CN1077935C - Aqueous oil and water repellent compositions - Google Patents
Aqueous oil and water repellent compositions Download PDFInfo
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- CN1077935C CN1077935C CN95193390A CN95193390A CN1077935C CN 1077935 C CN1077935 C CN 1077935C CN 95193390 A CN95193390 A CN 95193390A CN 95193390 A CN95193390 A CN 95193390A CN 1077935 C CN1077935 C CN 1077935C
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Abstract
The present invention discloses an oil-proof and water-proof composition for processing a base material such as cloth, etc. containing fiber products, a base material processed by the composition and a method for processing the base material. The composition of the present invention comprises polyalkaoxylated polyurethane (a), fluorous contained acrylate polymers(b), fluorous contained acrylic acid polyalkylene glycol ester copolymers (c) and fluorous contained adipic acid ester (d), wherein the fluorous contained acrylate polymers contain fluorous contained acrylate or methacrylate ester monomers, at least one kind of acrylic acid octadecy l phosphite or alkyl methacrylate monomers and polymeric reaction products of polymerisable cationic emulsifiers containing quaternary amine surface active agents. The components are mixed together according to the weight ratio of (a): (b) or (a) +(c): (b) or (a) +(c) +(d): (b) of 19: 1-1: 19, particularly the weight ratio of (a): (b) or (a) +(c): (b) or (a) +(c) +(d): (b) of 1: 1. The composition can be applied to different base materials containing fiber products to obtain extensive oil-proof performance and water-proof performance.
Description
The present invention relates to be used under environmental condition, handling the grease proofing and water-proofing composition of fabric and other fibre-bearing product substrate, and relate to the method for treated base material and these base materials of processing.
The background of invention
After the use of a period of time, base material (as woven fabric, carpet, cover, pad etc.) is understood dirty and is tarnished, and often needs and repeated washing.Propose many Chemical composition thats already and be used to protect this base material to avoid water-based and oiliness to stain and/or tarnish, and in patent documentation, also described many this compositions.For example, the inventory and the description of the patent documentation of the composition that partly relates to the fluorochemical that is used to handle textiles etc. have been comprised in people's such as Smith the United States Patent (USP) 5,350,795.Pointed as patent documentation, successfully used fluorochemical to handle various base materials already, make base material prevent from better to tarnish, and easier washing.
Although find that fluorochemical has purposes quite widely, fluorochemical need comprise the unwelcome often organic solvent that use is a large amount of usually.Use aqueous fluorine-containing compound composition (as the sort of composition that does not contain a large amount of organic solvents) although be more welcome, but not too satisfactory, because needing additional step just can be applied on the base material usually, this waterborne compositions (is applied on the base material) as heat.From above-mentioned, need a kind of the grease proofing of a large amount of organic solvents and waterproof fluorochemical composition of not needing of exploitation, this composition can be applied on the base material under environmental condition and be dry under environmental condition, makes base material have grease proofing and water proofing property.
For estimating the grease proofing and water proofing property of treated base material, use some known test methods to measure effective waterproof of base material and grease proofing degree under different condition.On a series of different base materials (as different fabric type), any given composition is carried out identical test to estimate the significant degree of said composition protection certain material all sidedly.Found that, although some fluorochemical composition can obtain good or acceptable result of the test at least according to above-mentioned test method, this technology can't provide the composition that does not contain organic solvent substantially (and the latter can provide a series of improved grease proofing and water proofing properties).Therefore, need a kind of composition that is suitable for handling the fibre-bearing product substrate of exploitation, and preparation and need not a large amount of organic solvents when applying said composition, said composition can provide a series of improved grease proofing and water proofing properties (just can at room temperature use as the heat treatment that said composition does not need to add) under environmental condition.
The summary of invention
The invention provides a kind of base material (for example fabric and Textile Fibre Product (comprising cotton, nylon, polyester, polyolefin, acrylic acid, acetate, leather or its blend)) and clothes that are suitable at various fibre-bearing goods, the fluorochemical composition that uses on cover, pad and the carpet material makes described material have grease proofing widely and water proofing property.The present composition is an aqueous formulation; can be applied directly to not dry on the base material (i.e. dry getting final product under environmental condition) by heat treatment; the applicant finds and a kind of fluorinated acrylate polymer blending that is mixed with the polymerizable cationic emulsifier can be protected composition to form a kind of fabric to the blend that contains polyurethane that this composition has improved grease proofing and water proofing property.
On the other hand, the invention provides the composition that a kind ofly is used to handle the fibre-bearing product substrate, gives the grease proofing and water proofing property of base material, said composition comprises:
(a) a kind of polyurethane with poly-alkoxylation of perfluoroalkyl side group, the poly-hydrogen ester of described poly-alkoxylation comprise aliphatic series or aromatics trimerization or more isocyanates, fluorine-containing alcohol, amine or the mercaptan of poly and the product of poly-(oxyalkylene) glycol or two coloured glaze alcohol;
(b) a kind of fluorinated acrylate polymer, it comprises fluorinated acrylate or methacrylate monomers, at least a alkyl acrylate or alkyl methacrylate monomer and a kind of product that contains the polymerizable cationic emulsifying agent of quaternary amine surfactants.
Composition directly also contains (c) a kind of fluorine-containing aklylene glycol ester polymer, it comprises fluorinated acrylate or methacrylate monomers, the product of polyacrylic acid alkylidene diol ester or polymethylacrylic acid alkylidene diol ester (polyalkylene glycol acrylate or methacrylate) and poly-diacrylate alkylidene diol ester or poly dimethyl acrylic acid alkylidene diol ester.In composition of the present invention, also can randomly comprise (d) fluorine-containing adipate ester, said components is with (a): (b), or (a)+(c): (b), or (a)+(c)+(d): be 25 (b): 1-1: 25 weight ratio, the weight ratio that is preferably 1: 1 is blended together in composition.
Fluorochemical acrylate polymer can be by following general formula:
Wherein: R
fIt is fluorine-containing aliphatic group;
Q is organic linking group;
R
bAnd R
b' be identical or different, be selected from H and have the straight or branched alkyl of 1-4 carbon atom or the carbon ring group of formation about 3-12 carbon atom together, and composition thereof;
R
d, R
d', R
d", R
d" ' can be identical or different, be selected from H or-CH
3
R
a, R
a', R
a" can be identical or different, be selected from alkyl with 1-18 carbon atom;
R
cBe saturated aliphatic series (straight or branched) base or cycloalkyl, or cycloalkyl and have the combination of the aliphatic alkyl of (have 4-30 usually, preferably have a 8-20) carbon atom at least;
Z is an anion, is selected from chlorine, bromine, iodine, sulfonate radical, alkyl azochlorosulfonate, phosphate radical etc., and composition thereof;
n
1, n
2, n
3Be respectively the number of 10-70;
n
4Be to be at least 1, be generally the number of 1-6.
The present composition preferably only contains the water-based emulsion of a small amount of organic solvent.Except said components, composition can also comprise pH regulator agent and corrosion inhibitor.Can waterborne compositions of the present invention be used with the form of spraying by adding spray (for example iso-butane).
In description of the invention, used some term, its meaning is defined as follows: " environmental condition " is meant common room temperature and humidity and do not use extra heat treatment and/or drying equipment." base materials of fibre-bearing goods " or " base material " refer to fabric, Textile Fibre Product or long filament, by cotton, polyester, polyolefin, nylon, acrylic acid, acetate, and product and clothes, cover for furniture, pad and carpet that the fabric that leather and blend thereof form is made." polymerisable emulsifying agent " refers to that the while is as a kind of quaternised organic salt of monomer reactant and stabilizing agent in emulsion polymerisation.Except as otherwise noted, the meaning of " stabilizing agent ", " emulsifying agent ", " surfactant " is identical and replaceable use.When describing acrylate and methacrylate compound, acrylate and these two species of methacrylate are represented with term " (methyl) acrylic acid " together.
On the other hand, the invention provides a kind of method of handling base material, making it to have grease proofing and water proofing property, comprise with the present composition and handle base material and dry treated base material, more on the one hand, the invention provides and a kind ofly have grease proofing and base material water proofing property through what the present composition was handled.
After having studied the following content of the present invention (comprising the detailed description of better example and additional claim), the those of skill in the art in this area will be expressly understood details of the present invention.
The detailed description of better example
The composition of fluorochemical of the present invention is to be the blend of base with water, and can as described belowly be applied on the various base materials under environmental condition, makes base material have anti-widely Shan and water resistance.As described below, when describing preferably example of the present invention, with the component out of the ordinary of discussing respectively and describing in the composition.Fluorine-containing industry alkyl diol ester polymer
The present composition comprises fluorine-containing aklylene glycol ester polymer " or fluorine-containing industry alkyl diol ester ", it comprises fluorinated acrylate or methacrylate monomers, the product of polyacrylic acid alkylidene diol ester or polymethylacrylic acid alkylidene diol ester monomer and poly-diacrylate alkylidene diol ester or poly dimethyl acrylic acid alkylidene diol ester monomer.The fluorine-containing alkylidene diol ester is present in the best example of the present invention, so as to add to during at a small amount of co-solvent, especially at preparation spraying blend corrosion inhibitor in the composition in the presence of, make composition remain stable.Fluorine-containing industry alkyl diol ester also helps the moistening base material of the present composition.The fluorochemical acrylate polymer of Shi Yonging is disclosed in the present invention, and for example United States Patent (USP) 5,350,795 (people such as Smith), 3,787,351 (Olson) and 4,795,793 (people such as Amimoto), and all these is listed in this and draws and be reference.
The fluorine-containing alkylidene diol ester has the repetitive of following random arrangement preferably:
Wherein, R
fBe fluorine-containing aliphatic group, R
3Be H or CH
3, R
4Be the alkylidene with 2-4 carbon atom, Q is organic connection base, and X is at least 5, and 10-75 normally can be up to 100 integer.
