EP0202471A2 - Dispersion aqueuse anionique - Google Patents

Dispersion aqueuse anionique Download PDF

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Publication number
EP0202471A2
EP0202471A2 EP86105191A EP86105191A EP0202471A2 EP 0202471 A2 EP0202471 A2 EP 0202471A2 EP 86105191 A EP86105191 A EP 86105191A EP 86105191 A EP86105191 A EP 86105191A EP 0202471 A2 EP0202471 A2 EP 0202471A2
Authority
EP
European Patent Office
Prior art keywords
formula
aqueous anionic
anionic dispersion
bis
compound
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
EP86105191A
Other languages
German (de)
English (en)
Other versions
EP0202471A3 (en
EP0202471B1 (fr
Inventor
Karl Dr. Hintermeier
Heinrich Dr. Bathelt
Frank Dr. Wehowsky
Hans Wagener
Manfred Seidel
Manfred Müller
Klaus Kaschub
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.)
Sanofi Aventis Deutschland GmbH
Cassella Farbwerke Mainkur AG
Original Assignee
Cassella AG
Cassella Farbwerke Mainkur 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
Application filed by Cassella AG, Cassella Farbwerke Mainkur AG filed Critical Cassella AG
Priority to AT86105191T priority Critical patent/ATE65809T1/de
Publication of EP0202471A2 publication Critical patent/EP0202471A2/fr
Publication of EP0202471A3 publication Critical patent/EP0202471A3/de
Application granted granted Critical
Publication of EP0202471B1 publication Critical patent/EP0202471B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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

