EP0202471B1 - Aqueous anionic dispersion - Google Patents
Aqueous anionic dispersion Download PDFInfo
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- EP0202471B1 EP0202471B1 EP86105191A EP86105191A EP0202471B1 EP 0202471 B1 EP0202471 B1 EP 0202471B1 EP 86105191 A EP86105191 A EP 86105191A EP 86105191 A EP86105191 A EP 86105191A EP 0202471 B1 EP0202471 B1 EP 0202471B1
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- EP
- European Patent Office
- Prior art keywords
- denotes
- formula
- ycf2
- anionic dispersion
- ch2ch2
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- 0 Cc(cccc1)c1N*N Chemical compound Cc(cccc1)c1N*N 0.000 description 2
Classifications
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- 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
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- 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.
- 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 can also have an H atom according to the above definitions in the ⁇ position for Y.
- 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 admixed and then to 10 o C higher than the melting point temperature of the tolylene di-isocyanate at a approximately 5 or mixture of tolylene di-isocyanate is added dropwise with stirring.
- the mixture is then heated to temperatures of approximately 130 ° C. in the course of an hour, the reaction proceeding 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 by using high shear forces, for example by using a high-speed stirrer, such as, for example, in an Ultraturrax type dispersion machine, and the predispersion obtained is then subjected, for example, to an ultrasound treatment or a treatment in a high-pressure homogenizer. After this treatment has ended, the particle size in the dispersion is more than 80%, preferably more than 95%, at or below 1 ⁇ m.
- Water-soluble solvents such as, for example, mono- or di-alcohols, lower ketones, polyglycol esters and polyglycol ethers, or mixtures of such solvents, are used for solvent component D.
- Component D advantageously contains at least one high-boiling, water-soluble solvent, ie a solvent whose boiling point is above approximately 150 ° C.
- a solvent mixture used can also contain one or more water-insoluble solvents, such as esters, ethers and / or higher ketones.
- Low-boiling solvent fractions can optionally be removed again at a later time, for example distilled off.
- Suitable water-soluble, high-boiling solvents are in particular the (C1-C4) monoalkyl and dialkyl ethers of diethylene glycol and / or dipropylene glycol.
- 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 C1 to C18 alcohols and can be prepared, for example, in a manner known per se.
- Methacrylic ester copolymers are preferred, particularly when the monomer mixture used for their preparation contains at least 80% by weight of esters of C1 to C4 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 o 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 application amount 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 of 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 the disappearance of the isocyanate bands on samples taken controlled.
- 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. Mp: 116 to 120 o C. Average F content: 60.5%.
- the polymerization reaction will then begin immediately, as can be seen from a rise in temperature to about 57 ° C. and a change in color (bluish fluorescent).
- the dropwise addition of the monomer solution from the storage vessel and a separately prepared catalyst solution consisting of 0.2 g of sodium pyrosulfite (Na2S2O5) and 10 g of water are started.
- 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 o C with an unchanged bath temperature of 55 o C.
- the polymer emulsion is heated to 60 to 62 o C (65 o C bath temperature) and stirred for 1 h under these conditions, then on 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 initially kept at 40 to 45 ° C by water cooling, towards the end by cooling with ice water to 20 lowered to 30 o 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 CF3 (CF2) 5-CH2CH2-O-CO-NH-CH2CH2-SSO3Na (VII) 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 first kept at 40 to 45 o C by water cooling, and finally reduced to 20 to 30 o C by cooling with ice water.
- 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.
- the oil repellency is tested according to the 3M / AATCC 18-1966 method, the hydrophobization / spray according to the AATCC 22-1952 method and the dry soiling according to the following regulation:
- the carpet sample is laid out in a cylindrical vessel that can be closed with a lid and is 20 cm long and 10 cm in diameter. Then 200 g of steel balls with a diameter of 3 mm and 20 g of sieved vacuum cleaner dirt are added, the vessel is closed and rolled on a trolley for 1 hour. Then the sample is taken, vacuumed with a vacuum cleaner and assessed.
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- 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)
Abstract
Description
Die vorliegende Erfindung betrifft eine wäßrige anionische Dispersion, die ein Bis-(2-perfluoralkyl-ethoxy-carbonylamino)-toluol enthält, ihre Herstellung und ihre Verwendung zur Oleophob- und Hydrophob-ausrüstung von Textilien, sowie den in der Dispersion enthaltenen Wirkstoff.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.
Aus der US-A-3 171 861 ist es z.B. bekannt, daß 3-(Perfluoroctyl)-propanol mit Toluoldiisocyanat zur dem entsprechenden Diurethan umgesetzt werden kann und daß diese Verbindung, aus einer Lösung in einem Aceton/1,1,1-Trichlorethan-Gemisch auf verschiedene Textilien aufgebracht, den behandelten Textilien eine ölabstoßende Eigenschaft verleiht.From US-A-3 171 861 it is e.g. It is known that 3- (perfluorooctyl) propanol can be reacted with toluenediisocyanate to give the corresponding diurethane and that this compound, applied to various textiles from a solution in an acetone / 1,1,1-trichloroethane mixture, gives the treated textiles an oil-repellent finish Gives property.
Aus der JP-A-59 094621 (zitiert nach Textilbericht 10/85) ist es bekannt, daß Synthesefasern schmutzabweisend, wasser- und ölabstoßend ausgerüstet werden können, wenn auf sie vor dem Verstrecken zusammen mit dem Spinnöl eine fluorhaltige Verbindung, z.B. 2,4-Bis(2-perfluoralkyl-ethoxy-carbonylamino)-toluol in solcher Menge aufgebracht wird, daß der aufgebrachte Film mindestens 20 Gew.% Fluor enthält.From JP-A-59 094621 (cited from textile report 10/85) it is known that synthetic fibers can be made dirt-repellent, water and oil-repellent if a fluorine-containing compound, e.g. 2,4-bis (2-perfluoroalkyl-ethoxy-carbonylamino) toluene is applied in such an amount that the film applied contains at least 20% by weight of fluorine.