Fluorine-containing aliphatic group (R
f) be stablize, inertia, nonpolar, preferably saturated univalent perssad, and have oleophobic and hydrophobicity simultaneously.The acrylic acid alkylidene diol ester should comprise 2-25 R
fGroup, and should comprise about 5-30%, the fluorine of preferably about 8-20 weight % (by the gross weight of oligomer), wherein fluorine-based at R
fIn the group.R
fShould contain at least 3 carbon atoms, better contain 3-25 carbon atom, preferably contain 6-12 the carbon atom of having an appointment, R
fWhat can contain straight chain, side chain or ring-type contains fluoroalkyl or its combination, the combination of perhaps above-mentioned group and straight chain, side chain or cyclic alkyl.R
fPreferably do not contain polymerisable unsaturated ethylene linkage, but can randomly contain the hetero atom (as oxygen, sulphur two valencys or sexavalence or nitrogen) that connects usefulness.Each R
fShould contain the 40-78 weight % that has an appointment, the fluorine of preferably about 50-78 weight %.R
fThe end of group contains an end group of fluoridizing fully.End group preferably contains at least 7 fluorine atoms, i.e. CF
3CF
2CF
2-, (CF
3)
2CF-,-CF
2SF
5-etc.Preferred R
fBe the perfluorinate aliphatic group, promptly its general formula is C
nF
2n+1
Fluorine-containing aliphatic group (R
f) be connected on the ester group by connecting basic Q.Connecting base can be a covalent bond, hetero atom (as O or S) or organic group.Q preferably contains the organic group of 1-20 carbon atom, and randomly contain oxygen, nitrogenous or sulfur-containing group or its combination, and preferably not containing meeting disturbs the functional group of radical polymerization (as the two keys of polymerisable alkene, mercaptan, hydrogen atom that easily picked-off such as cumenyl hydrogen atom, and this type of degree of functionality of other known to the those of skill in the art in this area).Be suitable for comprising the alkylidene, arlydene, inferior aralkyl, oxo of straight chain, side chain or ring-type-(oxy), oxo bridge (oxo), sulphur, sulfonyl, sulfinyl, imino group, sulfonamido, amido link (carboxamido), ketonic oxygen base as the example of structure that connects basic Q; imino group Ethyl formate, 1, the 3-urylene, with and the combination as the sulfonamido alkyl.Connecting basic Q preferably can be according to being easy to preparation and can commercially availablely buying to principle and select it.Be the representative inventory of the suitable organic Q group of part below, for the purpose of tabulation, each k is respectively the integer of 1-20, and g is the integer of 0-10, and h is the integer of 1-20, and R is the alkyl of hydrogen, a phenyl or 1-4 carbon atom, and R is the alkyl of 1-20 carbon atom.
-SO
2NR’(CH
2)
k-
-CONR’(CH
2)
k-
-(CH
2)
kO(O)C-
-CH
2CH(OH)CH
2-
-CH
2CH(OR”)CH
2-
-(CH
2)
kC(O)-
-(CH
2)
kSC(O)-
-(CH
2)
kO(CH
2)
k-
-(CH
2)
kS(CH
2)
k-
-(CH
2)
k(OCH
2CH
2)
k-
-(CH
2)
kSO
2(CH
2)
k-
-SO
2NR(CH
2)
kO(CH
2CH
2)
k-
-(CH
2)
kSO
2NR(CH
2)
k-
-(CH
2)
kSO
2-
-SO
2NR’(CH
2)
k-
-OC
6H
4CH
2-
-(CH
2)
kO((O)C(CH
2)
6O)
gC(O)(CH
2)
6-
-(CH
2)
kO((O)C(CH
2)
6NH)
gC(O)(CH
2)
6NHC(O)-
-C(O)O(CH
2)
2OC(O)NH(CH
2)
2-
In order to connect R
f, Q is alkylidene, sulfonamido or sulfonamido alkylidene preferably.
At polyoxyalkylene (OR
4)
xIn, R
4Be alkylidene with 2-4 carbon atom, as-CH
2CH
2-,-CH
2CH
2CH
2-,-CH (CH
3) CH
2-,-CH (CH
3) CH (CH
3)-, in the oxyalkylene group unit in the polyoxyalkylenes can be identical (as in the polypropylene oxide), it maybe can be a kind of mixture, as in ethylene oxide straight or branched or random or the propylene oxide unit, perhaps as in the straight or branched of the block of the block of ethylene oxide unit and propylene oxide unit.Can comprise one or more stretched wire keys (catenary linkages) in the polyoxyalkylene chain or interrupted that although this key does not preferably contain the active function groups with active hydrogen atom, the solubility that makes this key not change poly-epoxidation alkene chain is authorized characteristic by it.The term of Shi Yonging " active hydrogen atom " refers to can cause the hydrogen atom (hydrogen atom that is different from acid amides) of chain transfer or chain termination in radical polymerization in this application.When stretched wire be trivalent or during multivalence, they provide the means that make oxyalkylene units obtain side chain.
Polyoxyalkylenes in oligomer can be identical or different, and can hang and connect.Be about 500-5000 or higher with the appropriate to the occasion molecular weight of polyoxyalkylenes that makes, promptly 100,000 or higher, be preferably 2000-4000, with the solubility that obtains to require.
Fluorine-containing aklylene glycol polymer can make with poly-single acrylic acid oxyalkylene group ester, diacrylate oxyalkylene group ester or its mixture copolymerization by the acrylate of the fluorine-containing aliphatic group that causes as free radical, can be by the concentration and temperature of regulating initiator concentration and activity, monomer and the molecular weight that passes through chain-transferring agent (as mercaptan, as n-octyl mercaptan) control perfluoroalkyl acrylate aklylene glycol polymer.Acrylic acid fluorine lipidol ester (described in above-mentioned preparation) is well-known (for example, can referring to United States Patent (USP) 2,803,615,2,642,416,2,826,564,3,102,103,3,282,905,3,304,278) in the art.The polyacrylic acid oxyalkylene ester that is used for above-mentioned preparation can be reacted in known manner with acrylic acid, methacrylic acid, acryloyl chloride or acrylic anhydride by commercially available hydroxyl and alkoxyl polyoxyalkylene sill (for example being called the commodity of " PLURONIC " (available from New Jersey BASF Corp.ofParsipanny), the commodity of " CARBOWAX " and " TRITON " (available from Union Carbide Corp) by name) with other acrylate and make.
Other be suitable for the preparation (for example by several undersaturated comonomers of hot ethylene linkage that contain polyoxyalkylene accordingly of copolymerization) polymer of the present invention contain fluorine-containing aliphatic group, end group is the monomer of unsaturated ethylene linkage, be well known in the art (for example, can be referring to United States Patent (USP) 2,592,069,2,995,542,3,078,245,3,081,274,3,291,842 and 3,325,163; The unsaturated material of ethylene linkage that is suitable for forming fluorine-containing aliphatic group construction unit is disclosed in United States Patent (USP) 3,574, in 791), fluorine-containing aklylene glycol ester polymer also can randomly contain the unit from other monomer (as alkyl acrylate, vinyl chloride and N hydroxymethyl acrylamide).
A kind of fluorine-containing alkylidene diol ester of polyethoxylated preferably is the polyoxyethylated trimer of following compounds:
C
8F
17SO
2N(CH
3)C
2H
4OCOCH＝CH
2， (a)
CH
2＝C(CH
3)COO(CH
2CH
2O)
76H， (b)
With
CH
2＝C(CH
3)COO(CH
2CH
2O)
76COC(CH
3)＝CH
2， (c)
A preferably: weight ratio (b+c) is 1: 1, and the weight ratio of b: c is the polyurethane of 3: 1 poly-alkoxylations
The present composition comprises a kind of polyurethane (below abbreviate polyurethane as) of poly-alkoxylation, this polyurethane should have the outstanding fully-fluorinated group that connects and comprise by the aliphatic trimerization or the isocyanates of poly more, the product that fluorine-containing alcohol, amine or mercaptan and polyoxyalkylene diols or two mercaptan generate.The scope of the polyurethane that can use in the present composition is same as the scope that is disclosed in the above-mentioned United States Patent (USP) 5,350,795 (people such as Smith), and can be expressed from the next:
Wherein: R
fIt is fluorine-containing fat-based;
R
hIt is not fluorine-containing alkyl;
Q is organic connection base;
A is trimerization or poly isocyanate group more, promptly trimerization or more poly isocyanate partly deduct active-group that the NCO base forms;
(R
1)
yBe the polyoxyalkylene segment, R
1Be the oxyalkylene group with 2-6 carbon atom, perhaps have the cyclic ethers or the ester moiety of 2-6 carbon atom, y is the number of 10-50;
X is O, S or is that the connection base of end is (as-CH with O or S
2CH
2O);
R
2Be trimerization or poly isocyanate base more, this trimerization or more two isocyanate group of poly isocyanate form described polyurethane-base, other isocyanates radical reaction formation-QR
fOr-QR
hSide group;
S is at least 1, can be 3 or bigger number;
Z is 0 or high to about 4 number;
S+z is about 4 or bigger number;
T is at least 10, is preferably the number of 15-35.
It is about 40,000 that the weight average molecular weight of the polyurethane of poly-alkoxylation is at least usually, preferably about 65,000-250,000.
In above-mentioned polyurethane preferably, have many identical or different Rf bases.Many Q, A, R are also arranged
1And R
2Group.The Polyurethane of poly-alkoxylation contains the 5-40 weight % that has an appointment usually, preferably about 10-30 weight % with the carbon atom fluorine of bonding mutually.If fluorine content less than about 10 weight %, then needs the big not polymer of the amount of gearing to actual circumstances that gets usually,, be difficult in the present composition, use effectively if fluorine content greater than about 35 weight %, can make the solubility of polymer too little usually.
In above-mentioned polyurethane, randomly contain not fluorine-containing alkyl R
hAt one preferably in the example, z 0 (does not comprise R as this polyurethane
hGroup).But contain R
hDuring group, it can be the alkyl of straight chain, side chain or ring-type, R
hPreferably do not contain polymerisable unsaturated ethylene linkage but can randomly contain hetero atom such as oxygen, divalence or the sexavalence sulphur or the nitrogen of side joint, not fluorine-containing alkyl also can randomly contain epoxy or aziridine degree of functionality.Not fluorine-containing alkyl should contain 1-36 carbon atom, preferably contains 10-24 carbon atom.
In polyoxyalkylenes, R
1 y, R
1Be oxyalkylene group with 2-4 carbon atom, as-OCH
2CH
2-,-OCH
2CH
2CH
2-,-OCH (CH
3) CH
2-,-OCH (CH
3) CH (CH
3The oxyalkylene group unit of)-, in polyoxyalkylenes can be identical, as in the poly(propylene oxide); Or different, as in the mixture of oxirane straight or branched or random and propylene oxide units, or as in the polymer segments of the polymer segments of the ethylene oxide unit of straight or branched and propylene oxide units.One or more stretched wire keys (catenary linkages) can cut off or be included in the polyoxyalkylene chain, this stretched wire can be trivalent or multivalence, they provide the means that obtain side chain or oxyalkylene units.The molecular weight of polyoxyalkylenes can be 750-2000, is preferably 900-1750.
The residue R of the isocyanates more than three or three
2Can be by such isocyanate compound, as polyaromatic polyisocyanate (" Papi ", as commodity available from " VORANATE " M220 by name of Michigan State Dow Chemical Co.of Midland, or available from " DESMODUR " N-100, " DESMODUR " N-3200 and " DESMODUR " N-3300 of New York Farbenfabriken Bayer AG ofNewYork) form.
Can use known method preparation to be used for the oxyalkylene polyurethane with fluorine-containing aliphatic group of the present invention, as can use solution, suspension or bulk polymerization technology by equal polycondensation or copolymerization it (referring to, as PreparativcMethods of Polymer Chemistry, Sorenson and Campbell, 2nd ed., IntersciencePublishers (1968)).As in this area those of skill in the art understood, also other fluorochemical urethane can be used for the present composition.The detailed description of useful fluorine-containing oxyalkylene can referring to, for example United States Patent (USP) 3,787,351 and 4,289,892.Fluorinated acrylate polymer with polymerisable emulsifying agent
But the present composition also comprises the fluorinated acrylate polymer of the surfactant that is mixed with copolymerization.The polymeric reaction product of fluorinated acrylate polymer preferably fluorine-containing (methyl) acrylate monomer, at least a (methyl) alkyl acrylate monomer and polymerizable cationic emulsifying agent (comprising quaternary amine surfactants).
