EP0213580A2 - Uréthanes contenant des groupements perfluoralcoyle et épichlorhydrine, leur dispersion aqueuse et leur application - Google Patents

Uréthanes contenant des groupements perfluoralcoyle et épichlorhydrine, leur dispersion aqueuse et leur application Download PDF

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Publication number
EP0213580A2
EP0213580A2 EP86111699A EP86111699A EP0213580A2 EP 0213580 A2 EP0213580 A2 EP 0213580A2 EP 86111699 A EP86111699 A EP 86111699A EP 86111699 A EP86111699 A EP 86111699A EP 0213580 A2 EP0213580 A2 EP 0213580A2
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EP
European Patent Office
Prior art keywords
weight
component
water
leather
urethanes
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.)
Granted
Application number
EP86111699A
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German (de)
English (en)
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EP0213580A3 (en
EP0213580B1 (fr
Inventor
Heinrich Dr. Bathelt
Winfried Dr. Ehrl
Frank Dr. Wehowsky
Rolf Dr. Kleber
Werner Dr. Lotz
Wolfgang Glenz
Hubert Herdt
Lothar Jäckel
Jan-Hilbert Mast
Karl Dr. Hintermeier
Manfred Müller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte Deutschland GmbH
Original Assignee
Hoechst AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE19853530967 external-priority patent/DE3530967A1/de
Priority claimed from DE19863605844 external-priority patent/DE3605844A1/de
Application filed by Hoechst AG filed Critical Hoechst AG
Priority to AT86111699T priority Critical patent/ATE54661T1/de
Publication of EP0213580A2 publication Critical patent/EP0213580A2/fr
Publication of EP0213580A3 publication Critical patent/EP0213580A3/de
Application granted granted Critical
Publication of EP0213580B1 publication Critical patent/EP0213580B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/425—Carbamic or thiocarbamic acids or derivatives thereof, e.g. urethanes
    • D06M13/428—Carbamic or thiocarbamic acids or derivatives thereof, e.g. urethanes containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00—Purpose of the treatment
    • B27K2240/70—Hydrophobation treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B27K3/38—Aromatic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B27K3/50—Mixtures of different organic impregnating agents

