CN1148394C - Mixed fluorochemical hydrocarbon condensates to impart oil and water repellency to substrate - Google Patents
Mixed fluorochemical hydrocarbon condensates to impart oil and water repellency to substrate Download PDFInfo
- Publication number
- CN1148394C CN1148394C CNB971821054A CN97182105A CN1148394C CN 1148394 C CN1148394 C CN 1148394C CN B971821054 A CNB971821054 A CN B971821054A CN 97182105 A CN97182105 A CN 97182105A CN 1148394 C CN1148394 C CN 1148394C
- Authority
- CN
- China
- Prior art keywords
- fluoro
- containing composition
- methylolation
- base material
- carbon atom
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The present invention provides a fluorine-containing composition which comprises one or multiple condensation compounds of the following components: (i) hydroxymethyl amine or an alkoxyl derivative thereof, (ii) hydrocarbons of alcohol, thiol, amide or acid at least containing 6 carbon atoms, which are selected from alkyl selectively substituted by 3 substituents, and (iii) fluoride represented in the general formula (I) disclosed in the specification. Rf in the general formula (I) is a fluorinated aliphatic series group, X1 is an organic bivalent linking group, Z1 is selected from hydroxy, thiol, amide or acid, and n is 0 or 1. The present invention also provides the application of the composition to enable base materials, particularly fabric or leather, to have water repellency and oil repellency, and also provides a method for treating the base materials by using the fluorine-containing composition and the treated base materials. The fluorine-containing composition is easily dissolved in a non-fluorinated solvent so as to generate fine water repellency and fine oil repellency, particularly on leather base materials.
Description
1. invention field
The present invention relates to make base material (particularly fibrous substrate, as fabric or leather) to have the fluoro-containing composition (fluorochemical composition) of water repellency and/or oil repellent.Specifically, the present invention relates to fluoro-containing composition based on the condenses of the aminoresin that contains fluoro aliphatic group and alkyl.The present invention also relates to the preparation method of these condensess and handle the method for base material with it.
2. background of invention
Organofluorine compound (being fluorochemical) is to contain the partly material of (being that chemical reactivity is arranged in organic reaction) of fluorocarbon character part (promptly hydrophobic, oleophobic and unreactiveness) and organic or hydrocarbon properties.Some fluorochemical is known for general public, as SCOTCHGARD
TMThe carpet protective material, it makes carpet produce water and oil repellant and anti-spot and didirtresistance.Other this class material has various industrial uses, as reducing the surface tension of liquid, reduces the vapo(u)rability and the inflammableness of volatile organic liquid, and the levelling property that improves organic polymer paint.
According to H.C.Fielding, " organofluorine compound and application thereof " R.E.Banks, Ed., among the Society ofChemical industry described in the 214th page (1979), organofluorine compound as tensio-active agent and surface treatment agent mainly due to C
6-C
12The fluorine-based extremely low free surface energy of carbon.Above-mentioned organic fluorine material generally is to contain with unit price fluoro aliphatic group (as perfluoroalkyl, to be generally C
nF
2n+1, n is at least 3 in the formula, and the terminal portions of this group is trifluoromethyl-CF
3) material of fluorine of form and bond with carbon.
Be used to handle the fluoride-based of base material (particularly fabric and leather) and refuse water and/or refuse oily composition to have sizable commercial significance.The refusing water and/or refuse to have in the oil compositions with aminoresin of the processing base material that is known in the art, particularly the condenses of formaldehyde and melamine is the composition on basis.For example, the water miscible liquid that contains the fluorochemical (FC-melamine) of melamine is refused oil and water repllents industrial being used as.Yet,, with the high-energy emulsifying device this solution is distributed in the water that contains emulsifying agent then because the poor solubility of FC-melamine in common organic solvent generally needs earlier the FC-melamine to be dissolved in fluorated solvent or the chlorofluorination solvent.Can reclaim this solvent by distillation then.This method is a trouble, expensive, and needs to use the disadvantageous solvent of environment.
DE 3133303 has described the FC-melamine that the condensation by the hexamethylol melamine of height etherificate and perfluorination mercaptan makes.The aqueous emulsion of these compounds is used to handle fabric and leather, so that water and oil repellent are refused in its generation.Though can obtain good effect at fabric, the effect of FC-melamine on leather requires further improvement.In addition, as mentioned above, these compounds generally only are dissolved in the fluorated solvent.
United States Patent (USP) 3,510,455 have disclosed the method for fluoridizing prepolymer by the prepared in reaction thermoset between aldehyde, nitrogenous compound (as urea or melamine) and aliphatic fluoride.Above-mentioned aliphatic fluoride contains perfluoroalkyl chain and has at least one functional group of active hydrogen atom.These prepolymers are dissolvable in water and are solidified into the successive adhesive film in the common solvent and on polar surfaces.It is said that the prepolymer for preparing by this patent is not suitable for handling textile material.
United States Patent (USP) 3,362,782 have disclosed the selective etherification methylolation compound and 1 of heterocyclic nitrogen, 1-dihydro perfluoroalkyl alcohol or perfluorocarboxylic acid acid amides (as with perfluor oxygen in heptan ylmethyl five (methoxymethyl) melamine) condensation product in the application aspect the soil-repellent finishing of cellulosic fabric material.Organic solvent is used for this purposes.Yet, refuse oil and refuse the water effect and can not satisfy present needs with what these condensation products obtained.In addition, must use a large amount of this condensation products.
United States Patent (USP) 3,506,661 have disclosed a kind of fabric that is used to handle, especially for the derivative of fatty acid of the melamine of refusing water retting.It is said that these melamine derivatives are dissolvable in water in chlorinated hydrocarbon, the aromatic hydrocarbons (as benzene, crude benzol and toluene).Yet these compounds are uncomfortable as oil-repellent agent, nor can produce required water repellency at present at fabric.
United States Patent (USP) 3,480,579 have disclosed the application that the condenses of six alkoxy methyl melamines and longer chain fatty acid produces water repellency in the composition on fabric.According to this announcement, said composition better also contains to fluoridize refuses oil and refuses the fluorine-containing aliphatic cpd of hydrate, particularly polymeric.