Ein Handelsprodukt zur Textilausrüstung enthält derartige fluorhaltige Bisurethane zusammen mit kationischen Dispergierhilfsmitteln in einer wäßrigen Dispersion. Nachteilig bei der Anwendung dieser Dispersion ist jedoch, daß damit behandelte Fasern bzw. Textilien Schmutzpartikel anziehen, die normalerweise anionisch geladen sind. Aus diesem Grund müssen die kationischen Dispersionen der fluorhaltigen Bisurethane einen speziellen Antistatikzusatz enthalten, falls man nicht gezwungen sein will, die ausgerüsteten Waren später einer zusätzlichen Antistatik-Ausrüstung zu unterziehen.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, however, 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.
Aus den genannten Gründen ist es daher wünschenswert, die fluorhaltigen Bisurethane in Form einer anionischen, wäßrigen Dispersion auf die zu behandelnden Textilien aufzubringen. Es war jedoch bisher nicht möglich, fluorhaltige Bisurethane in eine wäßrige anionische Dispersion zu überführen, welche die Forderungen der Praxis, insbesondere der Langzeitstabilität bei Temperaturen von -20oC bis +40oC, erfüllte.For the reasons mentioned, it is therefore desirable to apply the fluorine-containing bisurethanes to the textiles to be treated in the form of an anionic, aqueous dispersion. However, it was previously not possible to convert fluorine-containing bisurethanes in an aqueous anionic dispersion containing the requirements of practice, especially the long-term stability at temperatures of -20 o C to +40 o C fulfilled.
Es wurde nun überraschenderweise gefunden, daß sich derartige, die Praxisforderungen erfüllende wäßrige anionische Dispersionen von fluorhaltigen Bisurethanen herstellen lassen.It has now surprisingly been found that such aqueous anionic dispersions of fluorine-containing bisurethanes which meet practical requirements can be prepared.
Die erfindungsgemäße wäßrige anionische Dispersion enthält:
- A) a % eines Produktes, das mindestens ein Bis-(2-fluoralkyl-ethoxy-carbonylamino)-toluol der Formel I
YCF₂-(CF₂)n-CH₂CH₂OH (II)
wobei n und Y die bereits genannten Bedeutungen besitzen, mit Tolylen-di-isocyanat im Molverhältnis (1,8 bis 2) : 1 in Gegenwart von 2 bis 5 % N-Methyl-pyrrolidon, bezogen auf die Verbindung der Formel II, herstellbar ist, - B) b % mindestens eines Emulgators der Formel III
YCF₂(CF₂)p-CH₂CH₂O-CO-NH-CH₂CH₂-SSO₃X (III)
wobei p eine Zahl von 5 bis 15, Y = -H oder -F und X ein einwertiges Kation bedeuten, - C) c % mindestens eines nichtionischen Emulgators der Formel IV
YCF₂-(CF₂)q-CH₂CH₂-(OCH₂CH₂)r-OH (IV)
wobei Y = -H oder -F, q eine Zahl von 5 bis 15, r eine Zahl von 0 bis 10 bedeuten und - D) d % eines Lösungsmittels oder Lösungsmittelgemischs, wobei a eine Zahl von 5 bis 25, b eine Zahl von 1 bis 14, c eine Zahl von 1 bis 14, d eine Zahl von 5 bis 30 bedeuten und dabei die Zahlenwerte für b und c so gewählt sind, daß die Summe (b + c) = 2 bis 15 beträgt.
- A) a% of a product containing at least one bis (2-fluoroalkyl-ethoxy-carbonylamino) toluene of the formula I.
YCF₂- (CF₂) n -CH₂CH₂OH (II)
where n and Y have the meanings already mentioned, can be prepared with tolylene di-isocyanate in a molar ratio (1.8 to 2): 1 in the presence of 2 to 5% of N-methylpyrrolidone, based on the compound of the formula II , - B) b% of at least one emulsifier of the formula III
YCF₂ (CF₂) p -CH₂CH₂O-CO-NH-CH₂CH₂-SSO₃X (III)
where p is a number from 5 to 15, Y = -H or -F and X is a monovalent cation, - C) c% of at least one nonionic emulsifier of the formula IV
YCF₂- (CF₂) q -CH₂CH₂- (OCH₂CH₂) r -OH (IV)
where Y = -H or -F, q is a number from 5 to 15, r is a number from 0 to 10 and - D) d% of a solvent or solvent mixture, where a is a number from 5 to 25, b is a number from 1 to 14, c is a number from 1 to 14, d is a number from 5 to 30 and the numerical values for b and c are chosen so that the sum (b + c) = 2 to 15.
Die vorstehend angegebenen Prozente stellen Gewichtsprozente dar. Die Prozentangaben für a, b, c und d sind auf das Gesamtgewicht der wäßrigen Dispersion bezogen. Im Rahmen der vorliegenden Erfindung können die vorstehend und nachfolgend erwähnten Perfluoralkyl-reste bzw. Perfluoralkyl-verbindungen nach den vorstehenden Definitionen in ω-Stellung für Y auch ein H-Atom besitzen. Die echten Perfluoralkyl-reste bzw. Perfluoralkyl-verbindungen, d.h. diejenigen Verbindungen der Formeln I bis IV, bei denen Y = -F bedeutet, sind jedoch bevorzugt.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. In the context of the present invention, the perfluoroalkyl radicals or perfluoroalkyl compounds mentioned above and below can also have an H atom according to the above definitions in the ω position for Y. The real perfluoroalkyl residues or perfluoroalkyl compounds, i.e. however, those compounds of the formulas I to IV in which Y is = -F are preferred.
Die Verbindungen der Formel II, III und IV können in Form ihrer technischen Gemische eingesetzt werden, die in der Regel mehrere Verbindungen der genannten Art mit verschiedenen Indexzahlen n, p, q und/oder r enthalten.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.