Definitions

  • the invention relates to new perfluoroalkyl and epichlorohydrin groups containing urethanes, these new urethanes containing aqueous dispersions and the use of these urethanes and dispersions.
  • urethanes of the formula given above have particularly advantageous properties with regard to the treatment of textiles, leather and furs when R f , Q, m, R 1 , R 2 , p, o and R 3 have special meanings or assume numerical values, namely if R f is a selected fluoroaliphatic radical, namely a straight-chain perfluoroalkyl radical, Q -CH z -, m 1, R, and R 2 H, p 1 to 7, preferably 1 to 3, o 2 and R 3 is the 2,4- or 2,6-tolylene diisocyanate radical.
  • the invention therefore relates to compounds of the formula I below, in which a is a number from 5 to 17, preferably 7 to 15, and b is a number from 1 to 7, preferably 1 to 3.
  • the urethanes according to the invention are preferably prepared by first preparing the perfluoroalkylethanol-epichlorohydrin adduct and reacting this adduct with tolylene diisocyanate.
  • the procedure is preferably such that a perfluoroalkylethanol of the formula II below wherein a has the meaning given above, or a mixture of such perfluoroalkylethanols with epichlorohydrin in the presence of Lewis acids as a catalyst at a temperature of 50 to 150 ° C., preferably 70 to 90 ° C.
  • a and b have the meaning given above, are intended to illustrate this:
  • Perfluoroalkylethanol is generally an inexpensive, commercially available mixture in which the average value of a is preferably 8 to 12.
  • the type of Lewis acid is not critical.
  • the amount of catalyst is generally 0.01 to 5% by weight, preferably 0.1 to 1% by weight, based on perfluoroalkylethanol.
  • the reaction is preferably carried out with stirring and at the pressure which is established, the liquid epichlorohydrin (boiling point under normal conditions 116 ° C.) being added to the alcohol presented.
  • the reaction time is in the range of about 0.5 to 7 hours.
  • solvents are halogenated hydrocarbons such as carbon tetrachloride, trichlorethylene, 1,2-dichloroethane, trichloroethane, pentafluoromonochloroethane and trifluorodichloroethane; Ketones such as methyl ethyl ketone and cyclohexanone; Ethers such as diisopropyl ether and tetrahydrofuran; Dimethylformamide and N-methylpyrrolidone.
  • halogenated hydrocarbons such as carbon tetrachloride, trichlorethylene, 1,2-dichloroethane, trichloroethane, pentafluoromonochloroethane and trifluorodichloroethane
  • Ketones such as methyl ethyl ketone and cyclohexanone
  • Ethers such as diisopropyl ether and tetrahydrofuran
  • the implementation in question is quantitative.
  • the solvent which may be used is distilled off, and any volatile constituents, such as unreacted epichlorohydrin, which may be present are also removed.
  • the distillation can also be carried out under vacuum (water jet vacuum).
  • the Lewis acid used as catalyst which does not interfere with the subsequent reaction with tolylene diisocyanate, can be washed out or neutralized with the aid of alkaline agents, preferably with the aid of an aqueous sodium bicarbonate solution or an amine such as triethylamine.
  • the procedure is preferably such that the adduct compound is initially introduced (melts by heating), at a temperature of 50 to 150 ° C., preferably 70 to 120 ° C., the tolylene diisocyanate is added and the latter mentioned Allows temperature to react.
  • This reaction is also preferably carried out with stirring and at the pressure which is established.
  • the implementation time is in the range of 1 to 15 hours. If it is expedient, the solvents mentioned above can also be used here.
  • Suitable tolylene diisocyanates are 2,4- and / or 2,6-tolylene diisocyanate, preferably in the form of a commercial product containing about 80% by weight of 2,4-tolylene diisocyanate and about 20% by weight of 2,6-tolylene diisocyanate contains.
  • the reaction of the perfluoroalkylethanol-epichlorohydrin adduct with tolylene diisocyanate proceeds quantitatively and provides the urethanes according to the invention as solid (waxy) products with the desired purity.
  • the compounds according to the invention are surprisingly good treatment agents for textiles, leather and furs (fur velor) and for unpainted wood, in particular for textiles, leather and furs. Above all, they give these articles excellent hydrophobicity and oleophobicity. They also have, to an unexpectedly high degree, the ability to withstand the heavy loads to which the finished textiles and leather and furs are subjected, for example during stretching, texturing, dyeing and washing or during tensioning and milling, without any loss of effectiveness.
  • the textile material can be natural and / or synthetic in nature. It preferably consists of polyamide, polyester and / or polyacrylonitrile, polyamide being particularly preferred.
  • the textile material can be in any form, for example as thread, fiber, yarn, flake, fabric, knitted fabric, knitted fabric, carpet or fleece.
  • the application amount of compound according to the invention is chosen so that 0.02 to 1% by weight of fluorine, preferably 0.04 to 0.4% by weight of fluorine, is present on the textile material, calculated from the amount of fluorine in the invention Connection; Percentages by weight based on the treated textile material.