United States Patent (USP) 5,292,796 have disclosed the fluoro-containing composition that contains fluorochemical.Described fluorochemical contain by-O-,-S-,-NH-or CO
2-fluorine-containing oligomer the part that is connected with the part that contains the group that obtains by aminoresin.The concrete aminoresin that discloses comprises methylolation melamine, benzoguanamine and acetoguanamine and their derivative that methylates.Said composition can be used for producing the competent wear-resistant oily water repellency of refusing.In addition, according to the announcement of this patent, aminoresin can contain long-chain aliphatic group, and if necessary, in order to improve the hydrophobicity of pending base material, can comprise the compound of the condenses and so on of lipid acid and melamine or urea derivatives.According to the embodiment of this patent, with fluoride dissolution in hexafluoro dimethylbenzene, then with solution in water the emulsification of tensio-active agent with gained.
3. summary of the invention
The invention provides a kind of fluoro-containing composition, it is easy to be dissolved in the nonfluorinated organic solvent, and can on base material (particularly fabric or leather substrate), provide good and/or improved refuse water and/oil repellent.
Fluoro-containing composition of the present invention contains one or more condensess of following component: (i) methylolation amine or its alkoxy derivative, (ii) be selected from that alkyl contains 6 carbon atoms at least and optionally by the hydrocarbon compound of the alcohol that replaces up to 3 substituting groups, mercaptan, acid amides or acid with (iii) use the fluorochemical of general formula (I) expression:
R
f-(X
1)
n-Z
1 (I)
In the formula:
R
fBe to fluoridize aliphatic group;
X
1It is organic divalent linker;
Z
1Be hydroxyl, mercaptan, acid amides or acidic group; N is 0 or 1.
The present invention also provides this fluoro-containing composition to make base material have the purposes of oil repellent and/or water repellency.
The present invention also provides with the base material that contains this fluoro-containing composition on the method for this fluoro-containing composition processing base material and the surface.
The present invention also provides the preparation method of fluoro-containing composition.
4. Fa Ming detailed description
This fluoro-containing composition can make following component reaction make in the presence of acid catalyst: (i) methylolation amine or its alkoxy derivative, (ii) be selected from that alkyl contains 6 carbon atoms at least and optionally by the hydrocarbon compound of the alcohol that replaces up to 3 substituting groups, mercaptan, acid amides or acid with (iii) use the fluorochemical of general formula (I) expression:
R
f-(X
1)
n-Z
1 (I)
In the formula:
R
fBe to fluoridize aliphatic group;
X
1It is organic divalent linker;
Z
1Be hydroxyl, mercaptan, acid amides or acidic group (as the carboxylic acid group); N is 0 or 1.
Methylolation melamine or its alkoxy derivative can be selected from methylolation melamine, methylolation urea, methylolation benzoguanamine, methylolation acetoguanamine or their alkoxy derivative.Example comprises hexamethoxy methyl cyanuramide, trimethoxy methylmelamine, dimethoxy-methyl urea, dimethoxy-methyl ethylidene-urea, dimethoxy-methyl propylidene urea.
The alkoxy derivative of methylolation amine is most preferred in the present invention, because they have better stability in acidic medium, and can avoid forming a large amount of cross-linked materials in the process of preparation condenses of the present invention.Particularly preferably be C
1-C
4Alkoxy derivative, more preferably C
1-C
2Derivative.The alkoxy derivative of methylolation amine is better by the height etherificate, and promptly at least 70%, better at least 90% alcohol radical is by etherificate.The alkoxy derivative of particularly preferred methylolation amine comprises hexamethylol melamine ether, its methylol pure etherificate that contains 1-4 (particularly 1-2) carbon atom.Be used for commercially available hexamethoxy methyl cyanuramide of the present invention and comprise CYMEL
TM300, CYMEL
TM301, CYMEL
TM303 and CYMEL
TM350, they are different on the content of free methylol.
The mixture of methylolation amine and/or its alkoxy derivative also can be used for preparing fluoro-containing composition.
The preferred hydrocarbons compounds that is used to prepare fluoro-containing composition can be represented with general formula I I:
R
h-(X
2)
m-Z
2 (II)
R
hIt is alkyl;
X
2It is organic divalent linker;
Z
2Be hydroxyl, mercaptan, acid amides or acidic group (as the carboxylic acid group); With m be 0 or 1.
The group that is made of hydrogen and carbon not only represented in used term " alkyl " among the present invention, and the expression group that can be replaced arbitrarily by functional group's (as halogen, hydroxyl, amino etc.).
R
hComprise and contain 6 carbon atoms alkyl of (better containing 8 carbon atoms at least) at least.These alkyl can randomly contain 1-3 substituting group, and these substituting groups better are selected from chlorine, bromine, fluorine, hydroxyl, amino, alkoxy carbonyl, alkoxyl group etc.Yet this alkyl is more preferably unsubstituted, and is preferably saturated.Particularly preferred R
hGroup comprises unsubstituted straight or branched alkyl.These alkyl better contain 8 carbon atoms at least.R
hGroup also can contain alicyclic radical, as cyclohexyl or cyclohexenyl.According to the present invention, also can in the condensation reaction of preparation fluoro-containing composition, use the mixture of hydrocarbon compound, thereby produce the condenses that contains different alkyl.Preferred mixture comprises R
hBe the hydrocarbon compound and the R of straight chained alkyl
hIt is the hydrocarbon compound of branched-chain alkyl.
The R that is suitable for the fluorochemical of general formula (I)
fGroup be fluoridize, stablize, inertia, better be saturated, nonpolar, unit price aliphatic group.They can be straight chain, side chain, ring-type or their combination.They only can contain the heteroatoms with carbon atom bonding, as oxygen, divalence or sexavalence sulphur or nitrogen.R
fBetter be complete fluorizated group, if but do not have more than one hydrogen or chlorine atom on per two carbon atoms, hydrogen or chlorine atom can be used as substituting group and exist.R
fGroup contains 3 carbon atoms at least, better contains 3-14 carbon atom, and better contains the fluorine of the 40-80% weight of having an appointment, and better contains the fluorine of the 50-78% weight of having an appointment.R
fThe terminal portions of group is a full-fluorine group, and it better contains 7 fluorine atoms at least, as CF
3CF
2CF
2-, (CF
3)
2CF-, F
5SCF
2-.Preferred R
fGroup is a fluorizated fully fully or basically, better is that general formula is C
tF
2t+1The perfluoroaliphatic group group of (t is 3-14 in the formula).