A kind of fluorinated acrylate polymer is preferably represented by following general formula:
Wherein: R
fIt is aforesaid fluorine-containing aliphatic group;
Q is aforesaid organic linking group;
R
bAnd R
b' be identical or different, be selected from H and have 1-4 carbon atom straight chain or branched hydrocarbyl or the carbon ring group of the about 3-12 of a formation carbon atom together, and composition thereof;
R
d, R
d', R
d", R
d" ' can be identical or different, be selected from H or-CH
3
R
a, R
a', R
a" can be identical or different, be selected from alkyl with 1-18 carbon atom;
R
cBe saturated aliphatic series (straight or branched) or cyclic alkyl, or cycloalkyl and have at least
The combination of the aliphatic alkyl of (have 4-30 usually, preferably have 8-20) carbon atom;
Z is an anion, is selected from chlorine, bromine, iodine, sulfonate radical, alkyl azochlorosulfonate, phosphate radical etc., and composition thereof;
n
1, n
2, n
3Be respectively 10-70 number;
n
4Be to be at least 1, be generally 1-6 number.
At one preferably in the example of the present invention, fluorinated acrylate polymer can be expressed from the next:
As mentioned above, R
d, R
d', R
d", R
d" ' can be identical or different, be selected from H or-CH
3, so that acrylate and methacrylate all can be used as the monomer of above-mentioned fluorinated acrylate polymer.Be used for suitable fluorine-containing (methyl) acrylate monomer of the present invention and be selected from (methyl) acrylic acid (N-methyl perfluoro capryl sulfonamido) ethyl ester, (methyl) acrylic acid (N-ethyl perfluoro capryl sulfonamido) ethyl ester etc.Fluorine-containing (methyl) acrylate monomer is (methyl) acrylic acid (N-methyl perfluoro capryl sulfonamido) ethyl ester preferably.In final copolymer, fluorine-containing (methyl) acrylic monomers accounts for 15-40 moles of %, preferably accounts for 20-30 moles of % (by the sum of polymerizable species in the final copolymer).
Fluorinated acrylate polymer is made by at least a (methyl) alkyl acrylate monomer.Use two kinds of (methyl) alkyl acrylate monomers when being preferably in this polymer of preparation.Suitable (methyl) alkyl acrylate monomer is alkyl R wherein
aOr R
a' be selected from C respectively
1-C
18The alkyl acrylate or the alkyl methacrylate of alkyl (this alkyl can be the alkyl of straight chain, side chain, ring-type or the many rings in above-mentioned carbon atom number range).(methyl) alkyl acrylate is selected from methyl acrylate, ethyl acrylate, butyl acrylate, Hexyl 2-propenoate, Isooctyl acrylate monomer, isodecyl acrylate, acrylic acid octadecane ester, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate and composition thereof preferably, best (methyl) alkyl acrylate monomer comprises a kind of alkyl acrylate and a kind of alkyl methacrylate, preferably n-butyl acrylate and n-BMA.
The polymerizable cationic emulsifying agent is a kind of quaternary amine surfactants, and it can carry out Raolical polymerizable with one or more monomers that is used for synthetic fluorinated acrylate polymer.Emulsifying agent preferably contains the two keys of at least one carbon one carbon, and its position makes this pair bond energy participate in Raolical polymerizable (for example this pair key should be no steric hindrance) on three-dimensional and electron configuration.But the cationic emulsifier of copolymerization preferably has the quaternary amine of the alkyl acrylate of following general formula:
R wherein
a", R
b, R
b', R
c, R
d" ' with Z with top described the same.
But the cationic emulsifier of copolymerization preferably includes methacrylic acid N, N-dimethylamino ethyl ester and have about 4-30 carbon atoms, preferably a product of the alkyl halide of 8-12 carbon atoms.Alkyl halide is a bromohexadecane preferably, because it can be buied from market and it is operated when the preparation Emulgating polymers easily.Other quaternary amine of top general formula is described in United States Patent (USP) (U.S.Letters Patent) 3,780,092; 3,928,423; 3,936,492 and 4,001,259, the disclosed content of these patents is listed in this as a reference.But the preferably about 0.5-10% of the content of the cationic emulsifier of copolymerization (by the gross weight of other monomer in the fluorinated acrylate polymer), preferably about 2-6%.
Quaternary ammonium salt can be prepared as follows: at first make methacrylic acid N, N-dimethylamino ethyl ester and alkyl halide react according to following general preparation process A.Make emulsifying agent and other monomer carry out emulsion polymerisation subsequently.Water, fluorochemical monomer, alkyl methacrylate monomer and surfactant are mixed thoroughly with known method (as 55-70 ℃) under heating up.Then, in blanket of nitrogen, use water-soluble radical initiator to handle emulsion.Preferably initator is added to and makes initiator concentration reach about 0.05-2% in the emulsion, preferably reach 0.1-0.5% (by the gross weight of monomer in the emulsion).The selection of suitable initator is that those skilled in the art are known.Suitable initator comprises 2,2 '-azo is two-and (2-cyano group third-1-sulfonate), two hydrochloric acid 2,2 '-azo is two-and (2-amidine propane), α, two hydrochloric acid fourth amidines (bis-butyramidinium) of α-azo and azo be two-(N, N '-dimethylene NSC 18620) and its strong acid salt and composition thereof.The better water solubility initator is two hydrochloric acid 2,2 '-azo is two-(2-amidine propane), and available from Virginia Wako Chemicals USA, the commodity of Inc.ofRichmond " V-50 " by name.Before the polymer and other comonomer blending in the present composition that will obtain, as described below such, this polymer emulsion of first dilute with water.Fluorinated ester
In the present composition, can randomly comprise fluorinated ester, ester that in the present composition, uses and above-mentioned United States Patent (USP) 5,350,795 disclosed scopes are identical, and these esters in composition help treated fabric to keep its soil resistance in for example wearing and tearing back.If do not use ester in the present composition, treated base material its antifouling property under situation about being worn can descend, but as described in this manual, this composition is still useful for handling base material.Be used for mixture that fluorinated ester of the present invention can be by perfluoroalkyl aliphatic alcohol or alcohol and have 3-30 carbon atom, can have other substituent unit carboxylic acid or polybasic carboxylic acid and react and make.Perhaps, use the mixture of polybasic carboxylic acid esterification perfluoroalkyl aliphatic alcohol and hydrocarbon alcohol, this ester for example is described in the United States Patent (USP) 4,029,585 people such as () Dettre.
A kind of preferred fluorinated ester is the fluorine-containing adipate ester that is expressed from the next:
{R
fQ[OCH
2CH(CH
2Cl)]
nO
2CCH
2CH
2-}-
2
R wherein
fWith the definition of Q as above, n is 1-5, preferably the number of 1-3.
Fluorine-containing adipate ester can and contain chloropharin and adipic acid by the fluorine-containing fat-based of precursor and react and make.A kind of ester preferably is expressed from the next:
The alcohol precursor can make by chloropropylene oxide and the alcohol reaction with fluorine-containing aliphatic group.The alcohol that can be used for this preparation and can easily obtain is expressed from the next:
Wherein: R
fWith Q as defined above;
R
5Be hydrogen or low alkyl group;
R
6Be hydrogen, low alkyl group, or the aryl of 6-12 carbon atom, R
5And R
6Can be joined together to form circulus, aryl or fatty cyclic group, they contain the carbon atom that is connected with hydroxyl.But when containing fluorine-containing aliphatic group alcohol and chloropropylene oxide reaction and generating corresponding fluorine-containing aliphatic alcohol, the latter can have following general formula:
R wherein
f, Q, R
1And R
2As defined above, p is the integer of 1-5.
Contain in the United States Patent (USP) 4,289,892 of the United States Patent (USP) 4,043,823 that can be disclosed in Loudas for example and Soch with the representative fluorine-containing aliphatic compounds of epoxy reactive hydrogen atom (they can be used for preparing corresponding fluorine-containing aliphatic group and contain chloropharin).
Suitable fluorine-containing adipate ester is disclosed in the United States Patent (USP) 4,264,484 of Patel, and this patent is listed in this and drawn and be reference.Composition preferably
Composition of the present invention comprises the blend of said components, and the preparation of this blend is described in detail in the general preparation process and embodiment of this specification.Usually, the present composition is the blend of first and second key components, and wherein first key component comprises the polyurethane of poly-alkoxylation, preferably has the poly-alkane diol copolymer of fluorine-containing, and randomly comprises aforesaid fluorine-containing adipate ester.Second key component comprises the fluorinated acrylate polymer with aforesaid polymerizable cationic emulsifying agent.
With regard to first key component, can use the polyurethane in water-based emulsion separately, this polyurethane can make (15% solid according to appointment) according to general preparation process B, but can change monomer and substituting group according to above-mentioned parameter.Can make the fluorine-containing alkylidene diol ester according to general preparation process C, but can change monomer and substituting group according to above-mentioned parameter.It is polyurethane that perfluoroalkyl acrylate alkylidene diol ester and polyurethane are blended into weight ratio: the fluorine-containing alkylidene diol ester is about 3: 2.When containing optional adipate ester in first key component, the blending in deionized water of polyurethane, fluorine-containing alkylidene diol ester and adipate ester also can be stirred with thorough mixing, from mixture, remove excessive solvent subsequently, should about 5-20%, the preferably blend of about 10-16% with the amount of solid that is formed in the water.Polyurethane should account for the 50-90 weight % of first component, preferably accounts for about 50%.The fluorine-containing alkylidene diol ester should account for 10-50 weight %, preferably accounts for about 33%.The amount of optional adipic acid accounts for 10-20 weight % usually, preferably accounts for 17%.
With regard to second key component, fluorinated acrylate polymer is made into water-based emulsion, and usually according to general preparation process A preparation, but can be according to the parameter change monomer and the substituting group of this paper proposition.Make solids content be preferably about 3 weight % two kinds of key component blending in deionized water, the solid weight ratio between two kinds of components is about 25: 1-1: 25, be preferably 9: 1-1: 9.Preferably the solid weight ratio of two kinds of key components is about 1: 1 in the composition that forms after the blending.
Then add a small amount of coagulating agent and a small amount of other solvent (as alcohol) to increase the wettability of fabric, improve the stability of composition and reduce the mottling that on treated base material, may form.Composition during with the packaged of spray, can added spray such as iso-butane etc.Equally, be preferably in this spray product and add corrosion inhibitor, to prevent to be generally used for to pack the corrosion of the cylinder of steel of this product.
Suitable co-solvent comprises alkylene glycol ether, as the dipropylene glycol mono-n-butyl ether, and propylene glycol monomethyl ether, dipropylene glycol positive propyl ether, their ester and mixture.If solid concentration is about 3% preferably in composition, the co-solvent total content is 2-10 weight % in composition so, preferably is about 4%.Can add a small amount of alkylol such as ethanol or isopropyl alcohol helps the stable of composition and prevents that it from freezing as additional solvent.The content of alcohol in final composition is preferably about 0.5-3 weight %, preferred 1 weight %.Select suitable solvent with and relative concentration in composition be to have the technical staff of practical experience known in this area.Suitable corrosion inhibitor comprises morpholine, ammonium hydroxide (30%), natrium nitrosum, alkylamine and their combination.Suppose that the solid concentration in composition is about 3%, the concentration of corrosion inhibitor preferably is about 0.5-1.0 weight % often less than 1 weight %.