  • the type of leather and fur is not critical.
  • the leather can be, for example, cow, goat, sheep or pork leather and the like.
  • the fur can be, for example, sheep suede, mink, raccoon or a similar type of precious fur.
  • the application amount of compound according to the invention is selected so that 0.05 to 1.5% by weight of fluorine, preferably 0.1 to 1% by weight of fluorine, is present on the leather or fur, calculated from the amount of fluorine in the compound of the invention; Weight percentages based on the treated material (leather or fur).
  • Compounds A of formula I are preferably used as component A) which result when a is a number from 7 to 15 and b is a number from 1 to 3.
  • Cationic and betaine emulsifiers of the formula are preferably used as component B) used, in which R " f is a perfluoroalkyl radical with 5 to 13 C atoms, which may contain a terminal CF 2 H group, preferably C 5 F 11 , C 7 F 15 , C 9 F 19 , C 11 F 23 and C 13 F 27 , R 4 , R 5 and R 6 , which may be the same or different, is an alkyl group with 1 to 4 C atoms, which may be substituted with hydroxyl, and X is a monovalent anion, preferably chloride, bromide, sulfate or alkyl sulfate having 1 to 2 carbon atoms.
  • cationic Emulsifiers are particularly preferred. These emulsifiers can be used as such or dissolved in a solvent; Lower alkanols such as methanol, ethanol, propanol and / or isopropanol, optionally together with water, are preferably used as the solvent. The cationic emulsifiers are preferred.
  • Non-ionic emulsifiers of the type polyoxethylene sorbitan monooleate or polyoxethylene sorbitan monostearate with 10 to 30 ethylene oxide units are preferably used as component C).
  • Polyoxethylene sorbitan monooleates with 10 to 30 ethylene oxide units are particularly preferred, for example polyoxethylene sorbitan monooleate with 20 ethylene oxide units, which is known under the trade name Tween 80.
  • component D preferably butyl acetate, methyl propionate, methyl butyrate, glycol bisacetate, propanediol bisacetate, diethyl succinate, dimethyl adipate, dibutyl adipate, individually or as a mixture with one another.
  • Monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, the corresponding propylene glycols, the (C 1 -C 4 ) monoalkyl or dialkyl ethers of these ethylene and propylene glycols are preferably used as component E), diethylene glycol dimethyl ether and dipropylene glycol monomethyl ether being particularly preferred.
  • the compounds corresponding to components B) to E) are commercially available. They can also be used in the form of their technical mixtures, which generally contain several compounds of the type mentioned (homolog mixtures).
  • the aqueous dispersions according to the invention can also contain further useful components.
  • the dispersion may contain an aliphatic ketone which is insoluble or poorly soluble in water and has a boiling point above 100 ° C .; Examples of this are aliphatic ketones with 5 to 8 carbon atoms such as diethyl ketone, methyl propyl ketone, methyl isobutyl ketone and the like. These ketones are used in an amount of preferably 5 to 10% by weight, percentages by weight based on the aqueous dispersion, and can replace a corresponding part of component D).
  • the aqueous dispersions according to the invention are prepared by mixing the individual components together.
  • the procedure is preferably such that components A), B), C), D) and E) are dispersed in water (component F) while supplying a relatively large amount of energy.
  • the proportions for the Components are chosen so that the specified composition for the dispersion is achieved after dispersion.
  • component A) that is the compound according to the invention, the active ingredient
  • component D) and E is predispersed at least in part of the amount of component D) and E) used and is used in this form.
  • the predispersion is expediently carried out by using high shear forces, such as are present when using a high-speed stirrer, for example a stirrer (dispersing machine) of the Ultraturrax type, and the predispersion (crude dispersion) obtained is then expediently subjected to an ultrasound treatment or a treatment in a high-pressure homogenizer .
  • the particle size in the dispersion is more than 80%, preferably more than 95%, at or below 1 ⁇ m (fine dispersion).
  • the invention finally relates to the use of the aqueous dispersions described.
  • They are used according to the invention for the treatment of textiles, leather and fur and of unpainted wood (preferably unpainted furniture). They give these articles, especially textiles, leather and fur, excellent hydrophobic and oleophobic finishing.
  • the aqueous dispersions can be used in the form in which they are produced. Normally, however, they will be adjusted to a solids content of 1 to 10% by weight, preferably 1.5 to 5% by weight (percentages by weight based on the aqueous dispersion), with water and used in this more dilute form.
  • the aqueous dispersions can be used directly and without further predilution in the form in which they are produced to finish pre-broached leather and furs.
