula, p and q and above-mentioned same meaning.
In addition, nonionic surface active agent (b2) can be the tensio-active agent of following formula (24) expression.
R 1COO-(CH 2CH 2O) p-(R 2O) q-R7 formula (24)
In the above-mentioned formula, R 1Be that carbonatoms is that 1～22 alkyl or carbonatoms are 2～22 alkenyl; R 2Be that carbonatoms is the alkylidene group of (for example 3～10) more than 3; R 7Be H, R 1CO-or R 3(R 3Be that carbonatoms is that 1～22 alkyl or carbonatoms are 2～22 alkenyl); P is the number more than 2; Q is the number more than 0 or 1.
Specific examples with the nonionic surface active agent (b2) of formula (24) expression is:
C 17H 35COO-(CH 2CH 2O) p-H、
C 17H 33COO-(CH 2CH 2O) p-H、
C 17H 35COO-(CH 2CH 2O) p-(C 3H 6O) q-H、
C 17H 35COO-(CH 2CH 2O) p-OCC 17H 35、
C 15H 31COO-(CH 2CH 2O) p-H、
C 11H 23COO-(CH 2CH 2O) p-H etc.
In the above-mentioned formula, p and q and above-mentioned same meaning.
Can also be also with other nonionic surface active agent beyond above-mentioned.
Cationic surfactant (b3) is ammonium salt preferably.Cationic surfactant (b3) can be R 1 p-N +R 2 qX -The ammonium salt of structure, R 1 p-N +R 2 qX -In:
R 1Be that carbonatoms is a straight chain shape and/or catenate aliphatics (saturated and/or unsaturated) base of (for example being 12～50) more than 12;
R 2For H or carbonatoms are 1～4 alkyl, benzyl, polyoxyethylene groups (numerical example of oxyethylene group is as being 1 (be in particular 2, be more particularly 3)～50), this R 2Be preferably CH especially 3, C 2H 5
X is that halogen, carbonatoms are 1～4 lipid acid alkali;
P is 1 or 2, and q is 2 or 3, and p+q=4.
R 1Can have 12～50 carbon atoms, for example have 12～30 carbon atoms.
In the tensio-active agent (B), nonionic surface active agent (b1) is 1 weight %～100 weight % with respect to the ratio of tensio-active agent (B), for example is 5 weight %～100 weight %.Other nonionic surface active agent (b2) can be 0～1000 weight part with respect to the amount of 100 weight part nonionic surface active agent (b1), for example are 5 weight parts～500 weight parts.Measure 100 weight parts with respect to nonionic surface active agent (b1) and total (b2), the amount of cationic surfactant (b3) can be 0 weight part～500 weight parts, for example is 1 weight part～300 weight parts.
The total usage quantity of tensio-active agent (B) can be 0.1 weight part～20 weight parts with respect to the polymerizable monomer (A) of 100 weight parts, is preferably 1 weight part～15 weight parts.
Being used for aqueous medium of the present invention (C) and can only containing water, also can be the mixture of water and organic solvent.Aqueous medium (C) can in fact only contain water (content of water is at least 98 weight %, particularly is at least 99 weight %).
Organic solvent be preferably can with water blended organic solvent.Representative examples of organic can be enumerated ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, DPGME, acetone, butanone, ethanol, Virahol etc.
Under the situation with an organic solvent, consider incendivity, peculiar smell, to load of environment etc., preferred a small amount of as far as possible solvent that uses high flash point (for example being more than 20 ℃, to be preferably more than 50 ℃) (with respect to multipolymer (A) for example is below the 40 weight %, and it is following to be preferably 30 weight %).
The content of aqueous medium (C) can be to make fluorinated copolymer (A) be 0.01 weight %～80 weight %, for example be the amount of 0.02 weight %～50 weight % with respect to the content of waterborne compositions.
Aqueous water-and-oil repellant composition of the present invention can be made by following manufacture method: with polymerizable monomer (a1), (a2), (a3), tensio-active agent (B), aqueous medium (C) feed intake, emulsification, carry out polymerization then.Can adopt methods such as dripping polymerization, seeding polymerization as required.In addition, can also add nonionic surfactant (b1) after using (b1) tensio-active agent in addition to carry out letex polymerization makes.