Above-mentioned general formula (I) and (II) in linking group X
1And X
2Better contain about 20 carbon atoms of 1-.They can randomly comprise and contain oxygen, nitrogenous or sulfur-containing group or their combination.This linking group better is selected from straight chain, side chain or cyclic alkylidene, arylidene, inferior aralkyl, alkylsulfonyl, poly-(oxyalkylene), inferior urethane groups (urethanylene), ureylene, urea groups alkylidene group or sulfonamido alkylidene group.Representative X-ray
1Group is described in the following table.In this table, k represents the integer of 1-about 20 separately, and g is the integer of 0-about 10, and h is the integer of 1-about 20, and R ' is hydrogen, phenyl or the alkyl that contains 1-4 carbon atom, R
2' be the alkyl that contains about 20 carbon atoms of 1-.
-SO
2NR′(CH
2)
k-
-CONR′(CH
2)
k-
-(CH
2)
k-
-CH
2CH(OH)CH
2-
-CH
2CH(OR′
2)CH
2-
-CH＝CH
2(CH
2)
k-
-(CH
2)
k-O(CH
2)
k-
-(CH
2)
k-S(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-
-OC
6H
4CH
2-
-(CH
2)
hO(O)C(CH
2)
6O)
8(CH
2)
6-
Preferred X
1Group comprises-(CH
2CH
2)
k-and-SO
2N (R) CH
2CH
2-(k is 1 or 2, and R is C
1-C
4Alkyl).If R
fBe full-fluorine group, generally need linking group (X
1).
Fluorochemical can change with the relative mol ratio of hydrocarbon compound with methylolation amine or its alkoxy derivative in the reaction mixture.Any remaining alkoxyl group on the condenses of the present invention be used in the drying used and the curing schedule with base material on reactive group (hydroxyl or amino) carry out crosslinked.Those skilled in the art should understand that also the preparation method of this fluoro-containing composition can make the mixture of the condenses that contains different fluorine-containing (fluorochemical) groups of measuring and alkyl.According to the present invention, these mixtures need not to separate various condensess and just can use.
The known acid catalyst that can be used for condensation reaction can be used for aforesaid method.In general, strong acid catalyst (as tosic acid, amphene sulfonic acid, amberlyst IR-120 and methylsulfonic acid) is preferred.
According to the optimal way that carries out condensation reaction, methylolation amine or its alkoxy derivative, fluorochemical and hydrocarbon compound are mixed, and be heated to till the formation uniform mixture.Can add catalyzer then.This reaction does not more add under the condition of solvent to be carried out, and reduces viscosity though may need to add high boiling solvent.The term " high boiling point " relevant with this embodiment is meant the solvent on the boiling point of the alcohol (being generally methyl alcohol) that boiling point forms in condensation course.
In reaction process, can remove volatile alcohol of formation by distillation, thereby allow balance shift to the direction that forms condenses.In order to reach this purpose, higher at least 20 ℃ than the boiling point of the alcohol that forms in the condensation course more fortunately temperature is carried out condensation.In this concrete embodiment, condensation reaction is carried out in two steps: react at the reaction mixture that makes catalyzer and component (i) than the boiling point of the volatile alcohol that forms high at least 20 ℃ or higher temperature, (ii) reach (iii) (1), till from reaction mixture, steaming seldom or can not steaming the alcohol of waving property, and (2) raise the temperature of reaction mixture about 40-80 ℃ then, better about 40 or 50 ℃, generally last 1 or 2 hour.
Also need on the reaction surface of reaction mixture, keep flowing of rare gas element (as nitrogen), to avoid foaming or to add fast response.
This fluoro-containing composition may be dissolved in the various nonfluorinated organic solvents, as acetic ester (ethyl acetate), ether (dipropylene glycol monomethyl ether, tetrahydrofuran (THF), glycol ether), ketone (acetone, butanone, methyl iso-butyl ketone (MIBK)), alcohol (methyl alcohol, ethanol, Virahol, ethylene glycol), dimethyl pyrrolidone and their mixture.Therefore, this fluoro-containing composition can use by the solution in these organic solvents, perhaps prepares the aqueous emulsion of this fluoro-containing composition by well-known technology.For example under high degree of agitation, the solution of fluoro-containing composition in organic solvent (as ethyl acetate) can be added in the aqueous solution of emulsifying agent gradually.Then the premixture that makes is like this carried out supersound process or high-shear homogenizing, obtain the emulsified water emulsion of this fluoro-containing composition.If necessary, can remove organic solvent by underpressure distillation again.
Fluoro-containing composition of the present invention application process routinely uses, and can be used as aqueous emulsion.Perhaps used as the treatment compositions in the solvent.Aqueous emulsion generally contains water, make the base material of processing produce the significant quantity of rejection fluoro-containing composition, stablize the tensio-active agent of the significant quantity of this emulsion.By 100 weight parts fluoro-containing composition of the present invention, the content of water better is about the 70-20000 weight part.The content of tensio-active agent better is about the 1-25 weight part, and more preferably about 5-10 weight part is by the fluoro-containing composition of 100 weight parts.Conventional cationic, non-ionic type, anionic and amphoteric ionic surfactant are suitable for.
According to the present invention, select to be applied to the consumption of the treatment compositions of base material, make on substrate surface, to produce enough height or required water and the oil repellent refused.Described consumption generally makes and have 0.01-5% weight on the base material of handling, is preferably the fluoro-containing composition of 0.05-2% weight, by the weight of base material.Being enough to produce the required consumption of refusing water and oil repellent can rule of thumb determine, and increases on demand.
In fluoro-containing composition of the present invention, can add various additives,, for example can add the hydro carbons extender, also can add fat liquor or synthetic tanning agent in order to produce didirtresistance on the processing base material, to produce special performances.
Improve flexibility or " feel " of the base material of handling with the present composition if desired, can use floride-free softening agent, as hydrogen alkyl polysiloxane class or known other material of those skilled in the art of some polyethylene kind, polydimethylsiloxane class, modification.