  • they will normally be adjusted beforehand with water to a solids content of 1 to 10% by weight, preferably 4 to 8% by weight (percentages by weight based on the aqueous dispersion), and in use this thinner form.
  • aqueous dispersions according to the invention meet all practical requirements and in particular show excellent long-term stability at temperatures from -20 to +40 ° C. Although they freeze at sub-zero temperatures, the dispersion remains after thawing. In addition to the excellent oleophobization and hydrophobization, a general dirt repellency and also an improvement in conductivity are achieved.
  • aqueous dispersions described can be used both for the equipment in question, and in combination with, for example, conventional spin finishes or leather greasing agents or other finishing agents such as antistatic agents, optical brighteners, textile resins based on glyoxal or its derivatives, plasticizers and dispersions of polyvinyl alcohol and ethylene vinyl acetate polymers, mineral and synthetic tanning agents, and resin and polymer tanning agents.
  • the textile material can therefore be natural or synthetic in nature.
  • the aqueous dispersions are particularly advantageous in the case of a textile material made from polyamide, polyester and / or polyacrylonitrile, in particular from polyamide.
  • the textile material can be in any form; usually it will be threads, fibers, fabrics or carpets.
  • the treatment of textile material with the aqueous dispersions according to the invention is carried out by customary methods, for example by spraying, dipping, splashing, padding and the like.
  • the amount applied is chosen so that the amount of fluorine of the active ingredient (compound according to the invention) on the textile material is 0.02 to 1% by weight, preferably 0.04 to 0.4% by weight, percentages by weight based on the treated textile material .
  • drying is carried out at temperatures up to approximately 120 ° C., for example at 100 to 120 ° C., and then heat treatment is carried out at temperatures of approximately 130 to 190 ° C., preferably 140 to 180 ° C, which normally takes about 30 seconds to about 4 minutes (unless drying and heat treatment are not carried out in the course of the manufacture of the textile material anyway).
  • the treatment of the leather and furs with the aqueous dispersions according to the invention is carried out by the customary methods, for example in the bath, by dipping, brushing or spraying.
  • the application amount is selected so that the amount of fluorine offered for the active ingredient (compound according to the invention) for the leather and fur material is 0.05 to 1.5% by weight, preferably 0.1 to 1% by weight, based on percentages by weight the leather and fur material to be treated.
  • the leather and fur material can be dried and finished as usual.
  • the treatment with the aqueous dispersion according to the invention does not impair the color or the feel of the treated leather and furs, nor does the free play of the wool and hair of furs be impaired by adhesive bonding thereof.
  • the gross composition of the compounds obtained according to Examples 3 to 6 corresponds to the formula of the compound of Example 2, with the exception that the indexes 1.6, 1.8, 2.0 and 2.4 are used instead of the index 1.4.
  • the gross composition of the compounds according to the invention obtained according to Examples 8 to 12 corresponds to the formula of the compound of Example 7, with the exception that the radical C 8 F 17 -C 16 F 33 is substituted for the radical C 6 F 13 -C 14 F 29 and the indices 1.4, 1.6, 1.8, 2.0 and 2.4 are used instead of the index 1.2.
  • Example 13 It was adjusted as in Example 13 to 10 kg of aqueous dispersion using an appropriate amount of water. There was a nice, stable dispersion with an active fluorine content of 8% by weight.
  • the dispersion therefore consisted of A) 1.51 kg; B) 1.10 kg with a total of 0.16 kg of solvent; C) 0.20 kg; D) 1.50 kg; E) 0.50 kg; and F) 6.03 kg.
  • Example 13 It was adjusted as in Example 13 to 10 kg of aqueous dispersion using an appropriate amount of water. There was a nice, stable dispersion with an active fluorine content of 8% by weight.
  • Example 13 Because of the slight difference between 1.74 kg of component A) in Example 13 and the 1.76 kg in this example, the amounts of components A) to F ) in percentages by weight, based on the active substance or on the aqueous dispersion, are almost the same the corresponding amounts in Example 13
  • Example 13 10 kg of a beautiful, stable aqueous dispersion which had an active fluorine content of 8% by weight were obtained.
  • Example 15 With regard to the amounts of components A) to F) in percentages by weight, based on active substance or on aqueous dispersion, the statements made at the end of Example 15 also apply in this example.
  • the compounds of Examples 8 to 11 according to the invention were tested.
  • the compounds were applied to a fabric made of polyamide 6 filaments using a padder and with a liquor pickup of 30 to 40% by weight.
  • the amount of compound of the invention (active substance) in the liquor was in each case selected so that each about 0.05 G ew .-% edition of fluorine (effective fluorine) on the fabric after the condensation was present (percentages by weight based on the weight of the fabric ).