Can in above-mentioned spray agent, add the pH regulator agent to form the composition of quick froth breaking.Froth pulp can make the user of this composition observe the position that has applied this composition easily, thereby has avoided repeating to apply this composition and the increase of drying time of causing thus.
Also can in the present composition, add anti-fouling agent.This anti-fouling agent is defined as dispersible material in solid-state, inviscid, water-soluble or the water, and after composition dries, this material can make base material not be clamminess and can prevent and pollute, and adds anti-fouling agent and choose wantonly in the present composition.
Composition described here can be applied on the base material of various fibre-bearing goods.This base material comprises Textile Fibre Product (or long filament) and cover, pad and the carpet of the fabric (comprising the final products that fabric is made) that formed by cotton, polyester, polyolefin, nylon, acrylic acid, acetate or its blend and leather and clothes, furniture, can use the present composition to handle the combination of other fiber or long filament and this fiber and long filament, as yarn, fibre bundle, silk screen and weaving or knitting fabric.These base materials can use the present composition to handle, and promptly use the known technology commonly used that fluorochemical is applied on fibre and the fabric that the present composition is applied on the base material.Composition can be applied to final products (as cover, the pad of clothes and furniture) and go up and do not need to heat-treat, and not need to add a large amount of organic solvents and just can obtain good grease-proof and waterproof.Suitable this method for compositions that applies comprises, for example sprays, dips in brush, immerses or foaming (fbaming).The amount that is applied to the composition on the base material often is about 0.5-6 weight % solid, preferably 1-4% weight solid (by the weight of fibre or fabric).Test method
In the embodiment of back, according to the grease proofing and water proofing property of the treated base material of following test method test.Grease proofness
Grease proofness according to the treated base material of the method test of the No.118-1966 of AATCC (AATCC) test method.This test has provided the relative data of test substrate grease proofness.Drop in several test(ing) liquids on the base material lentamente and kept for 30 seconds.Inhale from base material with paper handkerchief subsequently and remove or wipe drop, observe the moistening vestige on the base material.Use 8 kinds of different greasy dirts (oil challenge) liquid, the easiest the wiping of No. 1 liquid (" medical lubricating oil " mineral oil) wherein, the most difficult the removing of No. 8 liquid (normal heptane).Various test(ing) liquids are listed in the table below in 1.Successively base material is tested, since No. 1 liquid and test successively, after 30 seconds, still can be observed it until a kind of liquid and stay moistening vestige on the base material.Use the not rank-numeral of the highest liquid sequence number of moistening base material during the report grease proofness.In order to carry out detailed comparison, get that many various liquid are tested and available whole numeral or the numeral of each part are given a report.Generally requiring the grease proofness rank is 5 or higher.Table 1-AATCCTM-118-1966
The wearing and tearing grease proofness
| The grease proofness grade | Test(ing) liquid |
| 8 | Normal heptane |
| 7 | Normal octane |
| 6 | N-decane |
| 5 | N-dodecane |
| 4 | N-tetradecane |
| 3 | Hexadecane |
| 2 | Hexadecane: medical lubricating oil is 35: 65 mixture |
| 1 | Medical lubricating oil (mineral oil) |
The test of wearing and tearing grease proofness provides the relative data of base material grease proofness equally.But in this test method, treated base material at first is put on the ATTCC fastness to rubbing analyzer (as employed in AATCC test method 8-1985, available from Illinois Atlas Electric Devices Co.ofChicago), use No. 600 sandpaper disks (available from the commodity of Minnesota State 3M company " Wetordry Tri-M-ite " by name) of 1.6 centimetres of diameters that it is carried out the grinding of 20 circles.After the grinding, use the test oil of describing in the anti-oil test test substrate to be tested with the method identical with it.Usually, requiring the grease proofness rank is 4 or bigger.Waterproof/alcohol drips
Waterproof/alcohol drips test and is used for the ability that test substrate is resisted various water and isopropyl alcohol blend.The test drop of liquid solution is applied on the treated base material successively, after 30 seconds,, then uses paper handkerchief that its suction is gone or wipe and observe surface wettability on the substrate surface if the drop that is applied is not inhaled in the base material.Use the blend (seeing the following form 2) of 11 kinds of water and alcohol, wherein 100% water is the easiest wipes, 100% isopropyl alcohol is the most difficult wipes, and treated base material provides a numerical value, and this numerical value can be wiped the aqueous isopropanol of the maximum concentration that does not stay observable moistening vestige corresponding to treated base material.For example, if treated base material can be wiped the solution of 60% water and 40% isopropyl alcohol, the number that then provides is 4.
Table 2 test(ing) liquid (volume, 21 ℃ (70))
The water spray test
| Solution | The composition of experimental liquid (weight %) |
| W | 100 water |
| 1 | 90/10 water/isopropyl alcohol |
| 2 | 80/20 water/isopropyl alcohol |
| 3 | 70/30 water/isopropyl alcohol |
| 4 | 60/40 water/isopropyl alcohol |
| 5 | 50/50 water/different third ferment |
| 6 | 40/60 water/isopropyl alcohol |
| 7 | 30/70 water/isopropyl alcohol |
| 8 | 20/80 water/isopropyl alcohol |
| 9 | 10/90 water/isopropyl alcohol |
| 10 | 100 isopropyl alcohols |
Carry out the water spray test according to AATCC test method 22.Water proofing property with the treated base material of the surface wettability figure assessment of following table 3 descriptions.During test, that treated base material is tight in the ring that is 45 of 15 cm diameters.The water that with the 250ml temperature is 27 ℃ (± 1 ℃) is that 15.2 centimeters are dripped to base material from base material central authorities top distance.Water droplet add finish after, pat base material lightly to remove excessive water and to assess according to the method for table 3.Higher numerical value shows preferable water proofing property.Usually the numerical value that requires is 65 or higher.Table 3
Drenched degree
| Evaluation grade | The waterproof degree |
| 100 | The no moistening vestige in surface |
| 90 | The surface only has several points moistening |
| 80 | The surface has 6-15 point moistening |
| 70 | The surface has point in blocks wetting |
| 50 | Fabric center is moistening fully |
| 0 | Whole fabric face is moistening fully |
Drenched degree is to test immediately after above-mentioned water spray test on the treated base material.The treated base material of doing assessment in the superincumbent water spray test is overturn immediately, perusal is carried out at the back side of this base material, and touch to measure whether the water infiltration is arranged through the observer.To the degree of treated base material, provide 1 to 6 osmotic value then according to " moistening ".Numerical value " 1 " represents that this base material thoroughly permeates, and numerical value " 6 " is represented this base material and done fully.Comprehensive resisting property rank
By summing up the data that obtain in the superincumbent method of testing, comprehensively the resisting property rank of various compositions on various base materials is listed as into table, except the data that will in water spray test, obtain at first divided by 10.Comprehensively resisting property rank maximum possible value is 42.General preparation procedure A fluorinated acrylate polymer and polymerizable cationic emulsifying agent
In the reaction vessel that condenser, mechanical agitator and thermometer are housed, add 9.0 gram methacrylic acid N, the N-dimethylamino ethyl ester is (available from Aldrich Chemicals of Milwaukee, Wisconsin), 0.036 restrain 2,6-BHT (BHT) (Aldrich Chemicals), 18.8 gram acetone and 17.5 gram 1-bromine hexadecanes (Aldrich Chemicals).This mixture is heated at 75 ℃ (165-170 °F), and until through gas chromatography determination, the content of unreacted amine is lower than 0.05%.Make the reaction solution cooling then, observe and formed sediment.In this reaction solution, add people's 18.1 gram ethyl acetate (Aldrich Chemicals), and make this solution be cooled to 16 ℃ (60 °F).Be settled out white solid (Diethylaminoethyl acrylic acid 2-(dimethyl cetyl amino) ethyl ester) from solution, leach this solid, with cold ethyl acetate washed twice, 50 ℃ of dryings are 8 hours in vacuum drying oven.
In the suitable flask that mechanical agitator and thermometer are housed, with laboratory homogenizer (for example, model is HC-8000, available from Microfiuidics Corp.of Newton, Massachusetts) make the mixture of 139.46 gram deionized waters and 2.34 gram Diethylaminoethyl acrylic acid 2-(dimethyl cetyl amino) ethyl esters about 10 minutes of 60 ℃ of emulsifications.In 16 ounces of (0.47 liter) amber bottles, add 34.86 gram acrylic acid N-methyl perfluoro capryl sulfonamido ethyl esters (available from Minnesota Mining and Manufacturing Company of St.Paul, Minnesota), 17.40 gram butyl acrylates (Aldrich Chemicals) and 5.86 restrain butyl methacrylates (Aldrich Chemicals).Under stirring gently, be heated to 60 ℃ with this bottle cap upper cover and with this mixture.This mixture is slowly added in the bromide salt solution of homogenizing, make the emulsion that obtains twice of chamber homogenizer by experiment.This emulsion is transferred in the amber bottle of 16 ounces (0.47 liters), and with 0.06 the gram radical initiator (2,2 '-azo two-(2-amidine propane) dichloride hydrogen (" V-50 " is available from Wako Chemicals USA, Inc.)) is handled, and passes through this emulsion one minute with nitrogen bubble.Cover bottle stopper and keep 60 ℃ in launderometer, to mix 5 hours with about 50rpm.Latex (having about 30% solid) cooling, filtration with obtaining are ready to use in the following batching then.General preparation procedure B polyurethane
The 1.062 hot sulfonamido ethanol of gram (1.8 moles) N-methyl perfluor and 708 are restrained ethyl acetate (available from Mallinckrodt, Inc.ofParis Kentucky) is added in 5 liters of three-neck flasks that mechanical agitator, thermometer, reflux condenser, nitrogen inlet pipe and heating jacket are housed.In blanket of nitrogen, be heated to after about 55 ℃ under stirring, add the solution of premixed 616 gram (1.08 moles) trifunctional isocyanates (" DESMODUR " N-100 is available from Farbenfabriken Bayer AG) and 300 gram ethyl acetate.Then add 0.84 gram stannous octoate (Sigma Chemical Co.ofSt.Louis, Missouri), with this reactant mixture about 75 ℃ of stir abouts six hours.The solution that adds 1,044 gram (0.72 mole) premixed alkoxyl polyethylene glycol (commodity are called " CARBOWAX " 1450, available from Union Carbide) and 807 gram ethyl acetate.The mixture that obtains stirred and about 16 hours of reflux (about 83 ℃).The 150 gram polyurethane solutions that make are added in 1 liter of three-neck flask that mechanical agitator, dropping funel, thermometer and heating jacket are housed and are heated to 65 ℃.Slow adding has been heated to 65 ℃ distilled water (510 gram) under vigorous stirring.The mixture that obtains was stirred 10 minutes and remove ethyl acetate, obtain containing the translucent dispersion of 15% solid of having an appointment by coupling vacuum stripping.General preparation procedure C fluorine-containing alkylidene diol ester
At first (commodity are called " PLURONIC " 44 with the terminal two functional blocks polymer that have a hydroxyl of 120 gram toluene, 90 grams, available from BASF Company of Parsippany, New Jersey), 0.05 gram phenthazine (Aldrieh Chemicals), 4.45 gram acrylic acid (Aldrich Chemicals) and 1 restrain the acrylate solution that p-methyl benzenesulfonic acid (Aldrich Chemicals) is added to poly-to prepare (oxyalkylene) in the glass reactor that stirring, heating, cooling and reflux are housed.Under agitation the reactant in the reactor is reached constant 110 ℃ of-120 ℃ of reflux until acid content.Then the reactant in the reactor is cooled to 50 ℃, with the pulverous calcium hydroxide neutralization of 2 grams and with this reactant stir about 0.5 hour again.