Die Verbindungen der Formel I sind bekannt. Der Wirkstoff A, der erfindungsgemäß zur Herstellung der wäßrigen anionischen Dispersion benutzt wird, ist jedoch neu. Zur Herstellung des unter A angegebenen Produkts wird ein 2-Perfluoralkyl-ethanol der Formel II oder ein Gemisch verschiedener 2-Perfluoralkyl-ethanole der Formel II mit einem Tolylen-di-isocyanat oder einem Gemisch verschiedener Tolylen-di-isocyanate im Mol-Verhältnis (1,8 bis 2) : 1 in Gegenwart von 2 bis 5 Gew.%, vorzugsweise 2 bis 3,5 Gew.%, bezogen auf die Verbindung der Formel II, an N-Methyl-pyrrolidon umgesetzt. Als Ausgangsprodukt sind dabei technische Gemische von 2-Perfluoralkyl-ethanolen der Formel II gut geeignet, die Verbindungen mit n = 5 bis 11 enthalten. Besonders geeignet sind Verbindungen der Formel II mit n = 7 bis 11, und zwar sowohl in Form der Einzelverbindungen als auch in Form ihrer technischen Gemische.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. 2-perfluoroalkylethanol of the formula II or a mixture of different 2-perfluoroalkylethanols of the formula II with a tolylene di-isocyanate or a mixture of different tolylene di-isocyanates in a molar ratio (1.8 to 2): 1 in Presence of 2 to 5 wt.%, Preferably 2 to 3.5 wt.%, Based on the compound of the formula II, of N-methyl-pyrrolidone. Technical mixtures of 2-perfluoroalkylethanols of the formula II which contain compounds with n = 5 to 11 are very suitable as the starting product. Compounds of the formula II with n = 7 to 11 are particularly suitable, both in the form of the individual compounds and in the form of their industrial mixtures.
Als Tolylen-di-isocyanat kommen insbesondere das 2,4- und/oder das 2,6-Tolylen-di-isocyanat in Betracht, insbesondere in Form eines Handelsprodukts, das ca. 80 Gew.% 2,4-Tolylen-di-isocyanat und ca. 20 Gew.% 2,6-Tolylen-di-isocyanat enthält.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.
Die Umsetzung zur Herstellung des Produkts A wird in der Regel so durchgeführt, daß die Verbindung II oder das Gemisch der Verbindungen II aufgeschmolzen und zu der Schmelze 2 bis 5 Gew.%, vorzugsweise 2 bis 3,5 Gew.%, N-Methyl-pyrrolidon zugemischt wird und anschließend bei einer ca. 5 bis 10oC über dem Schmelzpunkt liegenden Temperatur das Tolylen-di-isocyanat oder das Gemisch der Tolylen-di-isocyanate unter Rühren zugetropft wird. Anschließend wird im Verlauf einer Stunde auf Temperaturen von ca. 130oC aufgeheizt, wobei die Reaktion ab Temperaturen von ca. 80oC leicht exotherm verläuft. Abschließend wird die Umsetzung durch eine ca. dreistündige Reaktionszeit bei ca. 130oC zum Abschluß gebracht. Das Fortschreiten der Reaktion wird laufend IR-spektroskopisch an entnommenen Proben auf das Verschwinden der Isocyanatbanden kontrolliert. Falls die Reaktion in der angegebenen Zeit noch nicht zum Abschluß gekommen ist, muß die Reaktionszeit, z.B. auf 6 Stunden, verlängert werden.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 admixed and then to 10 o C higher than the melting point temperature of the tolylene di-isocyanate at a approximately 5 or mixture of tolylene di-isocyanate is added dropwise with stirring. The mixture is then heated to temperatures of approximately 130 ° C. in the course of an hour, the reaction proceeding slightly exothermic from temperatures of approximately 80 ° C. Finally, 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.
Durch den Zusatz von N-Methylpyrrolidon werden vermutlich Nebenprodukte noch unbekannter Struktur gebildet, die bei der erfindungsgemäßen Dispergierung des Produkts als vorzügliche Dispersionsstabilisatoren wirken. Ein größerer Zusatz von N-Methylpyrrolidon bei der Herstellung des Produkts A beeinflußt den Effekt der Dispersionsstabilisierung nicht ungünstig, vermindert aber unnötigerweise die Ausbeute an der Wirksubstanz der Formel I.The addition of 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.
Das einwertige Kation X in den Verbindungen der Formel III stellt in der Regel ein Alkalimetallkation, insbesondere das Natrium- oder Kaliumkation oder das Ammoniumkation dar. Das Ammoniumkation kann gegebenenfalls auch durch organische Reste substituiert sein, beispielsweise Triethanolammonium darstellen. Verbindungen der Formel III sind insbesondere in Form der technischen Gemische mit p = 5 bis 11 oder 7 bis 11 handelsüblich. Vorzugsweise werden die Verbindungen der Formel III mit p = 7 bis 11 in Form der Einzelverbindungen oder in Form der technische Gemische verwendet.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. Compounds of the formula III are commercially available, in particular in the form of technical mixtures with p = 5 to 11 or 7 to 11. The compounds of the formula III with p = 7 to 11 are preferably used in the form of the individual compounds or in the form of the industrial mixtures.
Auch die Emulgatoren der Formel IV sind im Handel, zumeist in Form ihrer technischen Gemische, erhältlich. Dabei beträgt r insbesondere ca. 6. Es werden Emulgatoren der Formel IV bevorzugt, bei denen q = 5 bis 11, insbesondere 7 bis 11, und r = 4 bis 8 beträgt, und zwar in Form der Einzelverbindungen oder in Form der technischen Gemische.The emulsifiers of the formula IV are also commercially available, mostly in the form of their technical mixtures. In this case, r is in particular approximately 6. Emulsifiers of the formula IV are preferred in which q = 5 to 11, in particular 7 to 11, and r = 4 to 8, in the form of the individual compounds or in the form of the technical mixtures.
Die Zahlen b und c bedeuten vorzugsweise jeweils 1 bis 9, wobei diese Zahlenwerte vorzugsweise so gewählt werden, daß die Summe (b + c) = 2 bis 12 beträgt. d bedeutet vorzugsweise eine Zahl von 10 bis 25.The numbers b and c each preferably mean 1 to 9, these numerical values preferably being chosen so that the sum (b + c) = 2 to 12. d is preferably a number from 10 to 25.