When the part of polymerizable monomer is gaseous monomer, can make by the following method: with the material beyond this gaseous monomer feed intake, emulsification, before polymerization, gaseous monomer is fed intake then, polymerization.
Carrying out under the emulsive situation, as required, preferably utilize intimate mixing device (homomixer) etc. carry out pre-dispersed after, use ultrasonic emulsification machine or high pressure homogenisers to carry out emulsification, so that the particle diameter of the polymerizable monomer after the emulsification is below the 0.3 μ m.
When polymerization, can use the chain-transfer agent and the polymerization starter of the molecular weight that is used to adjust co-polymer.
As chain-transfer agent, can enumerate octyl mercaptan, lauryl mercaptan, stearyl mercaptan, 2-hydroxyethyl mercaptan etc.
In addition, as polymerization starter, can enumerate 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2-amidine propane) dihydrochloride, 2, azo-initiators such as 2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride, peroxide initiators such as t-butylperoxy pivarate, tert-butyl hydroperoxide neodecanoic acid ester, redox class initiator etc.
In resulting composition of waterproofing and oil-proof agent, from the viewpoint of sedimentation stability, the particle diameter of dispersion resin is preferably below the 0.25 μ m, for example is below the 0.15 μ m.
In composition of waterproofing and oil-proof agent of the present invention, the additive etc. that can further comprise as required, linking agent, other polymkeric substance, other water-resisting agents, oil-proofing agent, stain control agent, insect-proof agent, fire retardant, static inhibitor, dye stabilizers, anti-creasing agent, sanforzing agent, quality machining agent, soft finishing agent, defoamer etc.
In order to improve water tolerance, preferred and use linking agent.
As linking agent, can enumerate with end-blocking isocyanate compound, melamine resin compound, oxalic dialdehyde resinoid compound, urea resinoid compound, cross-linking type monomer (the end-blocking thing of N hydroxymethyl acrylamide, methacrylic acid 2-isocyanate group ethyl ester etc.) serve as must polymerized unit polymkeric substance etc., preferred end-blocking isocyanate compound or melamine resin compound.Herein, the end-blocking isocyanate compound is preferably with the compound of end-capping reagent with the isocyanate-terminated structure of polyisocyanates for not having the compound of polymerizability unsaturated group.As the melamine resin compound, can enumerate tri methylol melamine, hexamethylol melamine etc.
For the object being treated that utilizes the resulting composition of waterproofing and oil-proof agent of the present invention to handle, can be fibre product, paper, timber, leather, plastics, glass, brick, cement, stone material etc., be preferably the fibre product of forms such as fiber, silk or cloth especially.
By composition of the present invention (particularly fluorinated copolymer) is attached on the object being treated, object being treated is handled.
When being administered to composition of the present invention on the object being treated, preferably utilize the combination of coating, dipping, spraying, filler, roller coat or these methods.Usually, object being treated is impregnated in the aqueous water-and-oil repellant composition, utilizes roll to remove excess liquid, carry out drying then and carry out thermofixation as required.When composition of the present invention was applied to object being treated, its treatment capacity was preferably and makes multipolymer (A) be the about 0.01 weight %～1 weight % of object being treated.
Embodiment
Provide embodiment below, the present invention is carried out specific description.Among the embodiment, if do not particularly point out, then " % " and " part " represents " weight % " and " weight part " respectively.
In an embodiment, each characteristic of estimating is determined as follows.
Water and oil-resistant
The dilute with water polymer dispersion liquid prepares treatment solution so that solid concentration is 0.6 weight %.With nylon taffeta cloth (Kanebo system Na チ ュ レ one ヌ, nylon 6, dark blue stained cloth) (Ny) and polyester/cotton blended fabric (twilled fabric, be unstained, the processing of mercerising yarn) (PET/C) be impregnated in the treatment solution, push with ironer, making wet pickup (wet pickup) is 40% (nylon), 60% (polyester/cotton blended fabric), in 100 ℃ of dryings 2 minutes, again in 160 ℃ of thermal treatments after 1 minute, the water and oil-resistant of Evaluation Division's removing the work.