The acrylate solution of 90 grams above-mentioned poly-(oxyalkylene) are added to 120 gram toluene and 36 gram acrylic acid N-butyl perfluor suffering sulfonamido ethyl esters (Minnesota Mining and Manufacturing Company) stirring are housed, vacuumize, in the glass reactor of ammonia input, heating, cooling and distilling apparatus.Under agitation the reactant in the reactor was heated 5 hours at 55 ℃, add 6 gram n-octyl mercaptan (Aldrich Chemicals) chain-transferring agents and 0.9 gram tert-butyl hydroperoxide promoter (t-C4H9OOH) (Aldrich Chemicals) then.Remove the oxygen in the reactor and be pressed into nitrogen again by vacuumizing as a means of cleaning.Then with reactant 65 ℃ of stir abouts 16 hours, from reactor, remove under the vacuum and desolvate (under the pressure of 95 ℃ of about 200mm mercury column 1 hour).General preparation procedure D adipate ester
In the glass flask that addition funnel, condenser, agitator, heating jacket and thermometer are housed, put into 670 gram ethanol (according to U.S. Patent No. 4,264, embodiment 2 preparation in 484), 73 restrain oneself diacid and 480 gram toluene, under agitation the reactant in the flask slowly is heated to about 80 ℃, adds the 2.2 gram concentrated sulfuric acids then.This reactant mixture is heated to backflow.Remove moisture with improved Dean-Stark trap then, after refluxing 16 hours, reaction is finished.Under atmospheric pressure distill then to remove toluene, obtain 691 gram residues, this product is for being beige solid, 64 ℃-82 ℃ of fusing points.General preparation procedure E fusion is according to the component of program B, C and D preparation
In 2 liters of three-neck flasks that overhead, thermometer and reflux condenser are housed, add 184.6 grams and restrain ethyl acetate and 960 gram deionized waters according to acrylate copolymer, 36 grams of general preparation procedure C preparation according to the fluorine-containing adipate ester, 125 of general preparation procedure D preparation as the polyurethane reactive mixture (in ethyl acetate, adding before the water) among the general preparation procedure B, 178.7 grams.With the mixture that obtains vigorous stirring 1 hour under 65-70 ℃ of heating.Remove solvent by coupling vacuum stripping, add 750 gram water as required, obtain containing the stable dispersion of 12% solid of having an appointment.General preparation procedure F fusion is according to the component of program B and C preparation
In 500 liters of three-neck flasks that overhead, thermometer and reflux condenser are housed, add the polyurethane reactive mixture (in ethyl acetate, adding before the water) among 27.5 grams as the general preparation procedure B, acrylate copolymer and the 144 gram deionized waters that 25.0 grams prepare according to above-mentioned general preparation procedure C.With the mixture that obtains, vigorous stirring is 60 minutes under 70 ℃ of heating.Remove solvent by coupling vacuum stripping, obtain containing the stable dispersion of 14% solid of having an appointment.General preparation procedure G
In the amber bottle of 16 ounces (0.47 liters), add 36 gram acrylic acid N-methyl perfluoro capryl sulfonamido ethyl esters (Minnesota Mining and Manufacturing Company), (commodity are called " ETHOQUAD " 18/25 for 18 gram butyl acrylates, 6 gram butyl methacrylates, 28 gram ethanol, 112 gram deionized waters and 3 gram methyl polyoxyethylene (15) octadecyl ammonium chloride cationic surfactants, available from AkzoChemicals of Chicago, Illinois).In launderometer with this mixture heated to 60 ℃.In the mixture of this heating, add 0.06 gram radical initiator (2,2 '-azo two-(2-amidine propane) dichloride hydrogen (" V-50 " is available from Wako Chemicals USA, Inc.)) and with nitrogen bubble by this mixture one minute.With this bottle cap upper cover and remain on 60 ℃, in launderometer, mixed 5 hours simultaneously.The latex that obtains is filtered, can be used in the reference examples.
The following examples have illustrated the preparation of the present composition and advantage by contrast.For described material, consumption and other condition and details do not have undue restriction in an embodiment.All percentage number averages by weight, except as otherwise noted.
Embodiment
Embodiment 1
In the 200ml flask of mechanical agitator is housed, under continuous stirring, 78 gram deionized waters, 5.0 grams are mixed according to the admixture of said procedure E preparation according to fluorinated acrylate polymer emulsion, 12.5 grams of said procedure A preparation.Then, under continuous stirring, in this flask, add 2.5 gram dipropylene glycol, one n-butyl ether, 1.0 gram propylene glycol-methyl ethers and 1.0 gram ethanol.The solution that obtains contains 3% the solid of having an appointment, and fluorinated acrylate polymer: the weight ratio of [polyurethane+poly-fluorine-containing acrylic aklylene glycol ester copolymer+adipate ester] is about 1: 1.Prop up and execute example 2
Basically the method by embodiment 1 prepares another kind of composition, difference is to use 0.5 gram fluorinated acrylate polymer, and 23.8 grams are mixed with fluorinated acrylate polymer according to the admixture and the 71.2 gram deionized waters of said procedure E preparation: the weight ratio of [polyurethane+poly-fluorine-containing acrylic aklylene glycol ester copolymer+hexanedioic acid ester] is about 1: 19 admixture.
Embodiment 3
Basically the method by embodiment 1 prepares another kind of composition, and difference is to use 1.0 gram fluorinated acrylate polymers, 22.5 grams to be mixed with fluorinated acrylate polymer according to the admixture and the 72 gram deionized waters of said procedure E preparation: the weight ratio of [polyurethane+poly-fluorine-containing acrylic aklylene glycol ester copolymer+hexanedioic acid ester] is about 1: 9 admixture.Embodiment 4
Basically the method by embodiment 1 prepares another kind of composition, and difference is to use 9.0 gram fluorinated acrylate polymers, 2.5 grams to be mixed with fluorinated acrylate polymer according to the admixture and the 84 gram deionized waters of said procedure E preparation: the weight ratio of [polyurethane+poly-fluorine-containing acrylic aklylene glycol ester copolymer+adipate ester] is about 9: 1 admixture.
Embodiment 5
Basically the method by embodiment 1 prepares another kind of composition, and difference is to use 9.5 gram fluorinated acrylate polymers, 12.5 grams to be mixed with fluorinated acrylate polymer according to the admixture and the 84.75 gram deionized waters of said procedure E preparation: the weight ratio of [polyurethane+poly-fluorine-containing acrylic aklylene glycol ester copolymer+adipate ester] is about 19: 1 admixture.
Embodiment 6
Basically the method by embodiment 1 prepares another kind of composition, and difference is to use 1.7 gram fluorinated acrylate polymers, 4.2 grams to be mixed with the admixture that contains 1% solid according to the admixture and the 89.6 gram deionized waters of said procedure E preparation.Fluorinated acrylate polymer: the weight ratio of [polyurethane+poly-fluorine-containing acrylic aklylene glycol ester copolymer+adipate ester] is about 1: 1.
Embodiment 7
Basically the method by embodiment 1 prepares another kind of composition, and difference is to use 10 gram fluorinated acrylate polymers, 25 grams to be mixed with the admixture that contains 6% solid according to the admixture and the 60.5 gram deionized waters of said procedure E preparation.Fluorinated acrylate polymer: the weight ratio of [polyurethane+poly-fluorine-containing acrylic aklylene glycol ester copolymer+adipate ester] is about 1: 1.
Embodiment 8
Basically prepare fluorinated acrylate polymer by said procedure A, difference is that the solution of 2-(trimethyl-amino) ethyl-methyl acrylate chloride salt in water that contains 75% solid with 3.12 grams substitutes the bromide salt monomer.Under continuous stirring, 78 gram deionized waters, 5.0 gram fluorinated acrylate polymers and the 12.5 grams admixture according to said procedure E preparation is mixed in flask.Then, connecting under the stirring, in this flask, adding 2.5 gram dipropylene glycol, one n-butyl ether, 1.0 gram Glycol Monomethyl ethers and 1.0 gram ethanol.The solution that obtains contains 3% the solid of having an appointment, and fluorinated acrylate polymer: the weight ratio of [polyurethane+poly-fluorine-containing acrylic aklylene glycol ester copolymer+adipate ester] is about 1: 1.
Embodiment 9
Basically prepare fluorinated acrylate polymer by said procedure A, difference is to substitute the bromo docosane with preparation 2-(dimethyl docosane amino) ethyl-methyl acrylate bromide salt with bromohexadecane.Identical with embodiment 1, under continuous stirring, 78 gram deionized waters, 5.0 gram fluorinated acrylate polymers and the 12.5 grams admixture according to said procedure E preparation is mixed in flask.Then, connecting under the stirring, in this flask, adding 2.5 gram dipropylene glycol, one n-butyl ether, 1.0 gram Glycol Monomethyl ethers and 1.0 gram ethanol.The solution that obtains contains 3% the solid of having an appointment, and fluorinated acrylate polymer: the weight ratio of [polyurethane+poly-fluorine-containing acrylic aklylene glycol ester copolymer+adipate ester] is about 1: 1.
Embodiment 10
Basically prepare fluorinated acrylate polymer by said procedure A, difference is with 23.26 gram methyl acrylate instead of propylene acid butyl ester and butyl methacrylates.Identical with embodiment 1, under continuous stirring, 78 gram deionized waters, 5.0 gram fluorinated acrylate polymers and the 12.5 grams admixture according to said procedure E preparation is mixed in flask.Then, connecting under the stirring, in this flask, adding 2.5 gram dipropylene glycol, one n-butyl ether, 1.0 gram Glycol Monomethyl ethers and 1.0 gram ethanol.The solution that obtains contains 3% the solid of having an appointment, and fluorinated acrylate polymer: the weight ratio of [polyurethane+poly-fluorine-containing acrylic aklylene glycol ester copolymer+adipate ester] is about 1: 1.
Embodiment 11
Basically prepare fluorinated acrylate polymer by said procedure A, difference is with 23.26 gram acrylic acid octadecane ester instead of propylene acid butyl ester and butyl methacrylates.Identical with embodiment 1, under continuous stirring, 78 gram deionized waters, 5.0 gram fluorinated acrylate polymers and the 12.5 grams admixture according to said procedure E preparation is mixed in flask.Then, connecting under the stirring, in this flask, adding 2.5 gram dipropylene glycol, one n-butyl ether, 1.0 gram Glycol Monomethyl ethers and 1.0 gram ethanol.The solution that obtains contains 3% the solid of having an appointment, and fluorinated acrylate polymer: the weight ratio of [polyurethane+poly-fluorine-containing acrylic aklylene glycol ester copolymer+adipate ester] is about 1: 1.