Definitions

  • the present invention relates to an aqueous anionic dispersion which contains a bis- (2-perfluoroalkyl-ethoxy-carbonylamino) toluene, its preparation and its use for finishing textiles with oleophobic and hydrophobic agents, and the active ingredient contained in the dispersion .
  • synthetic fibers can be made dirt-repellent, water-repellent and oil-repellent if they contain a fluorine-containing compound, e.g. 2,4-bis (2-perfluoroalkyl-ethoxycarbonylamino) toluene is applied in such an amount that the film applied contains at least 20% by weight of fluorine.
  • a fluorine-containing compound e.g. 2,4-bis (2-perfluoroalkyl-ethoxycarbonylamino) toluene is applied in such an amount that the film applied contains at least 20% by weight of fluorine.
  • a commercial product for textile finishing contains such fluorine-containing bisurethanes together with cationic dispersing agents in an aqueous dispersion.
  • a disadvantage of using this dispersion is that fibers or textiles treated with it attract dirt particles that are normally anionically charged. For this reason, the cationic dispersions of the fluorine-containing bisurethanes must contain a special antistatic additive if one does not want to be forced to subject the finished goods to additional antistatic treatment later.
  • the percentages given above represent percentages by weight.
  • the percentages for a, b, c and d are based on the total weight of the aqueous dispersion.
  • the perfluoroalkyl radicals or perfluoroalkyl compounds mentioned above and below, according to the above definitions in the w position for Y may also have an H atom.
  • the compounds of the formulas II, III and IV can be used in the form of their technical mixtures, which generally contain several compounds of the type mentioned with different index numbers n, p, q and / or r.
  • the compounds of formula I are known.
  • the active ingredient A which is used according to the invention for the preparation of the aqueous anionic dispersion, is new.
  • A is used to produce the product specified under A.
  • Suitable tolylene di-isocyanates are, in particular, 2,4-and / or 2,6-tolylene-di-isocyanate, in particular in the form of a commercial product which contains approximately 80% by weight of 2,4-tolylene-di- contains isocyanate and about 20% by weight of 2,6-tolylene di-isocyanate.
  • the reaction for the production of product A is generally carried out in such a way that the compound II or the mixture of the compounds II is melted and 2 to 5% by weight, preferably 2 to 3.5% by weight, of N-methyl pyrrolidone is mixed in and then the tolylene di-isocyanate or the mixture of tolylene di-isocyanates is added dropwise with stirring at a temperature which is about 5 to 10 ° C. above the melting point.
  • the mixture is then heated to temperatures of approximately 130 ° C. in the course of an hour, the reaction being slightly exothermic from temperatures of approximately 80 ° C.
  • the reaction is brought to a conclusion by an approximately three-hour reaction time at approximately 130 ° C.
  • the progress of the reaction is continuously checked by IR spectroscopy on the samples for the disappearance of the isocyanate bands. If the reaction occurs within the specified time has not yet been completed, the reaction time must be extended, for example to 6 hours.
  • N-methylpyrrolidone presumably forms by-products of still unknown structure, which act as excellent dispersion stabilizers in the inventive dispersion of the product.
  • a larger addition of N-methylpyrrolidone in the preparation of product A does not adversely affect the effect of dispersion stabilization, but unnecessarily reduces the yield of the active substance of the formula I.
  • the monovalent cation X in the compounds of the formula III generally represents an alkali metal cation, in particular the sodium or potassium cation or the ammonium cation.
  • the ammonium cation can optionally also be substituted by organic radicals, for example triethanolammonium.
  • emulsifiers of the formula IV are also commercially available, mostly in the form of their technical mixtures.
  • r is in particular approximately 6.
  • d is preferably a number from 10 to 25.
  • components A, B, C and D are dispersed in water, with the supply of a relatively large amount of energy.
  • the quantitative ratios for the components are chosen so that the specified composition for the dispersion is achieved after dispersion. It is essential to pre-dissolve product A in at least part of the amount of solvent or solvent mixture to be used, and it is expedient to divide the dispersion into two substeps and first to do a predispersion and then a fine dispersion.
  • the predispersion is expediently carried out using high shear forces, for example using a high-speed stirrer, e.g.
  • component D water-soluble solvents, such as e.g. Mono- or di-alcohols, lower ketones, polyglycol esters and polyglycol ethers or mixtures of such solvents are used.
  • component D contains at least one high-boiling, water-soluble solvent, i.e. a solvent with a boiling point above approx. 150 ° C.
  • a solvent mixture used can also include one or more water-insoluble solvents, such as e.g. Contain esters, ethers and / or higher ketones. Low-boiling solvent fractions can optionally be removed again at a later time, e.g. be distilled off.
  • water-insoluble solvents such as e.g. Contain esters, ethers and / or higher ketones.
  • Low-boiling solvent fractions can optionally be removed again at a later time, e.g. be distilled off.
  • Suitable water-soluble, high-boiling solvents are in particular the (C 1 -C 4 ) monoalkyl and dialkyl ether of diethylene glycol and / or dipropylene glycol into consideration.
  • a further advantage for the stability of the dispersion is the addition of isopropanol, glycol or glycerin, individually or in a mixture, preferably in an amount of 1 to 5% by weight, based on the final setting.
  • Such (meth) acrylic acid ester polymers or copolymers are advantageously added to the dispersions according to the invention in the form of a separately prepared aqueous anionic dispersion. It is also expedient to use the polymer or. Disperse copolymer dispersion using a compound of formula III or a mixture of such compounds.
  • the (meth) acrylic acid ester polymers or copolymers normally contain building blocks of esters of acrylic and / or methacrylic acid with C 1 to e 18 alcohols and can be prepared, for example, in a manner known per se.
  • Methacrylic ester copolymers are preferred, especially when the monomer mixture used for their preparation contains at least 80% by weight of esters of C 1 to C 4 alcohols.