Water-repellancy No. (with reference to following table 1) expression water-repellancy with the spray method of JIS-L-1092.
Drip and state the testing liquid shown in the table 2 at the local numbers that drip of test two on the cloth according to AATCC-TM118, observe the state that soaks into after 30 seconds, the vertex of the grease proofness of being given with the testing liquid that does not occur soaking into is as grease proofness.
Table 1
Water-repellancy No. State
5 The surface does not adhere to moistening
4 The faint adhesion in surface is moistening
3 Surface portion is moistening
2 Surface wettability
1 The surface is all moistening
Table 2
Grease proofness Testing liquid Surface tension (dyne/cm, 25 ℃)
8 Normal heptane 20.0
7 Octane 21.8
6 N-decane 23.5
5 N-dodecane 25.0
4 N-tetradecane 26.7
3 N-hexadecane 27.3
2 N-hexadecane 35/ whiteruss 65 mixing solutionss 29.6
1 Whiteruss 31.2
0 Do not reach 1 material -
This test of Bandaid
The dilute with water polymer dispersion liquid prepares treatment solution so that solid concentration is 0.6 weight %.Polyester/cotton blended fabric (twilled fabric, be unstained, mercerising yarn processing) (PET/C) is impregnated in the treatment solution, push with ironer, making wet pickup (wet pickup) is 60% (polyester/cotton blended fabric), in 100 ℃ of dryings 2 minutes, after 1 minute, estimate the outflow water yield of this processing cloth in 160 ℃ of thermal treatments again.
For flowing out the water yield, based on the outflow water yield (flow out the water yield, see through the water yield of handling cloth) of this test method determination of Bandaid after 10 minutes of DIN 53888.Flowing out the water yield is ideal less.
Sedimentation stability
With solid substance be 30 quality % composition of waterproofing and oil-proof agent in 40 ℃ leave standstill 1 month after, observe settled generation.Preferably there is not sediment.
Zero: do not have sediment fully
△: a small amount of sediment is arranged
*: a lot of sediments are arranged
Mechanically stable spare
It is 0.2 quality % that composition of waterproofing and oil-proof agent is diluted to solid concentration with tap water,, after 3000rpm stirs 10 minutes the scum silica frost that occurs is filled on the black cotton with the intimate mixing device.Preferably there is not scum silica frost.
Zero: do not have scum silica frost fully
△: a small amount of scum silica frost is arranged
*: a lot of scum silica frost are arranged
Chemical stability
It is 0.6 quality % that composition of waterproofing and oil-proof agent is diluted to solid concentration with tap water, to the dispersed dye that wherein add 0.006 weight %, observes the appearance of agglutinator behind the thorough mixing.Preferably there is not agglutinator.
Zero: do not have agglutinator to generate fully
△: agglutinator generates on a small quantity
*: agglutinator generates in a large number
Embodiment 1
Drop into the C of 38.1g 4F 9CH 2CH 2OCOC (CH 3)=CH 2(following note is 9FMA), 14.6g stearyl acrylate ester (following note is StA), 1.2g N hydroxymethyl acrylamide (following note is N-MAM), 0.6g methacrylic acid 3-chloro-2-hydroxy propyl ester (following note is CHPMA), 0.8g polyoxyethylene-polyoxypropylene alkyl oxide (nonionic surface active agent, HLB value 12) (Japanese grease (strain) make EBD-12), 3.0g polyoxyethylene sorbitan monolaurate (the HLB value is 17) (Japanese grease (strain) make LT-221), 1.4g palmityl trimethyl ammonium chloride (STMAC), the tripropylene glycol of 16g, the ion exchanged water of 70g, 0.03g lauryl mercaptan, 0.12g acetic acid.Be heated to 60 ℃, and with the intimate mixing device carry out pre-dispersed after, with ultrasonic emulsification machine emulsification 15 minutes.