Zur Herstellung der erfindungsgemäßen wäßrigen anionischen Dispersionen werden die Komponenten A, B, C und D in Wasser, unter Zufuhr einer verhältnismäßig großen Energiemenge, dispergiert. Die Mengenverhältnisse für die Komponenten werden dabei so gewählt, daß nach der Dispergierung die angegebene Zusammensetzung für die Dispersion erreicht wird. Es ist dabei unerläßlich, das Produkt A zumindest in einem Teil der zur Anwendung kommenden Menge des Lösungsmittels oder Lösungsmittelgemischs vorzulösen, und es ist zweckmäßig, die Dispergierung in zwei Teilschritte aufzuteilen und zuerst eine Vordispergierung und anschließend eine Feindispergierung vorzunehmen. Die Vordispergierung wird zweckmäßigerweise durch Anwendung hoher Scherkräfte, beispielsweise durch die Verwendung eines schnell laufenden Rührers, wie z.B. bei einer Dispergiermaschine vom Typ Ultraturrax, vorgenommen, und die dabei erhaltene Vordispersion wird anschließend z.B. einer Ultraschallbehandlung oder einer Behandlung in einem Hochdruckhomogenisator unterzogen. Nach der Beendigung dieser Behandlung liegt die Teilchengröße in der Dispersion zu über 80 %, vorzugsweise zu über 95 %, bei oder unter 1 µm. Für die Lösungsmittelkomponente D werden wasserlösliche Lösungsmittel, wie z.B. Mono-oder Di-Alkohole, niedere Ketone, Polyglykolester und Polyglykolether oder Gemische derartiger Lösungsmittel verwendet. Vorteilhafterweise enthält die Komponente D mindestens ein hochsiedendes, wasserlösliches Lösungsmittel, d.h. ein Lösungsmittel, dessen Siedepunkt über ca. 150oC liegt. Gegebenenfalls kann ein zur Anwendung kommendes Lösungsmittelgemisch auch ein oder mehrere wasserunlösliche Lösungsmittel, wie z.B. Ester, Ether und/oder höhere Ketone, enthalten. Niedrigsiedende Lösungsmittelanteile können gegebenenfalls zu einem späteren Zeitpunkt wieder entfernt, z.B. abdestilliert werden.To prepare the aqueous anionic dispersions according to the invention, 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 by using high shear forces, for example by using a high-speed stirrer, such as, for example, in an Ultraturrax type dispersion machine, and the predispersion obtained is then subjected, for example, to an ultrasound treatment or a treatment in a high-pressure homogenizer. After this treatment has ended, the particle size in the dispersion is more than 80%, preferably more than 95%, at or below 1 μm. Water-soluble solvents, such as, for example, mono- or di-alcohols, lower ketones, polyglycol esters and polyglycol ethers, or mixtures of such solvents, are used for solvent component D. Component D advantageously contains at least one high-boiling, water-soluble solvent, ie a solvent whose boiling point is above approximately 150 ° C. If appropriate, a solvent mixture used can also contain one or more water-insoluble solvents, such as esters, ethers and / or higher ketones. Low-boiling solvent fractions can optionally be removed again at a later time, for example distilled off.
Als geeignete wasserlösliche, hochsiedende Lösungsmittel kommen insbesondere die (C₁-C₄)Monoalkyl- und Dialkylether des Diethylenglykols und/oder Dipropylenglykols in Betracht. Günstig für die Stabilität der Dispersion ist ferner ein Zusatz von Isopropanol, Glykol oder Glyzerin, einzeln oder im Gemisch, vorzugsweise in einer Menge von 1 bis 5 Gew.%, bezogen auf die Endeinstellung.Suitable water-soluble, high-boiling solvents are in particular the (C₁-C₄) monoalkyl and dialkyl ethers of diethylene glycol and / or dipropylene glycol. 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.
Besonders günstige Effekte, insbesondere im Hinblick auf die schmutzabweisende Wirkung, werden erhalten, wenn die erfindungsgemäße Dispersion zusätzlich mindestens ein anionisch dispergiertes (Meth)Acrylsäureester-polymerisat oder -copolymerisat in Mengen von e Gew.% enthält, wobei e eine Zahl von 5 bis 25 bedeutet, die zweckmäßigerweise so gewählt ist, daß die Summe (a + e) = 15 bis 30 beträgt. Derartige (Meth)Acrylsäureester-polymerisate bzw. -copolymerisate werden zweckmäßigerweise in Form einer getrennt hergestellten wäßrigen anionischen Dispersion den erfindungsgemäßen Dispersionen zugesetzt. Außerdem ist es zweckmäßig, die Polymerisat-bzw. Copolymerisatdispersion unter Verwendung einer Verbindung der Formel III oder eines Gemisches derartiger Verbindungen zu dispergieren.Particularly favorable effects, in particular with regard to the dirt-repellent effect, are obtained if the dispersion according to the invention additionally contains at least one anionically dispersed (meth) acrylic acid ester polymer or copolymer in amounts of e% by weight, where e is a number from 5 to 25 means, which is expediently chosen so that the sum (a + e) = 15 to 30. 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.
Die (Meth)Acrylsäureester-polymerisate oder -copolymerisate enthalten normalerweise Bausteine von Estern der Acryl- und/oder Methacrylsäure mit C₁- bis C₁₈-Alkoholen und können z.B. in an sich bekannter Weise hergestellt werden. Methacrylester-copolymerisate sind bevorzugt, insbesondere dann, wenn das zu ihrer Herstellung benutzte Monomerengemisch mindestens 80 Gew.% Ester von C₁- bis C₄-Alkoholen enthält. Besonders bevorzugt sind Copolymerisate aus Methacrylsäuremethyl- und -isobutylester, insbesondere dann, wenn in dem Copolymerisat der Methylesteranteil überwiegt. Ganz besonders bevorzugt ist ein Copolymerisat, hergestellt aus Methacrylsäuremethylester und -isobutylester im Gewichtsverhältnis 3 : 1. Die Herstellung dieses Copolymerisats und seine Dispergierung ist in Beispiel 3 beschrieben. Andere (Meth)Acrylesterpolymerisate und -copolymerisate können analog hergestellt und dispergiert werden.The (meth) acrylic acid ester polymers or copolymers normally contain building blocks of esters of acrylic and / or methacrylic acid with C₁ to C₁₈ alcohols and can be prepared, for example, in a manner known per se. Methacrylic ester copolymers are preferred, particularly when the monomer mixture used for their preparation contains at least 80% by weight of esters of C₁ to C₄ 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.
Die erfindungsgemäßen wäßrigen anionischen Dispersionen erfüllen alle Forderungen der Praxis und zeigen insbesondere eine hervorragende Langzeitstabilität bei Temperaturen von -20 bis +40oC. Sie gefrieren zwar bei Minustemperaturen, die Dispersion bleibt aber nach dem Auftauen erhalten, im Gegensatz zu den bisher bekannten Dispersionen. Die erfindungsgemäßen wäßrigen anionischen Dispersionen zeigen bei der Textilausrüstung einen hervorragenden oleophobierenden, hydrophobierenden, schmutzabweisenden und leitfähigkeitsverbessernden Effekt. Sie können sowohl allein für die Textilausrüstung eingesetzt werden, wie auch in Kombination mit anderen Ausrüstungsmitteln, wie Textilharzen auf der Basis Glyoxal oder deren Derivaten, Weichmachern, PVA und EVA oder ähnlichen Dispersionen.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 o 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.