Embodiment 12
Under continuous stirring, in the 200ml flask of mechanical agitator is housed, 80.5 gram deionized waters, 5.0 grams are mixed according to the polyaminoester emulsion that said procedure B prepares according to the fluorinated acrylate polymer and 10 grams of said procedure A preparation.Then, connecting under the stirring, in this flask, adding 2.5 gram dipropylene glycol, one n-butyl ether, 1.0 gram Glycol Monomethyl ethers and 1.0 gram ethanol.The solution that obtains contains 3% the solid of having an appointment, and fluorinated acrylate polymer: the weight ratio of polyurethane is about 1: 1.
Embodiment 13
Under continuous stirring, in the 200ml flask of mechanical agitator is housed, 80.5 gram deionized waters, 5.0 grams are mixed according to the fluorinated acrylate polymer and 10 admixtures that restrain the polyurethane/acrylate polymer for preparing according to said procedure F of said procedure A preparation.Then, connecting under the stirring, in this flask, adding 2.5 gram dipropylene glycol, one n-butyl ether, 1.0 gram Glycol Monomethyl ethers and 1.0 gram ethanol.The solution that obtains contains 3% the solid of having an appointment, and fluorinated acrylate polymer: the weight ratio of [polyurethane+poly-fluorine-containing acrylic aklylene glycol ester copolymer] is about 1: 1.
Embodiment 14
Basically prepare fluorinated acrylate polymer by said procedure A, difference is with 23.26 gram methyl acrylate instead of propylene acid butyl ester and butyl methacrylates.Under continuous stirring, 81.7 gram deionized waters, 6.7 gram fluorinated acrylate polymers and the 7.1 grams admixture according to the polyurethane/acrylate polymer of said procedure F preparation is mixed in flask.Then, connecting under the stirring, in this flask, adding 2.5 gram dipropylene glycol, one n-butyl ether, 1.0 gram Glycol Monomethyl ethers and 1.0 gram ethanol.The solution that obtains contains 3% the solid of having an appointment, and fluorinated acrylate polymer: the weight ratio of [polyurethane+poly-fluorine-containing acrylic aklylene glycol ester copolymer] is about 2: 1.
Embodiment 15
Basically the method by embodiment 13 prepares another kind of composition, and difference is to use 81.7 gram deionized waters, 6.7 grams to restrain the admixture of the polyurethane/acrylate polymer for preparing according to said procedure F according to the fluorinated acrylate polymer and 7.1 of said procedure A preparation.The solution that obtains contains 3% the solid of having an appointment, and fluorinated acrylate polymer: the weight ratio of [polyurethane+poly-fluorine-containing acrylic aklylene glycol ester copolymer] is 2: 1.
Embodiment 16
Basically prepare polyether polyols with reduced unsaturation according to said procedure B, difference is to substitute polyethylene glycol (" Carbowax " 1450) with the propylene oxide of commercially available commodity " Pluronic " L62 by name, ethylene oxide copolymer (available from BASFCorporation of Parsippany, New Jersey).Under continuous stirring, in the 200ml flask of mechanical agitator is housed, 80.5 gram deionized waters, 5.0 grams are mixed according to the fluorinated acrylate polymer and the 10 gram polyurethane of said procedure A preparation.Then, connecting under the stirring, in this flask, adding 2.5 gram dipropylene glycol, one n-butyl ether, 1.0 gram Glycol Monomethyl ethers and 1.0 gram ethanol.The solution that obtains contains 3% the solid of having an appointment, and fluorinated acrylate polymer: the weight ratio of polyurethane is about 1: 1.
Embodiment 17
Basically prepare polyether polyols with reduced unsaturation according to said procedure B, difference is to substitute " Carbowax " 1450 ethylene glycol with " Carbowax " 400 ethylene glycol, substitutes " Desmodur " N100 triisocyanate with " Desmodur " N3300 triisocyanate.Under continuous stirring, in the 200ml flask of mechanical agitator is housed, 80.5 gram deionized waters, 5.0 grams are mixed according to the fluorinated acrylate polymer and the 10 gram polyurethane of said procedure A preparation.Then, connecting under the stirring, in this flask, adding 2.5 gram dipropylene glycol, one n-butyl ether, 1.0 gram Glycol Monomethyl ethers and 1.0 gram ethanol.The solution that obtains contains 3% the solid of having an appointment, and fluorinated acrylate polymer: the weight ratio of polyurethane is about 1: 1.
Embodiment 18
By method compositions formulated substantially the same manner as Example 1, difference is to use 72.5 gram deionized waters, and with 10 glycol ether and the ethanol that restrain in the dipropylene glycol one n-propyl ether alternate embodiment 1.
Embodiment 19
Under agitation, the 99.45 gram compositions that will prepare according to the method for embodiment 1 and 0.2 gram morpholine, 0.2 gram natrium nitrosum and 0.15 gram Ammonia (30% aqueous solution) are mixed with aerosol.This liquid is contained in the aerosol can, and adds 5.0 to 5.5 gram iso-butanes as propellant.Reference examples A
Under continuous stirring, in the 200ml flask of mechanical agitator is housed, 85.5 gram deionized waters and 10 grams are mixed according to the fluorinated acrylate polymer that said procedure A prepares.Then, connecting under the stirring, in this flask, adding 2.5 gram dipropylene glycol, one n-butyl ether, 1.0 gram Glycol Monomethyl ethers and 1.0 gram ethanol.The emulsion that obtains contains 3% the solid of having an appointment.Reference examples B
Under continuous stirring, in the 200ml flask of mechanical agitator is housed, 70.5 gram deionized waters and 25 grams are mixed according to the admixture that said procedure E prepares.Then, connecting under the stirring, in this flask, adding 2.5 gram dipropylene glycol, one n-butyl ether, 1.0 gram Glycol Monomethyl ethers and 1.0 gram ethanol.The emulsion that obtains contains 3% the solid of having an appointment.Reference examples C
Under continuous stirring, in the 200ml flask of mechanical agitator is housed, 78 gram deionized waters, 5 grams are mixed according to the admixture that said procedure E prepares according to the admixture and 12.5 grams of said procedure G preparation.Connecting under the stirring then, in this flask, adding 2.5 gram dipropylene glycol, one n-butyl ether, 1.0 gram Glycol Monomethyl ethers and 1.0 gram ethanol.The emulsion that obtains contains 3% the solid of having an appointment.Reference examples D
Under continuous stirring, in the 200ml flask of mechanical agitator is housed, 85.5 gram deionized waters and 10 grams are mixed according to the admixture that said procedure G prepares.Then, connecting under the stirring, in this flask, adding 2.5 gram dipropylene glycol, one n-butyl ether, 1.0 gram Glycol Monomethyl ethers and 1.0 gram ethanol.The emulsion that obtains contains 3% the solid of having an appointment.Reference examples E
In this reference examples E, select the solvent of commercially available protection fabric for use.This product is the fabric protectant of aerosol form, and its commodity are called " ScotchGard " (available from Minnesota Mining andManufacturing Company of St.Paul, fabric protectant Minnesota.).Reference examples F
Under agitation, 0.2 gram morpholines, 0.2 gram natrium nitrosums and the 0.15 gram Ammonias (30% aqueous solution) of 99.45 gram compositions that will prepare according to the method for reference examples C and adding are mixed with aerosol.Said composition is contained in 6-8 ounces of (0.18-0.23 liter) aerosol cans, and adds 5.0 to 5.5 gram iso-butanes as propellant.
According to above-mentioned test program the various embodiments described above are tested on different base materials with the composition in the reference examples.All base materials prepare through carry out the hand spray composition in 20.3 * 22.9cm area.Should note making various compositions for use evenly to cover, so that dried impost is about 2-3% of dry fabric weight.Before test, with treated base material dried overnight under environmental condition.
Various fabric substrates used in test are defined as follows:
Fabric A is that commercially available model is the polyester/cotton blending thing (65% polyester/35% cotton) through bleaching and washing of 7436 (available from Testfabrics, Inc.Of Middlerex, New Jersey.).
Fabric B be commercially available model be 428 (available from Testfabrics, cotton satin Inc.) (100% cotton) through destarch and bleaching.
Fabric C is that undressed rough machined green man-made silk velvet guard fabric is (available from Collins﹠amp; Aikman, Decorative Fabrics Division of Roxboro, NorthCarolina).
Fabric D is that model is that 62521 polypropylene velvet drapery is (available from Joan Fabrics ofLowell, Massachusetts).