Described emulsion is transferred in the four-hole boiling flask (having stirrer, prolong, thermometer, nitrogen ingress pipe) of 300ml, behind the nitrogen replacement, in 60 ℃ of polymerization starter azo diamidino propane dihydrochlorides that add 0.3g, initiated polymerization.In 60 ℃ stir 4 hours after, utilize GC to confirm that monomer disappears, obtain solid substance and be 40% aqueous dispersion.Dilute this aqueous dispersion with ion exchanged water, obtain solid substance and be 30% composition of waterproofing and oil-proof agent.The composition of polymkeric substance and the monomer of input are formed basically identical.
Characteristic to composition of waterproofing and oil-proof agent is estimated.The results are shown in Table 3.
Embodiment 2～5, comparative example 1～6
Operate with method similarly to Example 1, difference only is emulsifier type and amount to obtain solid substance thus and be 30% composition of waterproofing and oil-proof agent by changing shown in the table 3.For resultant composition, estimate each characteristic.The results are shown in Table 3.
Table 3
Emulsifying agent The HLB value Embodiment Comparative example
1 2 3 4 5 1 2 3 4 5 6
Nonionic surface active agent PP-40R(b1) LP-20R(b1) LT-221(b1) 7 9 17 3.0 3.0 3.0 0.8 3.0 0.8
EBD-12 (b2) EBD-9 (b2) EBD-4 (b2) BT-20 (b2) Pu Luolong 204 (b2) BO-20 (b2) BO-50 (b2) BS-20 (b2) 12 9 4 16 5 17 18 18 0.8 0.8 0.8 3.0 3.8 0.8 3.0 3.8 1.4 3.8 1.4
From the agent of face type table alive STMAC(b3) CPOEAC(b3) SPOEAS STDS 1.4 1.4 1.4 1.4 1.4 1.4 1.4 5.2 1.4 0.8 3.0
Water-repellancy Ny PET/C 5 4 5 4 5 4 5 4 5 4 5 3 5 3 5 2 5 2 1 2 1 2
Grease proofness Ny PET/C 2 4 2 4 2 4 2 4 2 4 2 2 2 1 1 2 1 2 0 0 0 0
This door of Bandaid flowed out the water yield (ml) after 10 minutes 9 8 5 7 8 52 36 37 48 343 288
Sedimentation stability mechanical stability chemical stability ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ △ △ × △ × × × △ × ○ △ × ○ ○ ○ ○
PP-40R: single palmitinic acid Isosorbide Dinitrate (Japanese grease (strain) manufacturing)
LP-20R: mono laurate Isosorbide Dinitrate (Japanese grease (strain) manufacturing)
LT-221: mono laurate Sorbitan ethoxylate (Japanese grease (strain) manufacturing)
EBD-12, EBD-9, EBD-4: polyoxyethylene polyoxy-propylene (Japanese grease (strain) manufacturing)
BT-20: the secondary alkyl oxide of polyoxyethylene (a day photochemistry (strain) is made)
BS-20: polyoxyethylene stearyl base ether (a day photochemistry (strain) is made)
BO-20, BO-50: polyoxyethylene oleyl ether (a day photochemistry (strain) is made)
Pu Luolong 204 (プ ロ ノ Application 204): polyoxyethylene polyoxypropylene block copolymer (Japanese grease (strain) manufacturing)
STMAC: stearyl trimethyl ammonium chloride
CPOEAC: Oleum Cocois alkyl two (polyoxyethylene) ammonio methacrylate
SPOEAS: Voranol EP 2001 sodium sulfate
STDS: tetradecene sodium sulfonate
Embodiment 6
Drop into the C of 32.7g 4F 9CH 2CH 2OCOC (CH 3)=CH 2(following note is 9FMA), 20.0g stearyl acrylate ester (following note is StA), 1.2g N hydroxymethyl acrylamide (following note is N-MAM), 0.6g methacrylic acid 3-chloro-2-hydroxy propyl ester (following note is CHPMA), 0.8g polyoxyethylene-polyoxypropylene alkyl oxide (nonionic surface active agent, HLB value are 9) (Japanese grease (strain) make EBD-9), 3.0g mono laurate Sorbitan ethoxylate (HLB value 17) (Japanese grease (strain) make LT-221), 1.4g palmityl trimethyl ammonium chloride, the tripropylene glycol of 16g, the ion exchanged water of 70g, 0.03g lauryl mercaptan, 0.12g acetic acid.Be heated to 60 ℃, and with the intimate mixing device carry out pre-dispersed after, with ultrasonic emulsification machine emulsification 15 minutes.