Die erfindungsgemäßen wäßrigen anionischen Dispersionen sind zur Ausrüstung von Textilien aus natürlichen oder synthetischen Fasern, insbesondere aus Polyamid, Polyester, Polyacrylnitril und Wolle, oder Gemischen dieser Faserarten geeignet. Das Textilmaterial kann in beliebiger Form vorliegen, so z.B. als Faden, Faser, Garn, Flocke, als Gewebe, Gestrick, Gewirk oder Vlies, insbesondere jedoch als Teppich.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.
Die erfindungsgemäßen Dispersionen können in der Form auf das Textilmaterial aufgebracht werden, in der sie bei der Herstellung anfallen. Normalerweise wird man sie jedoch zur Anwendung mit Wasser auf einen Feststoffgehalt von 1 bis 10 Gew.%, vorzugsweise von 1,5 bis 5 Gew.%, verdünnen. Die Aufbringung auf das zu behandelnde Textilmaterial kann in jeder geeigneten Weise erfolgen, so z.B. durch Spühen, Pflatschen, Foulardieren etc. Die Auftragsmenge wird so gewählt, daß auf dem Textilmaterial 0,01 bis 1 Gew.% Fluor, vorzugsweise 0,05 bis 0,2 Gew.% Fluor, vorhanden sind. Dies entspricht etwa einer Menge von 0,1 bis 10, vorzugsweise 0,5 bis 2 Gew.% Feststoffgehalt. Nach dem Aufbringen auf das zu behandelnde Textilmaterial erfolgt eine Trocknung bei Temperaturen bis ca. 120oC, z.B. bei 100 bis 120oC, und anschließend wird eine Wärmebehandlung bei Temperaturen von ca. 130 bis 190oC, vorzugsweise 140 bis 180oC, durchgeführt, die normalerweise etwa 4 min bis etwa 30 sec dauert.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 application amount 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. After application to the textile material to be treated, drying is carried out at temperatures of 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.
Es hat den Anschein, als ob die in der Dispersion vorzugsweise enthaltenen, hochsiedenden organischen Lösungsmittel auch eine wichtige Bedeutung bei der Fixierung des Wirkstoffs der Formel I auf der Faser im Sinne eines Art Carrier-Effekts besitzen.It appears as if 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.
In den nachfolgenden Beispielen bedeuten Prozentangaben, sofern nichts anderes angeben ist, Gewichtsprozente.In the following examples, percentages mean percentages by weight, unless stated otherwise.
1080 g (= 2 mol) eines handelsüblichen Gemisches von 2-Perfluoralkyl-ethanolen der Formel II, in der Einzelprodukte mit n = 7 bis 11 enthalten sind und Y = -F bedeutet, werden in einem Reaktionsgefäß über den bei 65oC liegenden Schmelzpunkt aufgeheizt und 30 g N-Methyl-pyrrolidon zugegeben. Bei einer Temperatur von 70 bis 75oC werden dann im Verlauf von 30 min 174.16 g (= 1 mol) eines technischen Gemisches aus 80 % 2,4- und 20 % 2,6-Tolylen-di-isocyanat unter Rühren zugetropft. Anschließend wird im Verlauf von 1 h auf 130oC aufgeheizt, wobei die Reaktion ab 80oC leicht exotherm verläuft, und die Temperatur ca. 3 h bis 130oC gehalten.1080 g (= 2 mol) of a commercially available mixture of 2-perfluoroalkylethanols of the formula II, in which individual products with n = 7 to 11 and Y = -F are contained, are in a reaction vessel above the melting point at 65 ° C. heated and 30 g of N-methyl-pyrrolidone added. At a temperature of 70 to 75 o C are then added dropwise over 30 minutes 174.16 g (= 1 mol) of a commercial mixture of 80% 2,4- and 20% 2,6-tolylene di-isocyanate while stirring. The mixture is then heated to 130 ° C. in the course of 1 h, the reaction being slightly exothermic from 80 ° C. and the temperature being held for about 3 hours to 130 ° C.
Das Fortschreiten der Reaktion wird an entnommenen Proben IR-spektroskopisch auf das Verschwinden der Isocyanatbanden kontrolliert. Gegebenenfalls wird die Reaktionszeit verkürzt oder verlängert.The progress of the reaction is IR-spectroscopically on the disappearance of the isocyanate bands on samples taken controlled. The response time may be shortened or extended.
Es werden 1184 g einer gelbbraunen Schmelze erhalten, die beim Erkalten zu einem leicht bräunlichen Kristallkuchen erstarrt.
Fp: 90 bis 118oC. Durchschnittlicher F-Gehalt: 59 %.1184 g of a yellow-brown melt are obtained, which solidify to a slightly brownish crystal cake when cooled.
Mp: 90 to 118 o C. Average F content: 59%.
Das Beispiel 1 wird ohne den Zusatz von N-Methyl-pyrrolidon wiederholt. Es werden 1154 g einer schwach gelblichen Schmelze erhalten, die beim Erkalten zu einem harten, schwach gelblichen Kristallkuchen erstarrt.
Fp: 116 bis 120oC. Durchschnittlicher F-Gehalt: 60,5 %.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.
Mp: 116 to 120 o C. Average F content: 60.5%.
In einem mit Rührer und Bodenauslauf versehenen 250 ml-Vorratsgefäß werden 75 g Methacrylsäuremethylester und 25 g Methacrylsäure-isobutylester vorgelegt und zu einer homogenen Lösung verrührt, worauf der Rührer abgestellt wird.75 g of methyl methacrylate and 25 g of isobutyl methacrylate are placed in a 250 ml storage vessel provided with a stirrer and bottom outlet and stirred into a homogeneous solution, whereupon the stirrer is switched off.