Fabric E is that model is that 9352 the textile decoration fabric that contains 48% polyolefin/18% artificial silk/34% polyester is (available from Chromatex of West Hazelton, Pa).Embodiment 1-18 and reference examples A-E
On fabric A and B, carry out the test of embodiment 1-18 and reference examples A-E according to above-mentioned method of testing.Provided correction data in table 4 below (fabric A) and the table 5 (fabric B).Table 4 (correction data-fabric A)
*Can expression embodiment be blended into aerosol table 5 (correction data-fabric B) by adding corrosion inhibitor and propellant as in the preparation of above-mentioned embodiment 19
*Can expression embodiment be blended into aerosol by adding corrosion inhibitor and propellant as in the preparation of above-mentioned embodiment 19,
| Embodiment | Water proofing property | Grease proofness | The wearing and tearing grease proofness | The spraying grade | Drenched | Compound | Aerosol stability * |
| 1 | 9.7±1.0 | 6.0±0 2 | 5.5±0.7 | 66±6 | 5.8±0.8 | 34±2 | Energy |
| Reference examples A | 9.8±0.9 | 6.0±0.2 | 3.8±1.6 | 66±6 | 5.9±0.4 | 32±2 | Can not |
| Reference examples B | 5.0±2.0 | 5.4±1.4 | 5.3±0.5 | 54±8 | 2.7±2.3 | 24±3 | Energy |
| Reference examples C | 4.0 | 4.3 | 4.0 | 63 | 2.0 | 21 | Energy |
| Reference examples D | 4.0 | 4.3 | 2.8 | 63 | 4 | 21 | Can not |
| 2 | 5 | 5 | 4.8 | 58 | 3 | 24 | |
| 3 | 7 | 6 | 6 | 62 | 4 | 29 | |
| 4 | 10 | 6.3 | 3.5 | 65 | 6 | 32 | |
| 5 | 10 | 6 | 4.3 | 68 | 6 | 33 | |
| 6 | 5 | 2.5 | 2 | 64 | 3 | 19 | |
| 7 | 10 | 7 | 6 | 64 | 6 | 35 | |
| 8 | 6 | 5.5 | 5.5 | 58 | 5 | 28 | |
| 9 | 9 | 5.3 | 5 | 67 | 6 | 32 | |
| 10 | 9 | 6 | 5 | 67 | 6 | 33 | |
| 11 | 6 | 4.5 | 3.8 | 63 | 5 | 26 | |
| Reference examples E | 9 | 5.5 | 4 | 72 | 5 | 31 | Energy |
| 12 | 9 | 5.5 | 4.8 | 65 | 6 | 32 | |
| 13 | 10 | 6.3 | 6 | 67 | 6 | 35 | |
| 14 | 9 | 5.3 | 5 | 67 | 6 | 32 | |
| 15 | 10 | 6 | 5.5 | 67 | 6 | 34 | |
| 16 | 8 | 4.5 | 4.3 | 64 | 5 | 28 | |
| 17 | 8 | 4.3 | 3.8 | 66 | 5 | 28 | |
| 18 | 10 | 6 | 5.8 | 65 | 6 | 34 |
| Embodiment | Water proofing property | Grease proofness | The wearing and tearing grease proofness | The spraying grade | Drenched | Compound | Aerosol stability * |
| 1 | 9.3±1.0 | 5.8±0.8 | 5.5±0.9 | 65±5 | 60±0.0 | 33±3 | Energy |
| Reference examples A | 9.6±1.1 | 6.0±0.0 | 5.1±1.0 | 64±4 | 5.7±0.9 | 32±2 | Can not |
| Reference examples B | 5.0±0.0 | 5.3±0.5 | 5.3±1.2 | 54±8 | 3.3±1.2 | 24±2 | Energy |
| Reference examples C | 5.0±0.0 | 4.0±0.0 | 4.0±0.0 | 63±1 | 3.5±1.4 | 23±2 | Energy |
| Reference examples D | 10±0.0 | 5.0±0.0 | 4.1±0.4 | 63±0 | 5.5±1.4 | 31±1 | Can not |
| 2 | 7 | 5 | 5 | 62 | 4 | 27 | |
| 3 | 9 | 5.8 | 6 | 63 | 5 | 32 | |
| 4 | 10 | 6.3 | 5.8 | 65 | 6 | 35 | |
| 5 | 10 | 6 | 5.3 | 65 | 6 | 34 | |
| 6 | 10 | 5 | 4.8 | 65 | 6 | 32 | |
| 7 | 10 | 6.3 | 6 | 65 | 6 | 35 | |
| 8 | 9 | 5 | 5.3 | 63 | 6 | 32 | |
| 9 | 9 | 5.3 | 5 | 65 | 6 | 32 | |
| 10 | 10 | 6 | 6 | 64 | 6 | 34 | |
| 11 | 6 | 3.8 | 3.5 | 64 | 5.5 | 25 | |
| Reference examples E | 10 | 6 | 5 | 75 | 6 | 35 | Energy |
| 12 | 10 | 6.3 | 6 | 63 | 6 | 35 | |
| 13 | 10 | 6 | 5.8 | 64 | 6 | 34 | |
| 14 | 9 | 6 | 3 | 66 | 6 | 33 | |
| 15 | 10 | 6 | 6 | 65 | 6 | 35 | |
| 16 | 10 | 6 | 5.8 | 64 | 6 | 34 | |
| 17 | 10 | 6 | 5.8 | 64 | 6 | 34 | |
| 18 | 10 | 6 | 5.8 | 64 | 6 | 34 |
Top data declaration composition of the present invention is compared with the composition of reference examples has superior protective value.For example table 4 shows that composition of the present invention has comprised than the composition of the reference examples protective value of wide region more.Equally, aerosol stability is typical for composition of the present invention.
For example, listed demonstrating about the data through the fabric of the compositions-treated of embodiment 1 has than the grease proofness of better wearing and tearing of the fabric with the compositions-treated of reference examples A in the table 4.Equally, the composition of embodiment 1 has the aerosol stability that composition did not have of reference examples A.The data of reference examples B-D demonstrate the composition obvious worse performance in nearly all test than embodiments of the invention 1.Through as seen with the data of the data of embodiment 1 and embodiment 2-7, the repulsion performance of the present composition be subjected to relative weight than and the influence of the percentage of solid constituent in composition.The embodiment 8-11 representative composition by the monomer preparation different of the present invention with used monomer in the proportioning of embodiment 1.
Reference examples E represents with the solvent to be the prescription of base.These data show that it is the same effectively grease proofness of prescription and the water proofing property (for example comparative control example and embodiment 1) of base at least with the solvent with this that composition of the present invention has.Embodiment 12-18 shows the present composition effectiveness of (comprising the variation of various components), and is consistent with above-mentioned explanation.
Embodiment 19 and reference examples E and F
The contrast test data of the aerosol preparations of embodiment 19 and reference examples E and F have been collected.The data of having collected fabric A, B, C, D and E are listed in the following table 6.
Table 6
| Embodiment | Water proofing property | Grease proofness | The wearing and tearing grease proofness | The spraying grade | Drenched | Compound |
| Fabric A 19 reference examples F reference examples E | 10 7 9 | 6 6 5.5 | 6 5 4 | 65 50 72 | 5 3 5 | 34 26 31 |
| Fabric B 19 reference examples F reference examples E | 10 9 10 | 6 6 6 | 6 6 5 | 68 68 75 | 6 5 6 | 35 33 35 |
| Fabric C 19 reference examples F reference examples E | 10 10 10 | 6.5 6.5 5 | 5.5 5.8 5 | 80 75 80 | 6 6 6 | 36 36 34 |
| Fabric D 19 reference examples F reference examples E | 6 4 6 | 5.5 4.8 1.8 | 5.5 4.8 1.8 | 70 68 80 | 4 4 4 | 28 24 22 |
| Fabric E 19 reference examples F reference examples E | 8 6 9 | 5.5 4.5 2 | 1.5 1.5 3.3 | 72 70 82 | 4 4 5 | 26 23 28 |
Above data show when with reference examples F be the aerosol formulations of base when comparing with water, the composition of the embodiment of the invention 19 has more superior protective capability, especially for fabric A, D and E, as reflecting in comprehensive score.The water base aerosol of embodiment 19 have at least with reference examples E be the commeasurable combination property of composition of base with the solvent, for fabric D, have augmented performance than reference examples E.
Though narrated better example of the present invention in more detail at this, the example of being narrated is illustrative, and do not mean that any qualification.Those skilled in the art be from should understanding, can carry out various changes and modifications and do not break away from by the following the spirit and scope of the present invention that claims limited for described example.
Claims (32)
1. a fabric of handling the fibre-bearing goods makes it to have the composition of improved grease proofing and water proofing property, comprising:
(a) a kind of polyurethane with poly-alkoxylation of perfluoroalkyl side group, the polyurethane of described poly-alkoxylation comprise the trimerization of aliphatic series or fragrance or the product of poly isocyanate, fluorine-containing alcohol, amine or mercaptan and poly-(oxyalkylene) glycol or two mercaptan more;
(b) a kind of fluorinated acrylate polymer, it comprises fluorinated acrylate or methacrylate monomers, at least a alkyl acrylate or alkyl methacrylate monomer and a kind of product that contains the polymerizable cationic emulsifying agent of quaternary amine surfactants.
2. composition as claimed in claim 1 also comprises
(c) a kind of fluorine-containing aklylene glycol ester copolymer, it comprises fluorinated acrylate or methacrylate monomers, the product of polyacrylic acid alkylidene diol ester or polymethylacrylic acid alkylidene diol ester and poly-diacrylate alkylidene diol ester or poly dimethyl acrylic acid alkylidene diol ester;
(d) fluorine-containing adipate ester,
3. as the defined composition of claim 2, it is characterized in that fluorine-containing adipate ester is expressed from the next:
[R
fQ[OCH
2CH(CH
2Cl]
nO
2C(CH
2)
2]
2
R wherein
fIt is fluorine-containing aliphatic group;
Q is organic connection base;
N is the number of 1-5,
4. composition as claimed in claim 3 is characterized in that described fluorine-containing adipate ester is expressed from the next:
5. the composition described in claim 2 is characterized in that the blend of second component that composition is formed by (a), (c) and first component of (d) forming with by (b); Described first component and the weight ratio of described second component in described blend are 1: 25-25: 1.
6. composition as claimed in claim 5 is characterized in that described first component and the weight ratio of described second component in described blend are 1: 1.
7. composition as claimed in claim 2 is characterized in that described fluorine-containing aklylene glycol ester polymer comprises the repetitive of following random arrangement:
Wherein, R
fBe fluorine-containing aliphatic group, each R
3Be respectively H or CH
3, R
4Be the alkylidene with 2-4 carbon atom, Q is organic connection base, and X is the integer of 5-100.
8. composition as claimed in claim 7 is characterized in that described fluorine-containing aklylene glycol polymer is the polyoxyethylene trimer of following compounds:
(a)C
3F
17SO
2N(CH
3)C
2H
4OCOCH＝CH
2，
(b)CH
2＝C(CH
3)COO(CH
2CH
2O)
76H，
With
(c)CH
2＝C(CH
3)COO(CH
2CH
2O)
76COC(CH
3)＝CH
2
Its weight ratio is a: (b+c) be 1: 1, b: c is 3: 1.
9. composition as claimed in claim 1 is characterized in that the poly-hydrogen ester of poly-alkoxylation is expressed from the next:
Wherein: R
fIt is fluorine-containing fat-based;
R
hIt is not fluorine-containing alkyl;
Q is organic connection base;
A is trimerization or poly isocyanate residue more, promptly trimerization or more poly isocyanate partly deduct active-group that the NCO base forms;
(R
1)
yBe the polyoxyalkylene part, R
1Be oxyalkylene group or the cyclic ethers with 2-6 carbon atom, or have the ester moiety of 2-6 carbon atom, y is the number of 10-50;
X is O, S or is the connection base of end with O or S;
R
2Be trimerization or poly isocyanate base more, this trimerization or more two isocyanate group of poly isocyanic acid form described polyurethane-base, other isocyanates radical reaction formation-QR
fOr-QR
hSide group;
S is at least 1, can be 3 or bigger number;
Z is 0 or high to about 4 number,
T is at least 10 number.
10. composition as claimed in claim 1 is characterized in that described fluorinated acrylate polymer can be by following general formula:
Wherein: R
fIt is fluorine-containing aliphatic group;
Q is organic linking group;
R
bAnd R
b' be identical or different, be selected from H and have 1-4 carbon atom straight chain or branched hydrocarbyl or the carbocyclic ring of the about 3-12 of a formation carbon atom together, and composition thereof group;
R
d, R
d', R
d", R
d" ' can be identical or different, be selected from H or-CH
3
R
a, R
a', R
a" can be identical or different, be selected from alkyl with 1-18 carbon atom;
R
cBe saturated aliphatic series (straight or branched) or cyclic alkyl, or cycloalkyl and have the combination of the aliphatic alkyl of (have 4-30 usually, preferably have a 8-20) carbon atom at least;
Z is an anion, is selected from chlorine, bromine, iodine, sulfonate radical, alkyl azochlorosulfonate, phosphate radical etc.,
And composition thereof;
n
1, n
2, n
3Be respectively the number of 10-70;
n
4Be to be at least 1, be generally the number of 1-6.
11. composition as claimed in claim 10 is characterized in that fluorinated acrylate polymer is expressed from the next
12. composition as claimed in claim 1 is characterized in that the described fluorinated acrylate of described fluorinated acrylate polymer or methacrylate monomers are selected from methacrylic acid (the hot sulfonamido of N-methyl perfluor) ethyl ester, methacrylic acid (the hot sulfonamido of N-ethyl perfluor) ethyl ester, acrylic acid (the hot sulfonamido of N-methyl perfluor) ethyl ester, acrylic acid (the hot sulfonamido of N-ethyl perfluor) ethyl ester and its composition.