Composition of the present invention also can be used in combination with other fluorinated product, polymkeric substance or auxiliary product, as the swelling agent of polyoxyethylene glycol, colloid (as starch, dextrin, casein, sizing agent or fixing agent), the material that improves anti-spot, detergency, flame retardant resistance or static resistance, buffer reagent, mycocide, white dyes, sequestrant, inorganic salt, tensio-active agent or promotion infiltration.Specially suitable subsidiary products and consumption thereof can be selected easily by those skilled in the art.
The base material of refusing water and oil repellent compositions-treated with the present invention has no particular limits, and comprises fibrous material, as fabric, fiber, non-woven fabrics, leather, paper, carpet, plastics, timber, metal, glass.This fluoro-containing composition is specially adapted to make leather to produce water repellency and oil repellent.These character produce when can be in the tannery of leather handling with rotary drum.Generally with at room temperature dry 24 hours of leather substrate, solidified 5-10 minute at 60-70 ℃ more then.
In order to handle fabric substrate, base material can be immersed in the emulsion of a dilution.Can remove unnecessary emulsion with saturated base material by a pad fix machine/rolling mill, drying and one period that is enough to the solidification treatment base material of curing in a baking oven then.Look used particular system and application process and different, this curing generally temperature between 110-190 ℃ carries out.In general, in 150-170 ℃ temperature-curable about 20 seconds to 10 minute, it is suitable being preferably 3-5 minute.Processing base material after the curing can use on demand, as is attached to or makes clothes.
Following the present invention is further illustrated with reference to embodiment, yet the present invention is not limited to these
Embodiment.
Embodiment
Preparation and treatment step
Preparation contains the processing bath of a certain amount of fluoro-containing composition.It all is commercially available being used to estimate the base material that the present invention handles, and lists in as follows:
PES/CO: gray polyester/cotton 65/35, model 2681.2, available from Utexbel N.V., Ghent,
Belgium
PA: polyamide microfibres, model 7819, available from Sofinal, Belgium
Leather: the Reutlingen leather, available from Reutlingen, Germany
The various relevant datas of refusing water and oil repellent shown in embodiment and the Comparative Examples record according to following measuring method, and judgement criteria is as follows:
Spray grade (SR)
The spray quinoline grade of handling base material is that the numerical value of base material to the dynamic water repellency that is injected in the water above it is handled in expression.This water repellency is measured with No. 22 standard test methodss as description among the Technical Manual and Yearbook of theAmerican Association of Textile Chemists and Colorists (AATCC) that published in 1985, and represents with " the spray quinoline grade " of testing substrates.This spray quinoline grade is by obtaining 250 ml waters spray quinoline 15 centimetres of distant places on base material.The visual assessment wetness degree: with the rank of 0-100,0 expression complete wetting, 100 expressions do not have wetting fully.
Water repellency (WR)
Water-isopropanol test liquid assay is handled the water repellency (WR) of base material, represents to handle the water repellency of base material with " WR " grade of handling base material.The base material that is permeated by water or the processing base material of the water of ability 100% (0% isopropyl alcohol) liquid (promptly not having most infiltrative test(ing) liquid) only, its grade is 0, and the processing base material of ability 0% water-100% isopropanol test liquid (promptly having most infiltrative test(ing) liquid), its grade is 10.Other intermediate value is measured with another kind of water-isopropanol test liquid.The percentage ratio of water and Virahol respectively multiply by 10 in this test(ing) liquid.The WR grade is corresponding to the most porous test(ing) liquid of porous or wetting base material not after 15 seconds contacts.In general, to be equal to or greater than 2 be suitable to the water repellency grade.
Oil repellent (OR)
Handling the oil repellent of base material measures with the standard test methods No.118-1983 of dying of U.S. textile chemical work NAB National Association 0f Broadcasters (AATCC).This test method is to handle tolerance that base material oozes different surfaces tensile oil.If handle only ability Nujol mineral oil (test oil that perviousness is the poorest) of base material, its grade is 1, and if handle base material ability heptane (test oil that perviousness is best), its grade is 8.Other intermediate value is determined with the mixture of other listed in the following table pure oil or oil.
Standard test liquid
| AATCC oil repellent grade point | Composition |
| 1 | Nujol |
| 2 | Nujol /n-hexadecane 65/35 |
| 3 | N-hexadecane |
| 4 | N-tetradecane |
| 5 | N-dodecane |
| 6 | N-decane |
| 7 | Octane |
| 8 | Normal heptane |
Washing procedure
The program that proposes below is used for " 5 washings (5L) " are appointed as in preparation at following embodiment processing base material sample.
In this test, will be generally square, weight is 230 grams, area is 400-900 centimetre
2A slice handle back base material and ballast sample (be generally square, weight be the fabric on the limit of sewing it up of 1.9 kilograms or 8oz, and its area is 8100 centimetres
2) put into a washing machine together.Add conventional washing composition (" Tide " 46 grams), hot water (40 ℃ ± 3 ℃) is added washing machine to high-water.With 12 minutes mode of a common circulation cleaning, with base material and ballast sample washing 5 times (need not be dry between each circulation), rinsing 5 times and centrifuge dehydration then.Be set in the base material after the flatiron flatiron oven dry of the specified temperature of each base fabrics with temperature.
Abbreviation
Use following abbreviation and trade name in an embodiment:
HMMM: hexamethoxy methyl cyanuramide, available from Dyno Cyanamid
MeFOSE：C
8H
17SO
2N(CH
3)CH
2CH
2OH
EtFOSE：C
8H
17SO
2N(CH
2CH
3)CH
2CH
2OH
The Guerbitol-18:2-alkyl chain triacontanol is called Guerbet alcohol, mean chain length C-18; Purchase
From Henkel, Dusseldorf, Germany
Prisorine
TM3515: the isooctadecanol of methyl-branched; Available from Unichema Chemie, Gouda,
The Netherlands
Ethoquad
TM18/25: methyl chloride polyoxyethylene (15) octadecyl ammonium, available from Akzo,
Littleborough，UK
Ethoquad
TMHT-25: methyl chloride polyoxyethylene (15) hydrogenated tallow ammonium, available from Akzo,
Littleborough，UK
Marlowet
TM5401: the polyethoxylated amine salt, available from Huls, Marl, Germany
Kotylene
TM: polyoxyethylene (20) anhydro sorbitol monooleate
Siponate
TMDS-10: Sodium dodecylbenzene sulfonate
If do not explain in addition, the umber in following embodiment or the specification sheets rest part, ratio, percentage ratio etc. are all by weight.