In einem 500ml-Polymerisationskolben, ausgerüstet mit Rührer, Thermometer, Gaseinleitungsrohr, Rückflußkühler, Tropftrichter und Zulaufmöglichkeit aus dem Vorratsgefäß werden 130 g Wasser, 30 g einer 25%igen isopropanolischen Lösung eines handelsüblichen Emulgators der Formel V
CF₃(CF₂)₅-CH₂CH₂O-CO-NH-CH₂CH₂-SSO₃Na (V)
und 22 ml der Monomerenlösung aus dem Vorratsgefäß vorgelegt. Unter Rühren und Einleiten eines schwachen Stickstoffstroms in die Lösung wird der Polymerisationskolben mittels eines elektrisch beheizten Wasserbads auf 50oC angeheizt (55oC Bad). Nach Erreichen dieser Temperatur werden 0,2 g Kaliumpersulfat in einer Portion zugegeben. Die Polymerisationsreaktion wird unmittelbar daraufhin einsetzen, was an einem Temperaturanstieg bis auf ca. 57oC sowie einer Farbänderung (bläulich fluoreszierend) festzustellen ist. Beim Überschreiten der Innentemperatur von 56oC wird mit dem Zutropfen der Monomerenlösung aus dem Vorratsgefäß sowie einer gesondert hergestellten Katalysatorlösung, bestehend aus 0,2 g Natriumpyrosulfit (Na₂S₂O₅) und 10 g Wasser, begonnen. Gleichzeitig kann das Einleiten von Stickstoff abgebrochen werden. Die Monomerenlösung soll nach ca. 1 h, die Katalysatorlösung etwas später zudosiert sein.130 g of water and 30 g of a 25% isopropanolic solution of a commercially available emulsifier of the formula V are placed in a 500 ml polymerization flask equipped with a stirrer, thermometer, gas inlet tube, reflux condenser, dropping funnel and inlet option from the storage vessel
CF₃ (CF₂) ₅-CH₂CH₂O-CO-NH-CH₂CH₂-SSO₃Na (V)
and 22 ml of the monomer solution from the storage vessel. The polymerization flask is stirred and a weak stream of nitrogen is introduced into the solution heated to 50 o C (55 o C bath) using an electrically heated water bath. After reaching this temperature, 0.2 g of potassium persulfate are added in one portion. The polymerization reaction will then begin immediately, as can be seen from a rise in temperature to about 57 ° C. and a change in color (bluish fluorescent). When the internal temperature of 56 o C is exceeded, the dropwise addition of the monomer solution from the storage vessel and a separately prepared catalyst solution consisting of 0.2 g of sodium pyrosulfite (Na₂S₂O₅) and 10 g of water are started. At the same time, 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.
Während dieser gesamten Zutropfphase liegt die Reaktionstemperatur bei 55 bis 60oC bei unveränderter Badtemperatur von 55oC. Nach beendetem Zutropfen wird die Polymeremulsion auf 60 bis 62oC (65oC Badtemperatur) angeheizt und 1 h unter diesen Bedingungen nachgerührt, anschließend auf Raumtemperatur abgekühlt und über einen PE-Siebbeutel (105 µm) filtriert. Es werden 270,4 g einer ca. 40%igen weißlichen, opaken Dispersion erhalten.During this entire dropping phase, the reaction temperature is 55 to 60 o C with an unchanged bath temperature of 55 o C. After the dropping has ended, the polymer emulsion is heated to 60 to 62 o C (65 o C bath temperature) and stirred for 1 h under these conditions, then on Cooled to room temperature and filtered through a PE sieve bag (105 µm). 270.4 g of an approximately 40% whitish, opaque dispersion are obtained.
Es wird wie in Beispiel 3 gearbeitet, jedoch werden die 30 g der isopropanolischen Lösung des dort benutzten Emulgators durch 4 g eines handelsüblichen, als Waschrohstoff benutzten Alkansulfonats (z.B. Handelsprodukt ®Warolat U der Firma Bayer AG) ersetzt.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).
Es werden 244,2 g einer ca. 40%igen weißlichen, opaken Dispersion erhalten.244.2 g of an approximately 40% whitish, opaque dispersion are obtained.
In einem 200ml-Schliff-Dreihalskolben in Becherform werden 12,1 g des nach Beispiel 1 hergestellten Produkts A, 5 g Diethylenglykol-dimethylether, 5 g Dipropylenglykolmonomethylether und 3 g Perfluoralkylethyl-polyglykol der Formel VI
CF₃(CF₂)₇₋₁₁-CH₂CH₂-(OCH₂CH₂)₆-OH (VI)
bei 80 bis 90oC gelöst. Dann werden bei 80oC 5 g einer 25%igen isopropanolischen Lösng einer Verbindung der Formel VII
CF₃(CF₂)₅-CH₂CH₂-O-CO-NH-CH₂CH₂-SSO₃Na (VII)
zugemischt.12.1 g of product A prepared according to Example 1, 5 g of diethylene glycol dimethyl ether, 5 g of dipropylene glycol monomethyl ether and 3 g of perfluoroalkylethyl polyglycol of the formula VI are placed in a 200 ml three-necked flask in the form of a cup
CF₃ (CF₂) ₇₋₁₁-CH₂CH₂- (OCH₂CH₂) ₆-OH (VI)
solved at 80 to 90 o C. Then, at 80 o C to 5 g of a 25% isopropanolic Lösng a compound of formula VII
CF₃ (CF₂) ₅-CH₂CH₂-O-CO-NH-CH₂CH₂-SSO₃Na (VII)
added.
In die Lösung wird bei 80oC unter der Anwendung von starken Scherkräften einer Dispergiermaschine vom Typ Ultraturrax im Laufe von 2 bis 3 min die Lösung von 1,25 g der Verbindung der Formel VII in 48,75 ml Wasser eingetropft, wobei die Temperatur auf 45 bis 50oC abfällt. Bei dieser Temperatur wird noch 10 bis 15 min weiterdispergiert. Hierbei entsteht bereits eine äußerlich ansprechende Emulsion, die aber in dieser Form noch nicht lagerbeständig ist, sondern sich bald absetzt.In the solution of a dispersing machine of the type Ultraturrax in the course of 2, wherein the temperature is g to 3 min, the solution of 1.25 of the compound of formula VII is added dropwise to 48.75 ml of water at 80 ° C under the application of strong shear forces on 45 to 50 o C drops. Dispersion is continued for a further 10 to 15 minutes at this temperature. This creates an externally appealing emulsion, which is not yet stable in this form, but will soon settle.