  • the liquor consisted of approximately 1.2 g of the compound according to the invention in 250 ml of acetone (acetone liquor).
  • the acetone-moist tissues were first air-dried and then condensed (fixed) at 160 ° C. for 1 minute.
  • the oil repellency values of the fabrics thus obtained were determined in accordance with AATCC test standard 118-1978, namely according to the Condensation and after 3 hours of treatment with an alkaline boil consisting of 1 l of water, 1 g of trisodium phosphate and 2 g of a fatty acid polyglycol ester obtained by oxethylating 1,4-butanediol with 15 mol of ethylene oxide and then esterifying the oxethylate with 1 mol of oleic acid . Furthermore, the fluorine coating (F coating in% by weight, based on the weight of the fabric) was determined after the condensation and after the alkaline boil. The results are summarized in the table below:
  • the aqueous dispersions of Examples 13 to 16 according to the invention were tested.
  • the dispersions were diluted with water to a solids content of 2 to 4% by weight.
  • the diluted dispersions (liquors) were applied to a fabric made of polyamide 6 filaments with the aid of a padder and with a liquor absorption of 30 to 40% by weight, so that each time about 0.05% by weight of fluorine ( effective fluorine) was present on the tissue after the condensation (percentages by weight based on the weight of the tissue).
  • the liquor-moist fabrics were first dried at temperatures up to 120 ° C. and then condensed at 200 ° C. for 3 minutes.
  • the oil repellency values of the fabrics thus obtained were determined in accordance with the AATCC test standard 118-1978, namely according to Condensation and after 3 hours of treatment with the above-mentioned alkaline hot wash. Furthermore, the fluorine coating (F coating in% by weight, based on the weight of the fabric) was determined after the condensation and after the alkaline boil. The results are summarized in the table below:
  • Example 17 to 20 the following compound described in Example 4 of the US patents was tested: The procedure was as in Examples 17 to 20. On that after treatment with the acetone liquor and the condensation obtained at 160 ° C., as in Examples 17 to 20, the oil repellency values were determined after the condensation and after 3 hours of treatment with the alkaline boil. Furthermore, the fluorine coating (F coating in% by weight, based on the weight of the fabric) was determined after the condensation and after the alkaline boil. The results are summarized below:
  • the compounds of Examples 8 to 11 according to the invention were tested.
  • the compounds were applied by spray application to untreated leather.
  • the applied amount of compound of the invention (active substance) were each chosen so that approximately 0.5 to 0.6 g fluorine p ro m 2 leather surface was coated.
  • the application was carried out as a 0.5% by weight acetone active substance solution. After evaporation of the solvent and one day La q of the treated leather was ren, the water repellent effect with the aid of the Wassertronfenprobe (measurement of the time that elapses until the Absorption of a drop of water of a defined size by the leather).
  • the dispersions were applied to untreated leather both by spraying and by bathing.
  • the aqueous dispersions according to the invention were diluted with water to a solids content of 4 to 8% by weight. Approx. 1.6 g of fluorine / m 2 of leather were applied with the spray gun. After drying, milling or brushing, the water-repellent effect was tested using the water drop sample and the oil-repellent effect using the AATCC test 118.
  • aqueous dispersions according to the invention were used in the usual process for finishing the leather in the bathroom leather production after chrome tanning, retanning, dyeing and greasing - added undiluted to the greasing bath (which had a fleet of 150% by weight water, based on the leather fold weight) in an amount of 0.3% by weight fluorine, based on the leather fold weight .
  • the water drop sample of the leather treated in this way gave a service life of more than 8 hours for the applied water drops to be absorbed, and oil repellency values of 5 and greater were achieved.
  • the compounds and aqueous dispersions according to the invention are excellent finishing agents for leather and furs.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Polyethers (AREA)
EP86111699A 1985-08-30 1986-08-23 Uréthanes contenant des groupements perfluoralcoyle et épichlorhydrine, leur dispersion aqueuse et leur application Expired - Lifetime EP0213580B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86111699T ATE54661T1 (de) 1985-08-30 1986-08-23 Perfluoralkyl- und epichlorhydrin-gruppen enthaltende urethane, diese urethane enthaltende waessrige dispersionen und ihre verwendung.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3530967 1985-08-30
DE19853530967 DE3530967A1 (de) 1985-08-30 1985-08-30 Perfluoralkyl- und epichlorhydrin-gruppen enthaltende urethane, diese urethane enthaltende waessrige dispersionen und ihre verwendung
DE3605844 1986-02-22
DE19863605844 DE3605844A1 (de) 1986-02-22 1986-02-22 Perfluoralkyl- und epichlorhydrin-gruppen enthaltende urethane, diese urethane enthaltende waessrige dispersionen und ihre verwendung