A. synthetic fluoro-containing composition
Now the listed several fluoro-containing compositions of table 1 have been prepared according to the following general step that is used for synthetic HMMM/EtFOSE/ stearyl alcohol 1/3/3.
In 1 liter of 3 mouthfuls of reaction flask that mechanical stirrer, thermometer, nitrogen ingress pipe, Dean-Rodney Stark condenser and heating jacket be housed, add 0.167 mole of HMMM, 0.5 mole of EtFOSE and 0.5 mole of stearyl alcohol.This mixture stirred and be heated to 80 ℃, until solution becomes get transparent till.Add 0.72 gram Catalyzed by p-Toluenesulfonic Acid agent then.This reaction mixture is heated to 90 ℃ gradually, keeps stable nitrogen gas stream simultaneously.Methyl alcohol is distilled in Dean-Rodney Stark condenser.Allow this be reflected at 90 ℃ and carried out 3 hours, then this mixture is heated to 140 ℃ gradually.After 3 hours, the final reacting product that obtains is a viscous batter 140 ℃ of heating.After reaction mixture is cooled to 100 ℃, add 319 gram ethyl acetate, obtain the solution of 60% melamine in ethyl acetate with dropping funnel.
Embodiment F C-1 to FC-15 and Comparative Examples C-FC-1 to C-FC-5
The emulsification of B fluoro-containing composition
According to following for Marlowet
TMThe general step of 5401 emulsifying agents carries out emulsification with different emulsifying agents or emulsifier mixture with the above-mentioned fluoro-containing composition that makes.
In the above-mentioned fluorine-containing amine condenses (40% solid) that makes of 66.7 grams, add 33.3 gram ethyl acetate.This solution is heated to 65 ℃, adds 126 gram deionized waters and 2 gram Marlowet then gradually
TMThe aqueous solution of 5401 emulsifying agents, high degree of agitation on the magnetic agitation plate simultaneously.Pass through ultrasound probe (Branson then
TM250Sonifier) in this formation pre-emulsion, soaking 3 minutes under the condition of peak power output, with its emulsification.Fall ethyl acetate at 55 ℃ with rotatory evaporator and injection water vacuum distilling.Obtain about 20% solid and stablize milky emulsion.The emulsion that makes like this is used to handle base material.
According to the method described above, synthetic different fluoro-containing composition (in the table 1 listed FC-1 to FC-15).Except that emulsification, basically by identical step preparation contrast condenses (C-FC-1 to C-FC-5).Because poorly soluble, these Comparative Examples can have ethyl acetate to carry out emulsification.They can not have phenylfluoroform or hexafluoro dimethylbenzene to carry out emulsification.
Table 1: the component of condenses
| The embodiment numbering | Fluoro-containing composition | Mol ratio | The % fluorine |
| FC-1 | The HMMM/EtFOSE/ stearyl alcohol | 1/3/3 | 26.8 |
| FC-2 | HMMM/EtFOSE/Prisorine 3515 | 1/3/3 | 34.9 |
| FC-3 | The HMMM/EtFOSE/2-ethylhexanol | 1/3/3 | 26.4 |
| FC-4 | HMMM/EtFOSE/Prisorine 3515 | 1/4/2 | 42.1 |
| FC-5 | The HMMM/EtFOSE/ stearyl alcohol | 1/4/2 | 35.5 |
| FC-6 | The HMMM/MeFOSE/ stearyl alcohol | 1/2/2 | 25.6 |
| FC-7 | HMMM/MeFOSE/Prisorine 3515 | 1/2/2 | 33.1 |
| FC-8 | The HMMM/MeFOSE/2-ethylhexanol | 1/2/2 | 25.3 |
| FC-9 | The HMMM/MeFOSE/ stearyl alcohol | 1/2/4 | 18.1 |
| FC-10 | The HMMM/MeFOSE/2-ethylhexanol | 1/3/3 | 26.8 |
| FC-11 | The HMMM/MeFOSE/ stearyl alcohol | 1/3/3 | 31.8 |
| FC-12 | The HMMM/MeFOSE/2-ethylhexanol | 1/4/2 | 35.8 |
| FC-13 | HMMM/MeFOSE/Prisorine 3515 | 1/4/2 | 42.9 |
| FC-14 | HMMM/MeFOSE/Guerbitol-18 | 1/2/2 | |
| FC-15 | HMMM/MeFOSE/Prisorine 3515 | 1/3/3 | |
| C-FC-1 | HMMM/EtFOSE | 1/2 | 43.3 |
| C-FC-2 | HMMM/EtFOSE | 1/3 | 47.6 |
| C-FC-3 | HMMM/EtFOSE | 1/4 | 50.1 |
| C-FC-4 | HMMM/MeFOSE | 1/2 | 44.2 |
| C-FC-5 | HMMM/MeFOSE | 1/3 | 48.7 |
In organic solvent commonly used, estimate the solvability of fluoro-containing composition, and compare with the solvability of HMMM/ fluorochemical condenses.25 gram fluoro-containing compositions and Comparative composition are mixed with 25 gram ethyl acetate (EtOAc) or methyl iso-butyl ketone (MIBK) (MIBK).Stirred 5 hours at 65 ℃ of mixtures gained.With this mixture cooling, be allowed to condition under the room temperature and placed 24 hours then, measure the concentration (being recorded as the % solid) of organic phase then.The results are shown in Table 2 for gained.