Described emulsion is transferred in the four-hole boiling flask (having stirrer, prolong, thermometer, nitrogen ingress pipe) of 300ml, behind the nitrogen replacement, in 60 ℃ of polymerization starter azo diamidino propane dihydrochlorides that add 0.3g, initiated polymerization.In 60 ℃ stir 4 hours after, utilize gas-chromatography (GC) to confirm that monomer disappears, obtain solid substance and be the aqueous dispersion of 40% polymkeric substance.Dilute this aqueous dispersion with ion exchanged water, obtain solid substance and be 30% composition of waterproofing and oil-proof agent.The composition of polymkeric substance and the monomer of input are formed basically identical.
Characteristic to composition of waterproofing and oil-proof agent is estimated.The results are shown in Table 4.
Embodiment 7～9, comparative example 7～8
Operate with method similarly to Example 6, difference only is monomeric kind and amount to obtain solid substance thus and be 30% composition of waterproofing and oil-proof agent by changing shown in the table 4.For resultant composition, estimate each characteristic.The results are shown in Table 4.
Embodiment 10
The polymkeric substance that comprises vinylchlorid:
Drop into the C of 87.2g 4F 9CH 2CH 2OCOC (CH 3)=CH 2(following note is 9FMA), 11.3g stearyl acrylate ester (following note is StA), 2.8g N hydroxymethyl acrylamide (following note is N-MAM), 0.7g methacrylic acid 3-chloro-2-hydroxy propyl ester (following note is CHPMA), 2.1g single palmitinic acid Isosorbide Dinitrate (nonionic surface active agent, HLB value 7) (Japanese grease (strain) make PP-40R), 2.1g polyoxyethylene oleyl ether (HLB value 18) (day a photochemistry (strain) make BO-50), 6.4g polyoxyethylene polyoxypropylene cetyl ether (HLB value 13) (day a photochemistry (strain) make PBC-44), 2.3g VARISOFT TA100 (cationic surfactant), 272.3g ion exchanged water, 0.5g lauryl mercaptan, 0.7g acetic acid.Be heated to 60 ℃, and with the intimate mixing device carry out pre-dispersed after, with ultrasonic emulsification machine emulsification 15 minutes.
Described emulsion is transferred in the 1000ml autoclave (having stirrer, thermometer, nitrogen ingress pipe), behind the nitrogen replacement, dropped into the vinylchlorid of 33.0g.Add the polymerization starter azo diamidino propane of 1.0g. dihydrochloride, be heated to 60 ℃ after, initiated polymerization.
After 4 hours, discharge unreacted vinyl chloride monomer in 60 ℃ of reactions.The reactivity of vinyl chloride monomer is 80%.Utilize GC, confirmed that other monomers disappear, obtain solid substance and be 32% aqueous dispersion.Dilute this aqueous dispersion with ion exchanged water, obtain solid substance and be 30% composition of waterproofing and oil-proof agent.
For resultant composition, estimate each characteristic.The results are shown in Table 4.
Embodiment 11～14
Operate with method similarly to Example 10, difference only is monomeric kind and amount to obtain solid substance thus and be 30% composition of waterproofing and oil-proof agent by changing shown in the table 4.For resultant composition, estimate each characteristic.The results are shown in Table 4.