Die erhaltene Rohdispersion wird dann einer abschließenden Feinbehandlung unterworfen, und zwar durch Beschallung mittels einer Ultraschallmaschine (z.B. vom Typ Sonifier der Firma Branson), bis 90 % der Teilchen eine Größe von 1 µm erreicht oder unterschritten haben. Dies dauert gewöhnlich 10 bis 15 min. Dabei wird die Temperatur zunächst durch Wasserkühlung bei 40 bis 45oC gehalten, gegen Ende durch Kühlung mit Eiswasser auf 20 bis 30oC gesenkt.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 μm. This usually takes 10 to 15 minutes. The temperature is initially kept at 40 to 45 ° C by water cooling, towards the end by cooling with ice water to 20 lowered to 30 o C.
Zu dieser so erhaltenen Feindispersion werden dann 20 g des ca. 40%igen, anionisch dispergierten Methacrylester-copolymerisats nach Beispiel 3 hinzugefügt. Die gesamte Formulierung wird dann nochmals ca 2 min. unter Kühlung bei 20 bis 30oC mit Ultraschall behandelt. Man erhält 100 g einer feinen, milchig opaken Dispersion mit einem Fluorgehalt von 7 % (bezogen auf Wirksubstanz), die auch bei Temperaturen von -20oC und +40oC sehr gut lagerstabil ist.20 g of the approximately 40% anionically dispersed methacrylic ester copolymer according to Example 3 are then added to this fine dispersion obtained in this way. The entire formulation is then again about 2 min. treated with ultrasound under cooling at 20 to 30 o C. This gives 100 g of a fine, milky opaque dispersion with a fluorine content of 7% (based on active substance), which is very stable in storage even at temperatures of -20 o C and +40 o C.
Nach einem 24stündigem Abkühlen auf -20oC konnte beim Wiederauftauen keine Veränderung der Dispersion beobachtet werden.After cooling to -20 o C for 24 hours, no change in the dispersion could be observed on thawing.
Das Beispiel 5 wird wiederholt, dabei wird jedoch das gemäß Beispiel 1 hergstellte Produkt A durch 11,8 g des nach Beispiel 2 hergestellten Bisurethans ersetzt.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.
Die erhaltene Dispersion ist nicht lagerbeständig, da sich bereits innerhalb von 24 h ein deutlicher Bodensatz bildet, der sich im Laufe der Zeit weiter verstärkt.The dispersion obtained is not stable in storage, since a clear sediment forms within 24 hours, which further increases over time.
In einem 200 ml-Schliff-Dreihalskolben in Becherform wird eine Lösung von 1,25 g einer Verbindung der Formel VII
CF₃(CF₂)₅-CH₂CH₂-O-CO-NH-CH₂CH₂-SSO₃Na (VII)
in 48,75 ml Wasser und 20 g des ca. 40%igen, anionisch dispergierten Methacrylester-copolymerisats nach Beispiel 4 vorgelegt. In diese Mischung wird unter der starken Scherwirkung einer Dispergiermaschine von Typ Ultraturrax eine 80oC heiße Lösung von 12,1 g des nach Beispiel 1 hergestellten Produkts A in 5 g Diethylenglykol-dimethylether, 5 g Dipropylengkyol-monomethylether, 3 g Perfluoralkylethyl-polyglykol der Formel VI
CF₃(CF₂)₇₋₁₁-CH₂CH₂-(OCH₂CH₂)₆-OH (VI)
und 5 g einer 25%igen Lösung der Verbindung der Formel VII in Isopropanol eingerührt, wobei die Temperatur auf ca. 35oC abfällt. Man behandelt die Mischung ca. 10 min lang ohne Kühlung weiter mit dem Ultraturrax, bis die Temperatur auf 45 bis 50oC angestiegen ist.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
CF₃ (CF₂) ₅-CH₂CH₂-O-CO-NH-CH₂CH₂-SSO₃Na (VII)
in 48.75 ml of water and 20 g of the approx. 40% anionically dispersed methacrylic ester copolymer according to example 4 submitted. In this mixture a dispersing machine of the Ultraturrax type, under the strong shearing effect a 80 ° C hot solution of 12.1 g of the product A obtained in Example 1 in 5 g of diethylene glycol dimethyl ether, 5 g Dipropylengkyol monomethyl ether, 3 g of perfluoroalkylethyl polyglycol of Formula VI
CF₃ (CF₂) ₇₋₁₁-CH₂CH₂- (OCH₂CH₂) ₆-OH (VI)
and 5 g of a 25% solution of the compound of formula VII stirred in isopropanol, the temperature dropping to about 35 ° C. Is the mixture is treated about 10 minutes without cooling further with an Ultraturrax, until the temperature at 45 ° to 50 ° C increased.
Hierbei entsteht eine äußerlich ansprechende Emulsion, die aber in dieser Form noch nicht lagerbeständig ist, sondern sich bald absetzt.This creates an externally appealing emulsion, which is not yet stable in this form, but will soon settle.
Diese Rohdispersion wird dann einer abschließenden Feinbehandlung unterworfen, und zwar durch Beschallung mittels einer Ultraschallmaschine (z.B. vom Typ Sonifier der Firma Branson), bis 90 % der Teilchen eine mittlere Größe von 1 µm erreicht oder unterschritten haben. Dies dauert gewöhnlich 10 bis 15 min. Dabei wird die Temperatur zunächst durch Wasserkühlung bei 40 bis 45oC gehalten, gegen Ende durch Kühlung mit Eiswasser auf 20 bis 30oC gesenkt.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 μm. This usually takes 10 to 15 minutes. The temperature is first kept at 40 to 45 o C by water cooling, and finally reduced to 20 to 30 o C by cooling with ice water.
Man erhält 100 g einer sehr feine, milchig opaken Dispersion mit einem Fluorgehalt von 7 % (bezogen auf Wirksubstanz), die auch bei Temperaturen -20oC und +40oC gut lagerstabil ist.This gives 100 g of a very fine, milky opaque dispersion with a fluorine content of 7% (based on active substance), the o and +40 o C is good storage stability even at temperatures of -20 C.