Embodiment 1-9 and Comparative Examples C1-C4
Table 2: the solubleness of fluoro-containing composition in organic solvent
| The embodiment numbering | FC | % solid in EtOAc | % solid among the MIBK |
| 1 | FC-1 | 14 | 15 |
| 2 | FC-3 | 50 | 50 |
| 3 | FC-4 | 45 | 46 |
| 4 | FC-6 | 44 | 45 |
| 5 | FC-7 | 43 | 43 |
| 6 | FC-10 | 45 | 46 |
| 7 | FC-11 | 9 | 9 |
| 8 | FC-14 | 50 | 50 |
| 9 | FC-15 | 35 | 34 |
| C1 | C-FC-2 | ＜10 | ＜10 |
| C2 | C-FC-3 | ＜5 | ＜5 |
| C3 | C-FC-4 | 18 | 17 |
| C4 | C-FC-5 | 9 | 9 |
These data show that fluoro-containing composition is more much higher than HMMM/ fluorochemical condenses solubleness.In general, the condenses that makes with branched hydrocarbyl alcohol (as 2-Ethylhexyl Alcohol, isooctadecanol or Guerbet type alcohol) produces best solubleness in organic solvent commonly used.
Embodiment 10-33 and Comparative Examples C-5 to C-12
In embodiment 10-33 and Comparative Examples C-5 to C-12, prepare fluoro-containing composition of the present invention and HMMM/ fluorochemical condenses by general step.By above-mentioned general step non-ionic type/anionic emulsifier (Kotylene
TM/ Siponate
TMDS10) with they emulsification.In rotary drum is handled, this emulsion is used for the Reutlingen leather by 1.8%SOF (solid on the fiber).Leather after the processing at room temperature solidified 24 hours, solidified 5 minutes at 60 ℃.Handling performance of leather result (hair side of leather and exasperate) lists in table 3 and 4.
Table 3: with leather (hair side) results of property of condenses processing
| The embodiment numbering | Treatment agent | OR | WR | SR | AOR | AWR |
| 10 | FC-2 | 2 | 7 | 70 | 2 | 9 |
| 11 | FC-3 | 5 | 8 | 80 | 5 | 9 |
| 12 | FC-4 | 1 | 3 | 80 | 1 | 3 |
| 13 | FC-5 | 5 | 10 | 80 | 6 | 10 |
| 14 | FC-6 | 7 | 10 | 80 | 7 | 9 |
| 15 | FC-7 | 7 | 9 | 80 | 7 | 10 |
| 16 | FC-8 | 7 | 9 | 80 | 7 | 10 |
| 17 | FC-9 | 6 | 9 | 80 | 5 | 8 |
| 18 | FC-10 | 7 | 9 | 80 | 7 | 10 |
| 19 | FC-11 | 5 | 8 | 80 | 6 | 8 |
| 20 | FC-12 | 6 | 9 | 80 | 6 | 8 |
| 21 | FC-13 | 7 | 9 | 70 | 6 | 9 |
| C-5 | C-FC-1 | 5 | 3 | 70 | 4 | 5 |
| C-6 | C-FC-2 | 5 | 8 | 80 | 5 | 8 |
| C-7 | C-FC-3 | 5 | 8 | 80 | 5 | 8 |
| C-8 | C-FC-5 | 1 | 2 | 70 | 1 | 2 |
Table 4: with leather (exasperate) results of property of fluoridizer processing
| The embodiment numbering | Treatment agent | OR | WR | SR | AOR | AWR |
| 22 | FC-2 | 0 | 2 | 70 | 0 | |
| 23 | FC-3 | 0 | 2 | 70 | 0 | 2 |
| 24 | FC-4 | 1 | 2 | 70 | 0 | 2 |
| 25 | FC-5 | 1 | 3 | 70 | 0 | 2 |
| 26 | FC-6 | 1 | 3 | 80 | 1 | 3 |
| 27 | FC-7 | 1 | 2 | 80 | 1 | 3 |
| 28 | FC-8 | 2 | 2 | 80 | 1 | 3 |
| 29 | FC-9 | 0 | 2 | 70 | 0 | 2 |
| 30 | FC-10 | 2 | 2 | 80 | 2 | 3 |
| 31 | FC-11 | 2 | 2 | 80 | 1 | 2 |
| 32 | FC-12 | 2 | 3 | 80 | 2 | 2 |
| 33 | FC-13 | 1 | 3 | 70 | 0 | 3 |
| C-9 | C-FC-1 | 0 | 2 | 70 | 0 | 1 |
| C-10 | C-FC-2 | 1 | 2 | 70 | 0 | 1 |
| C-11 | C-FC-3 | 1 | 2 | 80 | 0 | 1 |
| C-12 | C-FC-5 | 0 | 2 | 50 | 0 | 0 |
These data show that the leather of handling with fluoro-containing composition of the present invention generally has better properties than the leather of handling with HMMM/ fluorochemical condenses.
Embodiment 34-46 and Comparative Examples C-13 to C-12
In embodiment 34-46 and Comparative Examples C-13 to C-17, prepare fluoro-containing composition and HMMM/ fluorochemical condenses by above-mentioned general method.For these experiments, by above-mentioned general step cationic emulsifier system (Ethoquad
TMHT-25) emulsification fluoro-containing composition and HMMM/ fluorochemical condenses.With padding method this emulsion is being coated on the polyester/cotton base material under the 0.3%SOF concentration.At 150 ℃ the base material of handling was solidified 3 minutes.Handling the results of property of base material lists in the table 5.
Table 5: the results of property of the PES/CO that handles with condenses
| The embodiment numbering | FC amine condenses | Initial performance OR SR | 5 washing OR SR |
| 34 | FC-1 | 2 90 | 1 50 |
| 35 | FC-2 | 2 70 | 1 50 |
| 36 | FC-3 | 2 70 | 1 50 |
| 37 | FC-4 | 4 70 | 1 50 |
| 38 | FC-5 | 2 90 | 2 70 |
| 39 | FC-6 | 2 100 | 2 70 |
| 40 | FC-7 | 6 80 | 3 50 |
| 41 | FC-8 | 5 90 | 3 70 |
| 42 | FC-9 | 1 100 | 1 70 |
| 43 | FC-10 | 5 90 | 4 70 |
| 44 | FC-11 | 2 100 | 1 70 |
| 45 | FC-12 | 5 100 | 4 70 |
| 46 | FC-13 | 4 90 | 2 70 |
| C-13 | C-FC-1 | 3 80 | 2 70 |
| C-14 | C-FC-2 | 5 90 | 4 70 |
| C-15 | C-FC-3 | 3 90 | 2 70 |
| C-16 | C-FC-4 | 3 80 | 1 50 |
| C-17 | C-FC-5 | 3 80 | 3 70 |
These data show that though compare with only containing fluorine-based condenses, fluoro-containing composition has lower fluorine content, handle base material with it and can obtain similar performance.These data have also shown following tendency, promptly can improve spray quinoline grade with the hydrocarbon compound with straight chain hydrocarbon alkyl chain (as stearyl alcohol), and can improve total oil repellent with the hydrocarbon compound with branching generate longer-chain hydrocarbons alkyl alcohol.