Table 4
Monomer Embodiment Comparative example
6 7 8 9 10 11 12 13 14 7 8
Fluorochemical monomer 9FMA(a1) 13FMA(a1) 9FA(a1) 9FCA(a1) 13FCA(a1) 32.7 32.7 38.1 30.5 7.6 34.8 34.8 34.8 34.8 34.8 32.7 32.7
Comonomer StA(a2) TCDA(a2) VCl(a2) LA 2EHA BuA N-MAM(a3) CHPMA(a3) Tm＝56℃ Tg＝120℃ Tg＝81℃ Tg＝3℃ Tg＝50℃ Tg＝54℃ 20.0 1.2 0.6 20.0 1.2 0.6 14.6 1.2 0.6 14.6 1.2 0.6 47 13.2 1.2 0.6 4.7 13.2 1.2 0.6 10.5 7.4 1.2 0.6 13.2 4.7 1.2 0.6 4.7 13.2 1.2 0.6 20.0 1.2 0.6 20.0 1.2 0.6
Water-repellancy Ny PET/C 5 4 5 5 5 5 5 5 5 4 5 5 5 5 5 5 5 5 3 2 2 1
Grease proofness Ny PET/C 2 4 4 6 4 5 4 5 4 5 4 6 4 6 4 6 4 6 1 2 0 1
This door of Bandaid flowed out the water yield (ml) after 10 minutes 13 7 7 8 9 6 8 5 7 86 163
Sedimentation stability mechanical stability chemical stability ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○
9FMA：C 4F 9CH 2CH 2OCOC(CH 3)＝CH 2
13FMA：C 6F 13CH 2CH 2OCOC(CH 3)＝CH 2
9FA：C 4F 9CH 2CH 2OCOCH＝CH 2
9FCA：C 4F 9CH 2CH 2OCOCCl＝CH 2
13FCA：C 6F 13CH 2CH 2OCOCCl＝CH 2
StA: stearyl acrylate ester
TCDA: vinylformic acid three ring decyl ester
VCl: vinylchlorid
LA: lauryl acrylate
2EHA: 2-EHA
BuA: n-butyl acrylate
The N-MAM:N-n-methylolacrylamide
CHPMA: methacrylic acid 3-chloro-2-hydroxy propyl ester
Embodiment 15
The solid substance that dilute with water embodiment 6 obtains is 30% composition of waterproofing and oil-proof agent, and the formation solid substance is 0.45% processing bath.Use this processing to bathe, estimate water-repellancy, grease proofness, this outflow water yield of Bandaid similarly to Example 6.The results are shown in Table 5.
Embodiment 16
The solid substance that dilute with water embodiment 6 obtains is 30% composition of waterproofing and oil-proof agent, making solid substance is 0.45%, and add 0.3% melamine resin (Sumitomo Chemical manufacturing therein, Sumitex resin M-3), (the Sumitomo Chemical manufacturing of 0.1% catalyzer, Sumitex Accelerator ACX), making processing bathes.Use this processing to bathe, estimate water-repellancy, grease proofness, this outflow water yield of Bandaid similarly to Example 15.The results are shown in Table 5.
Embodiment 17
The solid substance that dilute with water embodiment 6 obtains is 30% composition of waterproofing and oil-proof agent, and making solid substance is 0.45%, and adds 0.5% end-blocking isocyanate crosslinking (the first industrial pharmacy manufacturing, Elastron BN-69) therein, makes to handle and bathes.Use this processing to bathe, estimate water-repellancy, grease proofness, this outflow water yield of Bandaid similarly to Example 15.The results are shown in Table 5.