  • Copolymers of methyl and isobutyl methacrylate are particularly preferred, particularly when the methyl ester content predominates in the copolymer.
  • a copolymer made from methyl methacrylate and isobutyl ester in a weight ratio of 3: 1 is very particularly preferred.
  • the preparation of this copolymer and its dispersion are described in Example 3.
  • Other (meth) acrylic ester polymers and copolymers can be prepared and dispersed analogously.
  • the aqueous anionic 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 contrast to the previously known dispersions.
  • the aqueous anionic dispersions according to the invention have an excellent oleophobic, hydrophobic, dirt-repellent and conductivity-improving effect in textile finishing. They can be used both for textile finishing alone, as well as in combination with other finishing agents, such as textile resins based on glyoxal or their derivatives, plasticizers, PVA and EVA or similar dispersions.
  • the aqueous anionic dispersions according to the invention are suitable for finishing textiles made from natural or synthetic fibers, in particular from polyamide, polyester, polyacrylonitrile and wool, or mixtures of these types of fibers.
  • the textile material can be in any form, e.g. as thread, fiber, yarn, flake, as fabric, knitted fabric, knitted fabric or fleece, but especially as a carpet.
  • the dispersions according to the invention can be applied to the textile material in the form in which they are produced. Normally, however, they will be diluted with water to a solids content of 1 to 10% by weight, preferably 1.5 to 5% by weight, for use.
  • the application to the textile material to be treated can be carried out in any suitable manner, for example by spraying, splashing, padding etc.
  • the order quantity is chosen so that 0.01 on the textile material up to 1% by weight of fluorine, preferably 0.05 to 0.2% by weight of fluorine. This corresponds approximately to an amount of 0.1 to 10, preferably 0.5 to 2% by weight solids content.
  • 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 4 minutes to about 30 seconds.
  • the high-boiling organic solvents preferably contained in the dispersion also have an important meaning in fixing the active ingredient of formula I on the fiber in the sense of a kind of carrier effect.
  • the progress of the reaction is IR-spectroscopically on removed samples on the disappearance of the isocyanate that controls.
  • the response time may be shortened or extended.
  • Example 1 is repeated without the addition of N-methyl-pyrrolidone. 1154 g of a pale yellowish melt are obtained which solidify on cooling to a hard, pale yellowish crystal cake.
  • the polymerization reaction will then begin immediately, as can be seen from a rise in temperature up to about 57 ° C. and a change in color (bluish fluorescent).
  • the monomer solution is added dropwise from the storage vessel and a separately prepared catalyst solution consisting of 0.2 g sodium pyrosulfite (Na 2 S 2 0 5 ) and 10 g water.
  • a separately prepared catalyst solution consisting of 0.2 g sodium pyrosulfite (Na 2 S 2 0 5 ) and 10 g water.
  • the introduction of nitrogen can be stopped.
  • the monomer solution should be metered in after about 1 hour and the catalyst solution a little later.
  • the reaction temperature is 55 to 60 ° C with an unchanged bath temperature of 55 ° C.
  • the polymer emulsion is heated to 60 to 62 ° C. (bath temperature 65 ° C.) and stirred for 1 h under these conditions, then cooled to room temperature and filtered through a PE sieve bag (105 ⁇ m). 270.4 g of an approximately 40% whitish, opaque dispersion are obtained.
  • Example 3 The procedure is as in Example 3, but the 30 g of the isopropanol solution of the emulsifier used there is replaced by 4 g of a commercially available alkane sulfonate used as a wash raw material (e.g. commercial product @Warolat U from Bayer AG).
  • a commercially available alkane sulfonate used as a wash raw material (e.g. commercial product @Warolat U from Bayer AG).
  • the crude dispersion obtained is then subjected to a final fine treatment, namely by sonication using an ultrasound machine (for example of the Sonifier type from Branson) until 90% of the particles have reached or fallen below a size of 1 ⁇ m. This usually takes 10 to 15 minutes.
  • the temperature is first kept at 40 to 45 ° C by water cooling, towards the end by cooling with ice water to 20 lowered to 30 ° C.
  • Example 5 is repeated, but product A produced according to example 1 is replaced by 11.8 g of the bisurethane prepared according to example 2.
  • the dispersion obtained is not stable in storage, since a clear sediment forms within 24 hours, which further increases over time.
  • a solution of 1.25 g of a compound of the formula VII is placed in a 200 ml three-necked flask in the form of a beaker in 48.75 ml of water and 20 g of the approx. 40% anionically dispersed methacrylic ester copolymer according to example 4 submitted.
  • This raw dispersion is then subjected to a final fine treatment, namely by sonication using an ultrasound machine (for example of the Sonifier type from Branson) until 90% of the particles have reached or fallen below an average size of 1 ⁇ m. This usually takes 10 to 15 minutes.
  • the temperature is initially maintained by water cooling at 40 to 45 0 C, lowered towards the end by cooling with ice water to 20 to 30 ° C.
  • the dispersion according to the invention prepared according to Example 5 or 7 is diluted with water to a solids content of 2 to 4% by weight.
  • the web to be treated is passed through the liquor thus obtained and squeezed off on a foulard. A repetition of this process promotes the penetration of the substrate and increases the effectiveness of the product according to the invention.
  • the textile substrate is dried in a drying unit at temperatures up to 120 ° C. and then fixed in the same or another unit by heat treatment at temperatures from 150 to 180 ° C. for 3 minutes to 3 seconds.
  • the dispersion prepared according to Example 5 is diluted with water to a solids content of 3% and sprayed onto a PA tufted carpet.
  • the carpet is then dried at 110 ° C and then subjected to a 3 minute heat treatment at 150 ° C.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Colloid Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Paints Or Removers (AREA)
EP86105191A 1985-04-20 1986-04-15 Dispersion aqueuse anionique Expired - Lifetime EP0202471B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86105191T ATE65809T1 (de) 1985-04-20 1986-04-15 Waessrige anionische dispersion.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853514373 DE3514373A1 (de) 1985-04-20 1985-04-20 Waessrige anionische dispersion
DE3514373 1985-04-20