Embodiment 47-59 and Comparative Examples C18 to C22
In embodiment 47-59 and Comparative Examples C18-C22, except that using polyamide substrate, by estimating with embodiment 34-46 and Comparative Examples C-13 to C-17 similar methods.The results are shown in Table 6 for oil repellent.
Table 6: the results of property of the PA that handles with condenses
| The embodiment numbering | FC amine condenses | Initial performance OR SR | 5 washing OR SR |
| 47 | FC-1 | 2 80 | 2 70 |
| 48 | FC-2 | 1 50 | 0 50 |
| 49 | FC-3 | 2 70 | 0 50 |
| 50 | FC-4 | 2 70 | 1 50 |
| 51 | FC-5 | 2 80 | 1 70 |
| 52 | FC-6 | 3 100 | 1 70 |
| 53 | FC-7 | 6 80 | 3 70 |
| 54 | FC-8 | 5 80 | 3 70 |
| 55 | FC-9 | 2 100 | 1 80 |
| 56 | FC-10 | 4 80 | 3 70 |
| 57 | FC-11 | 2 100 | 1 80 |
| 58 | FC-12 | 5 80 | 4 70 |
| 59 | FC-13 | 4 80 | 1 70 |
| C-18 | C-FC-1 | 3 80 | 2 70 |
| C-19 | C-FC-2 | 5 80 | 3 70 |
| C-20 | C-FC-3 | 3 80 | 2 80 |
| C-21 | C-FC-4 | 2 90 | 1 80 |
| C-22 | C-FC-5 | 4 100 | 2 80 |
Claims (23)
1. make base material have the purposes of the fluoro-containing composition of oil repellent and/or water repellency, it is characterized in that described fluoro-containing composition contains one or more condensess of following component: (i) methylolation amine or its C
1-C
4Alkoxy derivative, (ii) use the hydrocarbon compound of general formula (II) expression and (iii) use the fluorochemical of general formula (I) expression:
R
f-(X
1)
n-Z
1 (I)
In the formula:
R
fIt is the aliphatic group of fluoridizing that contains 3-14 carbon atom;
X
1It is the organic divalent linker that contains 1-20 carbon atom;
Z
1Be selected from hydroxyl, mercaptan, acid amides or acidic group;
N is 0 or 1;
R
h-Z
2 (II)
In the formula
R
hBe the alkyl that contains 6-18 carbon atom, it is optionally replaced by 1-3 substituting group;
Z
2Be selected from hydroxyl, mercaptan, acid amides or acidic group.
2. purposes as claimed in claim 1 is characterized in that R
hThe expression alkyl.
3. as each described purposes in the above-mentioned claim, it is characterized in that described methylolation amine or its C
1-C
4Alkoxy derivative is selected from methylolation melamine, methylolation urea, methylolation benzoguanamine, methylolation acetoguanamine or their alkoxy derivative.
4. purposes as claimed in claim 3 is characterized in that described methylolation amine or its C
1-C
4Alkoxy derivative is hexamethylol melamine or its methoxylation derivative.
5. purposes as claimed in claim 1 is characterized in that described base material is a fibrous material.
6. purposes as claimed in claim 5 is characterized in that described base material is fabric or leather.
7. purposes as claimed in claim 1 is characterized in that described fluoro-containing composition uses with the aqueous emulsion form.
8. handle the method for base material, it is characterized in that this method comprises described base material is contacted with fluoro-containing composition, described fluoro-containing composition contains one or more condensess of following component: (i) methylolation amine or its C
1-C
4Alkoxy derivative, (ii) use the hydrocarbon compound of general formula (II) expression and (iii) use the fluorochemical of general formula (I) expression:
R
f-(X
1)
n-Z
1 (I)
In the formula:
R
fIt is the aliphatic group of fluoridizing that contains 3-14 carbon atom;
X
1It is the organic divalent linker that contains 1-20 carbon atom;
Z
1Be selected from hydroxyl, mercaptan, acid amides or acidic group;
N is 0 or 1;
R
h-Z
2 (II)
In the formula
R
hBe the alkyl that contains 6-18 carbon atom, it is optionally replaced by 1-3 substituting group;
Z
2Be selected from hydroxyl, mercaptan, acid amides or acidic group.
9. method as claimed in claim 8 is characterized in that described base material is fabric or leather.
10. method as claimed in claim 8 or 9 is characterized in that described fluoro-containing composition is an aqueous emulsion.
11. a fluoro-containing composition is characterized in that described fluoro-containing composition contains one or more condensess of following component: (i) methylolation amine or its C
1-C
4Alkoxy derivative, (ii) use the hydrocarbon compound of general formula (II) expression and (iii) use the fluorochemical of general formula (I) expression:
R
f-(X
1)
n-Z
1 (I)
In the formula:
R
fIt is the aliphatic group of fluoridizing that contains 3-14 carbon atom;
X
1It is the organic divalent linker that contains 1-20 carbon atom;
Z
1Be selected from hydroxyl, mercaptan, acid amides or acidic group;
N is 0 or 1;
R
h-Z
2 (II)
In the formula
R
hBe the alkyl that contains 6-18 carbon atom, it is optionally replaced by 1-3 substituting group;
Z
2Be selected from hydroxyl, mercaptan, acid amides or acidic group.
12. fluoro-containing composition as claimed in claim 11 is characterized in that R
hThe expression alkyl.
13., it is characterized in that described methylolation amine or its C as claim 11 or 12 described fluoro-containing compositions
1-C
4Alkoxy derivative is selected from methylolation melamine, methylolation urea, methylolation benzoguanamine, methylolation acetoguanamine or their alkoxy derivative.
14. fluoro-containing composition as claimed in claim 13 is characterized in that described methylolation melamine or its C
1-C
4Alkoxy derivative is hexamethylol melamine or its methylolation derivative.