13. composition as claimed in claim 1 is characterized in that at least a described alkyl acrylate of described fluorinated acrylate polymer or alkyl methacrylate are selected from methyl acrylate, ethyl acrylate, butyl acrylate, Hexyl 2-propenoate, Isooctyl acrylate monomer, isodecyl acrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate and composition thereof.
14. composition as claimed in claim 13 is characterized in that described butyl acrylate is a n-butyl acrylate, described butyl methacrylate is a n-BMA.
15. composition as claimed in claim 1 is characterized in that described polymerizable cationic emulsifying agent is the quaternary amine of following general formula:
Wherein: R
a" be alkyl with 1-18 carbon atoms;
R
bAnd R
b' be identical or different, be selected from H and have 1-4 carbon atom straight chain or branched hydrocarbyl or the carbocyclic ring of the about 3-12 of a formation carbon atom together, and composition thereof group;
R
d" ' be H or-CH
3
R
cBe saturated aliphatic series (straight or branched) or cyclic alkyl, or have (have 4-30 usually, preferably have 8-20) aliphatic alkyl of carbon atom and the combination of cycloalkyl at least;
Z is an anion, is selected from chlorine, bromine, iodine, sulfonate radical, alkyl azochlorosulfonate, phosphate radical etc.,
And composition thereof.
16. composition as claimed in claim 1 is characterized in that the polymerizable cationic emulsifying agent is methacrylic acid N, N-dimethylamino ethyl ester and carbon chain lengths are about the product of the alkyl halide of 4-30 carbon atoms.
17. composition as claimed in claim 16 is characterized in that described alkyl halide is a bromohexadecane.
18., comprising as any one described composition among the claim 1-17:
(a) a kind of polyurethane with poly-alkoxylation of perfluoroalkyl side group, described polyurethane comprise the trimerization of aliphatic series or fragrance or the product of poly isocyanate, fluorine-containing alcohol, amine or mercaptan and poly-(oxyalkylene) glycol or two mercaptan more;
(b) a kind of fluorinated acrylate polymer, it comprises fluorinated acrylate or methacrylate monomers, first alkyl acrylate or alkyl methacrylate monomer, second alkyl acrylate or alkyl methacrylate monomer and a kind of polymeric reaction product that contains the polymerizable cationic emulsifying agent of quaternary amine surfactants;
(c) a kind of poly-fluorine-containing acrylic aklylene glycol ester copolymer, it comprises fluorinated acrylate or methacrylate monomers, polyacrylic acid alkylidene diol ester or polymethylacrylic acid alkylidene diol ester and
The product of poly-diacrylate alkylidene diol ester or poly dimethyl acrylic acid alkylidene diol ester;
(d) fluorine-containing adipate ester;
It is characterized in that said components is with (a)+(c)+(d): be 25 (b): 1-1: 25 weight ratio is blended together in composition.
19. composition as claimed in claim 18 is characterized in that poly-alkoxylation polyurethane is expressed from the next:
Wherein: R
fIt is fluorine-containing fat-based;
R
hIt is not fluorine-containing alkyl;
Q is organic connection base;
A is trimerization or poly isocyanate residue more, promptly trimerization or more poly isocyanate partly subtract
Deactivation-the basic group that forms of NCO;
(R
1)
yBe the polyoxyalkylene segment, R
1Be the oxyalkylene group with 2-6 carbon atoms, y is about 20-40 number;
X is O, S or is the connection base of end with O or S;
R
2Be trimerization or poly isocyanate residue more, this trimerization or more two isocyanate group of poly isocyanic acid form described polyurethane-base, other isocyanates radical reaction formation-QR
fOr-QR
hSide group;
S is at least 1, can be 3 or bigger number;
Z is 0;
T is at least 10 number.
20. composition as claimed in claim 18 is characterized in that described fluorine-containing aklylene glycol ester polymer is weight ratio a: (b+c) be 1: 1, b: c is 3: 1 a following formula polyethylene glycol oxide trimer:
(a)C
8F
17SO
2N(CH
3)C
2H
4OCOCH＝CH
2，
(b)CH
2＝C(CH
3)COO(CH
2CH
2O)
76H，
With
(c)CH
2＝C(CH
3)COO(CH
2CH
2O)
76COC(CH
3)＝CH
2。
21. composition as claimed in claim 18 is characterized in that described fluorine-containing adipate ester is expressed from the next:
22. composition as claimed in claim 18 is characterized in that described fluorinated acrylate polymer is by following general formula:
Wherein: R
fIt is fluorine-containing aliphatic group;
Q is organic linking group;
R
bAnd R
b' be identical or different, be selected from H and have the straight or branched alkyl of 1-4 carbon atom or the carbocyclic ring of formation about 3-12 carbon atom together, and composition thereof group;
R
d, R
d', R
d", R
d" ' can be identical or different, be selected from H or-CH
3
R
a, R
a', R
a" can be identical or different, be selected from alkyl with 1-18 carbon atom;
R
cBe saturated aliphatic series (straight or branched) or cyclic alkyl, or cycloalkyl and have the combination of the aliphatic alkyl of (have usually 4-30, preferably have 8-20 a) carbon atom at least;
Z is an anion, is selected from chlorine, bromine, iodine, sulfonate radical, alkyl azochlorosulfonate, phosphate radical etc., and composition thereof;
n
1, n
2, n
3Be respectively 10-70 number;
n
4Be to be at least 1, be generally 1-6 number.
23. composition as claimed in claim 22 is characterized in that described fluorinated acrylate polymer is expressed from the next:
24. composition as claimed in claim 18 is characterized in that the described fluorinated acrylate of described fluorinated acrylate polymer or methacrylate monomers are selected from methacrylic acid (the hot sulfonamido of N-methyl perfluor) ethyl ester, methacrylic acid (the hot sulfonamido of N-ethyl perfluor) ethyl ester, acrylic acid (the hot sulfonamido of N-methyl perfluor) ethyl ester, acrylic acid (the hot sulfonamido of N-ethyl perfluor) ethyl ester and its composition.
25. composition as claimed in claim 18 is characterized in that at least a described alkyl acrylate of described fluorinated acrylate polymer or alkyl methacrylate are selected from methyl acrylate, ethyl acrylate, butyl acrylate, Hexyl 2-propenoate, Isooctyl acrylate monomer, isodecyl acrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate and composition thereof.
26. composition as claimed in claim 25 is characterized in that described butyl acrylate is a n-butyl acrylate, described butyl methacrylate is a n-BMA.
27. composition as claimed in claim 18 is characterized in that described polymerizable cationic emulsifying agent is the quaternary amine of following general formula:
Wherein: R
a" be alkyl with 1-18 carbon atoms;
R
bAnd R
b' be identical or different, be selected from H and have 1-4 carbon atom straight chain or branched hydrocarbyl or the carbocyclic ring of the about 3-12 of a formation carbon atom together, and composition thereof group;
R
d" ' but H or-CH
3
R
cBe saturated aliphatic series (straight or branched) or cyclic alkyl, or have (have 4-30 usually, preferably have 8-20) aliphatic alkyl of carbon atom and the combination of cycloalkyl at least;
Z is an anion, is selected from chlorine, bromine, iodine, sulfonate radical, alkyl azochlorosulfonate, phosphate radical etc., and composition thereof.
28. composition as claimed in claim 18 is characterized in that the polymerizable cationic emulsifying agent is methacrylic acid N, N-dimethylamino ethyl ester and carbon chain lengths are about the product of the alkyl halide of 4-30 carbon atoms.
29. composition as claimed in claim 28 is characterized in that described alkyl halide is a bromohexadecane.
30. composition as claimed in claim 18 is characterized in that described fluorine-containing adipate ester is expressed from the next:
[R
fQ[OCH
2CH(CH
2Cl]
nO
2C(CH
2)
2]
2
Wherein: R
fIt is fluorine-containing aliphatic group;
Q is organic connection base;
N is 1-5 number.
31. composition as claimed in claim 30 is characterized in that described fluorine-containing adipate ester is expressed from the next:
32. the purposes of any one described composition in handling fiber containing base material among the claim 1-31.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95193390A CN1077935C (en) | 1995-03-31 | 1995-03-31 | Aqueous oil and water repellent compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95193390A CN1077935C (en) | 1995-03-31 | 1995-03-31 | Aqueous oil and water repellent compositions |
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| CN1149897A CN1149897A (en) | 1997-05-14 |
| CN1077935C true CN1077935C (en) | 2002-01-16 |
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|---|---|---|---|
| CN95193390A Expired - Fee Related CN1077935C (en) | 1995-03-31 | 1995-03-31 | Aqueous oil and water repellent compositions |
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| WO2005066224A1 (en) * | 2003-12-31 | 2005-07-21 | 3M Innovative Properties Company | Water-and oil-repellent fluoroacrylates |
| CN100342075C (en) * | 2004-02-24 | 2007-10-10 | 福盈科技化学股份有限公司 | Hydrophobic and oleophobic agent in fluoric solvent type and producing method |
| CA2698827C (en) * | 2007-09-28 | 2014-09-09 | Nichiban Co., Ltd. | Makeup-assisting patch and makeup method using the patch |
| JP2013136687A (en) * | 2011-12-28 | 2013-07-11 | Daikin Industries Ltd | Surface treating agent, and method for producing the same |
| CN104093757A (en) * | 2012-01-31 | 2014-10-08 | 旭硝子株式会社 | Fluorine-containing copolymer, method for producing same, and water repellent/oil repellent agent composition |
| JPWO2013115197A1 (en) * | 2012-01-31 | 2015-05-11 | 旭硝子株式会社 | Fluorine-containing copolymer, process for producing the same, and water / oil repellent composition |
| JP5242841B1 (en) * | 2012-10-13 | 2013-07-24 | 日本アエロジル株式会社 | Water- and oil-repellent coating films and articles containing the coating films |
| CN104342930A (en) * | 2013-08-08 | 2015-02-11 | 上海雅运纺织助剂有限公司 | Aqueous water and oil proofing agent composition and preparation method thereof |
| WO2021251302A1 (en) * | 2020-06-10 | 2021-12-16 | ダイキン工業株式会社 | Fluorine-containing compound |
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|---|---|---|---|---|
| EP0109171A1 (en) * | 1982-10-13 | 1984-05-23 | Minnesota Mining And Manufacturing Company | Fluorochemical copolymers and ovenable paperboard and textile fibers treated therewith |
| WO1993001349A1 (en) * | 1991-07-10 | 1993-01-21 | Minnesota Mining And Manufacturing Company | Aqueous oil and water repellent compositions |
-
1995
- 1995-03-31 CN CN95193390A patent/CN1077935C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0109171A1 (en) * | 1982-10-13 | 1984-05-23 | Minnesota Mining And Manufacturing Company | Fluorochemical copolymers and ovenable paperboard and textile fibers treated therewith |
| WO1993001349A1 (en) * | 1991-07-10 | 1993-01-21 | Minnesota Mining And Manufacturing Company | Aqueous oil and water repellent compositions |
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