Publications (3)

Publication Number Publication Date
EP0213580A2 true EP0213580A2 (fr) 1987-03-11
EP0213580A3 EP0213580A3 (en) 1988-03-02
EP0213580B1 EP0213580B1 (fr) 1990-07-18

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Application Number Title Priority Date Filing Date
EP86111699A Expired - Lifetime EP0213580B1 (fr) 1985-08-30 1986-08-23 Uréthanes contenant des groupements perfluoralcoyle et épichlorhydrine, leur dispersion aqueuse et leur application

Country Status (10)

Country Link
US (1) US4709074A (fr)
EP (1) EP0213580B1 (fr)
JP (1) JPH089588B2 (fr)
KR (1) KR940007742B1 (fr)
AU (1) AU591395B2 (fr)
BR (1) BR8604126A (fr)
CA (1) CA1276165C (fr)
DE (1) DE3672718D1 (fr)
ES (1) ES2001123A6 (fr)
NZ (1) NZ217383A (fr)

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DE3540147A1 (de) * 1985-11-13 1987-05-14 Hoechst Ag Perfluoralkylgruppen, epichlorhydringruppen und dialkoholreste enthaltende urethane, verfahren zu ihrer herstellung und ihre verwendung
WO1993010085A1 (fr) 1991-11-12 1993-05-27 Minnesota Mining And Manufacturing Company Derives de l'acide dimere fluoroaliphatique et leur utilisation
DE4244951C2 (de) * 1992-12-01 1998-08-06 Minnesota Mining & Mfg Fasersubstrat mit Wasser-, Öl-, Schmutzabweisungsvermögen und Weichgriffigkeit
GB9414570D0 (en) * 1994-07-19 1994-09-07 Secr Defence Oil and water repellent dyestuffs
GB9519824D0 (en) * 1995-09-29 1995-11-29 Secr Defence Fibre reactive polymers
US6294103B1 (en) 1996-11-07 2001-09-25 3M Innovative Properties Company Use of amphiphilic copolymers containing a fluorinated monomer to impart waterproofness to leather
EP0841405B1 (fr) 1996-11-07 1999-12-29 Minnesota Mining And Manufacturing Company Utilisation de copolymères amphiphiles contenant des monomères fluorés pour imperméabiliser des cuirs
US6525127B1 (en) 1999-05-11 2003-02-25 3M Innovative Properties Company Alkylated fluorochemical oligomers and use thereof in the treatment of fibrous substrates
US7049379B2 (en) * 1999-05-11 2006-05-23 3M Innovative Properties Company Alkylated fluorochemical oligomers and use thereof in the treatment of fibrous substrates
DK1210466T3 (da) * 1999-08-20 2004-06-01 Pirjo Kortelainen En kombinationsbeklædning af tekstil og pels og fremgangsmåde til fremstilling deraf
CA2493985A1 (fr) * 2002-08-06 2004-02-12 Daikin Industries, Ltd. Composes urethane fluores et compositions les contenant
US7160480B2 (en) * 2005-02-22 2007-01-09 E. I. Du Pont De Nemours And Company Leather treated with fluorochemicals
US8043645B2 (en) 2008-07-09 2011-10-25 Starbucks Corporation Method of making beverages with enhanced flavors and aromas
GB0919014D0 (en) * 2009-10-30 2009-12-16 3M Innovative Properties Co Soll and stain resistant coating composition for finished leather substrates
CN109942763B (zh) * 2019-03-12 2021-08-13 上海应用技术大学 一种改性水性树脂及其制备方法

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US4264484A (en) * 1979-01-24 1981-04-28 Minnesota Mining And Manufacturing Company Carpet treatment
US4468527A (en) * 1980-12-08 1984-08-28 Minnesota Mining And Manufacturing Company Fluorinated alcohols
DE3514373A1 (de) * 1985-04-20 1986-10-23 Cassella Ag, 6000 Frankfurt Waessrige anionische dispersion

Patent Citations (1)

* Cited by examiner, † Cited by third party
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US4340749A (en) * 1979-12-21 1982-07-20 Minnesota Mining And Manufacturing Company Carpet treatment

Also Published As

Publication number Publication date
NZ217383A (en) 1989-10-27
JPS6296457A (ja) 1987-05-02
KR940007742B1 (ko) 1994-08-24
JPH089588B2 (ja) 1996-01-31
BR8604126A (pt) 1987-04-22
EP0213580A3 (en) 1988-03-02
AU591395B2 (en) 1989-11-30
KR870001865A (ko) 1987-03-28
CA1276165C (fr) 1990-11-13
US4709074A (en) 1987-11-24
DE3672718D1 (de) 1990-08-23
AU6209586A (en) 1987-03-05
ES2001123A6 (es) 1988-04-16
EP0213580B1 (fr) 1990-07-18

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