15. fluoro-containing composition as claimed in claim 11 is characterized in that it is dissolved in the nonfluorinated organic solvent.
16. fluoro-containing composition as claimed in claim 11 is characterized in that it is an aqueous emulsion.
17. the preparation method of a fluoro-containing composition is characterized in that this method is included in to make following component reaction under the existence of acid catalyst: (i) methylolation amine or its C
1-C
4Alkoxy derivative, (ii) use the hydrocarbon compound of general formula (II) expression and (iii) use the fluorochemical of general formula (I) expression:
R
f-(X
1)
n-Z
1 (I)
In the formula:
R
fIt is the aliphatic group of fluoridizing that contains 3-14 carbon atom;
X
1It is the organic divalent linker that contains 1-20 carbon atom;
Z
1Be selected from hydroxyl, mercaptan, acid amides or acidic group;
N is 0 or 1;
R
h-Z
2 (I)
In the formula
R
hBe the alkyl that contains 6-18 carbon atom, it is optionally replaced by 1-3 substituting group;
Z
2Be selected from hydroxyl, mercaptan, acid amides or acidic group.
18. method as claimed in claim 17 is characterized in that described methylolation amine or its C
1-C
4Alkoxy derivative is hexamethylol melamine or its methoxylation derivative.
19. preparation method as the aqueous emulsion of each described fluoro-containing composition among the claim 11-14, it is characterized in that this method comprises is dissolved in described fluoro-containing composition in the nonfluorinated organic solvent, is dispersed in the water with the solution of emulsifying agent with gained then.
20. method as claimed in claim 19 is characterized in that described nonfluorinated organic solvent is selected from ethyl acetate or methyl iso-butyl ketone (MIBK).
21. a base material is characterized in that its surperficial base material of going up just like each described fluoro-containing composition among the claim 11-16.
22. base material as claimed in claim 21 is characterized in that described base material is a fibrous substrate.
23. base material as claimed in claim 22 is characterized in that described base material is fabric or leather.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB971821054A CN1148394C (en) | 1997-04-08 | 1997-04-08 | Mixed fluorochemical hydrocarbon condensates to impart oil and water repellency to substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB971821054A CN1148394C (en) | 1997-04-08 | 1997-04-08 | Mixed fluorochemical hydrocarbon condensates to impart oil and water repellency to substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1251595A CN1251595A (en) | 2000-04-26 |
| CN1148394C true CN1148394C (en) | 2004-05-05 |
Family
ID=5178293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB971821054A Expired - Fee Related CN1148394C (en) | 1997-04-08 | 1997-04-08 | Mixed fluorochemical hydrocarbon condensates to impart oil and water repellency to substrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1148394C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107592890A (en) * | 2015-04-30 | 2018-01-16 | 伯恩哈德·萨德内 | The compound of hydrophobic property and the preparation without fluorocarbon polymer, its purposes as finishing agent on flat material and thus obtained base material based on water and/or organic solvent |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060188729A1 (en) * | 2005-02-22 | 2006-08-24 | Kai-Volker Schubert | Washable leather with repellency |
| CN111155310A (en) * | 2020-01-15 | 2020-05-15 | 东莞市鸿运纺织助剂有限公司 | Water-proof and oil-proof finishing agent |
-
1997
- 1997-04-08 CN CNB971821054A patent/CN1148394C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107592890A (en) * | 2015-04-30 | 2018-01-16 | 伯恩哈德·萨德内 | The compound of hydrophobic property and the preparation without fluorocarbon polymer, its purposes as finishing agent on flat material and thus obtained base material based on water and/or organic solvent |
| CN107592890B (en) * | 2015-04-30 | 2020-05-19 | 特克萨帕特有限公司 | Hydrophobic compounds and formulations containing them and their use |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1251595A (en) | 2000-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4231983B2 (en) | Water-soluble water and oil repellent treatment agent and method for producing the same | |
| CN1236004C (en) | Aqueous dispersion for water-and-oil repellant and process for producing the same | |
| CN1461334A (en) | Water-and-oil repellant composition | |
| CN1036786C (en) | Polysiloxanes having fluoroaliphatic- and carboxyl-containing terminal groups, thir preparation, and their use in treatment of fibrous substrates | |
| CN1131147A (en) | Carbodiimide compound and water repellent compositions | |
| CN1098870C (en) | Products of reaction between isocyanates and hydroxyl compounds for textile finishing | |
| CN1249292C (en) | Sizing agent for carbonfiber, aqueous dispersion of the same, carbon fiber treated by sizing, sheet comprising the carbon fiber, and carbon fiber-reinforced composite material | |
| CN1053210C (en) | Fluoroaliphatic dimer acid derivatives and use thereof | |
| CN1784480A (en) | Surface-treating agent comprising fluoropolymer | |
| CN1930341A (en) | Treating textiles with emulsions containing silicone resins | |
| CN1582319A (en) | Coating composition comprising a fluorochemical polyether silane partial condensate and use thereof | |
| CN1188307C (en) | Wet cloth for washing,water-proof fine renovating and polishing car paint film | |
| CN100497419C (en) | Polymeric reaction products from substituted adminosiloxanes | |
| JPH09249748A (en) | Water-soluble fiber-treating agent and its production | |
| CN1370184A (en) | Fluorochemical water and oil repellents | |
| CN1148394C (en) | Mixed fluorochemical hydrocarbon condensates to impart oil and water repellency to substrate | |
| CA2560979C (en) | Fluorochemical composition and method for treating a substrate therewith | |
| CN1993513A (en) | Textile treatments using fluoropolymer-branched silicone polyethers | |
| CN1148481C (en) | Finishing oil for fine-denier polypropylene staple fibres | |
| JPH07252775A (en) | Fiber processing composition and treatment of base material therewith | |
| CN1882636A (en) | Polymeric products useful as oil repellents | |
| CN1161701A (en) | Fluorinated maleate, fluorinated fumarate, fluorinated copolymer, and antifouling agent | |
| US6440321B1 (en) | Mixed fluorochemical hydrocarbon condensates to impart oil and water repellency to a substrate | |
| CN1748000A (en) | Aqueous emulsion composition | |
| KR20080021113A (en) | Method for producing leather |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20040505 Termination date: 20140408 |