Publications (3)

Publication Number Publication Date
EP0202471A2 true EP0202471A2 (fr) 1986-11-26
EP0202471A3 EP0202471A3 (en) 1988-10-12
EP0202471B1 EP0202471B1 (fr) 1991-07-31

Family

ID=6268725

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86105191A Expired - Lifetime EP0202471B1 (fr) 1985-04-20 1986-04-15 Dispersion aqueuse anionique

Country Status (11)

Country Link
US (1) US4775488A (fr)
EP (1) EP0202471B1 (fr)
JP (1) JPH06104192B2 (fr)
KR (1) KR860008334A (fr)
AT (1) ATE65809T1 (fr)
AU (1) AU582229B2 (fr)
BR (1) BR8601773A (fr)
DD (1) DD248383A5 (fr)
DE (2) DE3514373A1 (fr)
ES (1) ES8802404A1 (fr)
NZ (1) NZ215882A (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3672718D1 (de) * 1985-08-30 1990-08-23 Hoechst Ag Perfluoralkyl- und epichlorhydrin-gruppen enthaltende urethane, diese urethane enthaltende waessrige dispersionen und ihre verwendung.
US5242487A (en) * 1988-11-11 1993-09-07 Daikin Industries Ltd. Water- and oil-repellant composition
KR102792804B1 (ko) 2018-11-19 2025-04-14 삼성디스플레이 주식회사 다결정 실리콘층의 제조 방법, 표시 장치 및 표시 장치의 제조 방법
US20200399823A1 (en) * 2019-06-18 2020-12-24 Nicca Chemical Co., Ltd. Method of manufacturing anti-soiling carpet, and anti-soiling carpet

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3171861A (en) * 1957-06-11 1965-03-02 Minnesota Mining & Mfg Fluorinated aliphatic alcohols
US3993380A (en) * 1976-01-21 1976-11-23 Lawrence Peska Associates, Inc. Combined extension cord and grounding device
CA1185731A (fr) * 1979-02-16 1985-04-16 John E. Bacino Compositions au fluorocarbure, et methode d'enduction par projection
JPS5994621A (ja) * 1982-11-12 1984-05-31 Unitika Ltd 防汚性繊維の製造法

Also Published As

Publication number Publication date
EP0202471A3 (en) 1988-10-12
US4775488A (en) 1988-10-04
KR860008334A (ko) 1986-11-14
NZ215882A (en) 1988-09-29
AU5638986A (en) 1986-10-23
JPS61249538A (ja) 1986-11-06
ES554146A0 (es) 1988-05-16
EP0202471B1 (fr) 1991-07-31
BR8601773A (pt) 1986-12-23
ATE65809T1 (de) 1991-08-15
DD248383A5 (de) 1987-08-05
ES8802404A1 (es) 1988-05-16
JPH06104192B2 (ja) 1994-12-21
DE3680580D1 (de) 1991-09-05
DE3514373A1 (de) 1986-10-23
AU582229B2 (en) 1989-03-16

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