Table 5
Embodiment
15 16 17
The composition of waterproofing and oil-proof agent of composition of waterproofing and oil-proof agent embodiment 6 1.5 1.5 1.5
Linking agent and catalyzer melamine resin (M-3) catalyzer (ACX) end-blocking isocyanic ester (BN-69) - - - 0.3 0.1 - - - 0.5
Dilution water 98 97.6 97.5
Water-repellancy Ny PET/C 5 4 5 4 5 4
Grease proofness Ny PET/C 2 4 2 4 2 4
This door of Bandaid flowed out the water yield after 10 minutes 16 6 8

Claims (10)

1. aqueous water-and-oil repellant composition, said composition comprises following fluorinated copolymer (A), tensio-active agent (B) and aqueous medium (C);
Wherein, described fluorinated copolymer (A) comprises following polymerizable monomer (a1) and polymerizable monomer (a2), and also comprises following polymerizable monomer (a3) as required, and the amount of described polymerizable monomer (a1) is more than the 20 weight % with respect to this multipolymer;
Described (a1) is 1～6 the perfluoroalkyl or the polymerizable monomer of perfluoro alkenyl for having carbonatoms;
Described (a2) be can with the polymerizable monomer of (a1) copolymerization, the glass transition temperature Tg of its homopolymer be more than 50 ℃ and/or fusing point Tm be more than 30 ℃;
Described (a3) is for containing the polymerizable monomer of polar group or reactive group;
Described tensio-active agent (B) is nonionic surface active agent (b1), and this nonionic surface active agent (b1) is Isosorbide Dinitrate and/or its epoxide affixture;
Described aqueous medium (C) is the medium that only contains water, or is the medium that contains the mixture of water and organic solvent.
2. aqueous water-and-oil repellant composition as claimed in claim 1, in the wherein said fluorinated copolymer (A), (a1) ratio is 40 weight %～95 weight %, and ratio (a2) is 5 weight %～60 weight %, and ratio (a3) is 0 weight %～15 weight %.
3. aqueous water-and-oil repellant composition as claimed in claim 1, wherein said nonionic surface active agent (b1) is for being selected from by the mono laurate Isosorbide Dinitrate, the Stearinsaeure Isosorbide Dinitrate, single palmitinic acid Isosorbide Dinitrate, single oleic acid Isosorbide Dinitrate, sesquialter stearic acid Isosorbide Dinitrate, three stearic acid Isosorbide Dinitrate, the mono laurate Sorbitan ethoxylate, single palmitinic acid Sorbitan ethoxylate, the Stearinsaeure Sorbitan ethoxylate, at least a tensio-active agent in the group that single oleic acid Sorbitan ethoxylate and three stearic acid polyoxyethylene Isosorbide Dinitrate are formed.
4. aqueous water-and-oil repellant composition as claimed in claim 1, wherein said tensio-active agent (B) also contains (b2) Isosorbide Dinitrate and epoxide affixture thereof nonionic surface active agent (b2) and/or cationic surfactant (b3) in addition except that containing nonionic surface active agent (b1).
5. aqueous water-and-oil repellant composition as claimed in claim 4, wherein said nonionic surface active agent (b2) are selected from by straight chain shape and/or catenate is saturated and/or the epoxide affixture of unsaturated aliphatic base, straight chain shape and/or a catenate are saturated and/or the epoxide affixture of polyalkylene glycol ester, polyoxyethylene (POE)/polyoxypropylene (POP) multipolymer and the acetylenediol of unsaturated fatty acids is formed group.
6. aqueous water-and-oil repellant composition as claimed in claim 4, wherein said cationic surfactant (b3) is an ammonium salt.
7. aqueous water-and-oil repellant composition as claimed in claim 4, wherein said cationic surfactant (b3) is a general formula R 1 p-N +R 2 qX -The ammonium salt of expression is at general formula R 1 p-N +R 2 qX -In:
R 1The expression carbonatoms is a straight chain shape and/or the saturated and/or undersaturated fatty group of catenate more than 12,
R 2Expression H or expression carbonatoms are 1～4 alkyl, benzyl, polyoxyethylene,
X represents that halogen, carbonatoms are 1～4 lipid acid alkali,
P represents 1 or 2, and q represents 2 or 3, and p+q=4.
8. aqueous water-and-oil repellant mixture, it contains each described composition of waterproofing and oil-proof agent of claim 1～7 and contains linking agent.
9. the treatment process of an object being treated, this treatment process comprises the step of object being treated being handled with each described aqueous water-and-oil repellant composition in the claim 1～7 or the described aqueous water-and-oil repellant mixture of claim 8.
10. object being treated, this object being treated obtains by the described treatment process of claim 9.
CN 200580027829 2004-08-25 2005-08-02 Water-repellent/oil-repellent composition Pending CN101006149A (en)

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