Jeweils 100g-Muster der Dispersionen nach den Beispielen 5 und 7 sowie nach dem Vergleichsbeispiel 6 und sowie zum Vergleich 100 g eines kationisch dispergierten Handelsprodukts werden in einem Kühlschrank 24 h auf -20oC abgekühlt. Alle Proben gefrieren dabei. Nach dem Auftauen sind die Muster der Beispiele 5 und 7 noch einwandfrei homogen und genauso wirksam wie vor dem Gefriertest. Die Dispersion des mitgetesteten, kationisch dispergierten Handelsprodukts ist dagegen völlig zerfallen, und auch die Probe des Vergleichsbeispiels 6 zerfällt beim Auftauen.In each case, 100 g samples of the dispersions according to Examples 5 and 7 and according to Comparative Example 6 and, for comparison, 100 g of a cationically dispersed commercial product are cooled to -20 ° C. in a refrigerator for 24 hours. All samples freeze. After thawing, the samples of Examples 5 and 7 are still perfectly homogeneous and just as effective as before the freeze test. The dispersion of the co-tested, cationically dispersed commercial product, on the other hand, has completely disintegrated, and the sample of comparative example 6 also disintegrates when thawed.
Die gemäß Beispiel 5 oder 7 hergestellte erfindungsgemäße Dispersion wird mit Wasser auf einen Feststoffgehalt von 2 bis 4 Gew.% verdünnt. Durch die so erhaltene Flotte wird zu behandelndes, bahnenförmiges Textilgut hindurchgeführt und auf einem Foulard abgequetscht. Eine Wiederholung dieses Prozesses fördert die Durchdringung des Substrats und erhöht die Effektivität des erfindungsgemäßen Produkts.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.
Das textile Substrat wird in einem Trockenaggregat bei Temperaturen bis 120oC getrocknet und anschließend im gleichen oder einem anderen Aggregat durch eine Wärmebehandlung bei Temperaturen von 150 bis 180oC 3 min bis 3 sek lang fixiert.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.
Die nach Beispiel 5 hergestellte Dispersion wird mit Wasser auf einen Festoffgehalt von 3 % verdünnt und auf einen PA-Tuffted Teppich aufgesprüht. Der Teppich wird dann bei 110oC getrocknet und anschließend einer 3 min langen Wärmebehandlung bei 150oC unterzogen.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.
An dem behandelten Teppich werden die Oleophobierung nach der Methode 3M/AATCC 18-1966, die Hydrophobierung/Spray nach der Methode AATCC 22-1952 und die Trockenanschmutzung nach folgender Vorschrift geprüft:
In einem zylindrischen, mit einem Deckel verschließbaren Gefäß von 20 cm Länge und einem Durchmesser von 10 cm wird die Teppichprobe ausgelegt. Dann werden 200 g Stahlkugeln von 3 mm Durchmesser und 20 g gesiebter Staubsaugerschmutz hinzugegeben, das Gefäß verschlossen und 1 h auf einem Rollgestell gerollt. Dann wird die Probe entnommen, mit einem Staubsauger abgesaugt und beurteilt.On the treated carpet, the oil repellency is tested according to the 3M / AATCC 18-1966 method, the hydrophobization / spray according to the AATCC 22-1952 method and the dry soiling according to the following regulation:
The carpet sample is laid out in a cylindrical vessel that can be closed with a lid and is 20 cm long and 10 cm in diameter. Then 200 g of steel balls with a diameter of 3 mm and 20 g of sieved vacuum cleaner dirt are added, the vessel is closed and rolled on a trolley for 1 hour. Then the sample is taken, vacuumed with a vacuum cleaner and assessed.
Bei den Ausprüfungen werden die in der nachfolgenden Tabelle I angegebenen Werte erhalten:
Die mit einem kationisch dispergierten Handelsprodukt erzielten Vergleichsergebnisse sind in Tabelle II angegeben:
Claims (10)
- Aqueous anionic dispersion containingA) a% of a product which contains at least one bis-(2-fluoroalkyl-ethoxy-carbonylamino)-toluene of the formula I
YCF₂-(CF₂)n-CH₂CH₂OH (II)
where n and Y have the previously mentioned meanings, with tolylene diisocyanate in a molar ratio of (1.8 to 2) : 1 in the presence of 2 to 5 % of N-methylpyrrolidone, relative to the compound of the formula II,B) b% of at least one emulsifier of the formula III
YCF₂(CF₂)p-CH₂CH₂O-CO-NH-CH₂CH₂-SSO₃X (III)
where p denotes a number from 5 to 15, Y denotes -H or -F and X denotes a monovalent cation,C) C% of at least one nonionic emulsifier of the formula IV
YCF₂-(CF₂)q-CH₂CH₂-(OCH₂CH₂)r-OH (IV)
where Y denotes -H or -F, q denotes a number from 5 to 15, r denotes a number from 0 to 10 andD) d% denotes a solvent or solvent mixture, a denoting a number from 5 to 25, b a number from 1 to 14, c a number from 1 to 14, c a number from 1 to 14, d a number from 5 to 30 and the numerical values for b and c being chosen in such a way that the sum (b + c) = 2 to 15. - Aqeous anionic dispersion according to Claim 1, characterized in that b denotes 1 to 9 and c denotes 1 to 9 and are chosen in such a way that the sum b + c denotes 2 to 12 and/or denotes 10 to 25.
- Aqeous anionic dispersion according to Claim 1 and/or 2, containing a product which contains at least one bis-(2-fluoroalkyl-ethoxy-carbonylamino)-toluene of the formula I
YCF₂-(CF₂)n-CH₂CH₂OH (II)
where n and Y have the previously mentioned meanings, with toluene diisocyanate in a molar ratio of (1.8 to 2): 1 in the presence of 2 to 3.5% by weight of N-methylpyrrolidone, relative to compound II. - Aqueous anionic dispersion according to one or more of Claims 1 to 3, characterized in that in the compounds of the formulae I, II, III and/or IV Y denotes -F and/or in the compounds of the formula I n denotes 5 to 11, preferably 7 to 11, in the compounds of the formula III P denotes 5 to 11, preferably 7 to 11, and/or in the compounds of formula IV q denotes 5 to 11, preferably 7 to 11, and r denotes 4 to 8.
- Aqueous anionic dispersion according to one or more of Claims 1 to 4, characterized in that the dispersion contains at least one (C₁-C₄)monoalkyl- or dialkyl ether of diethylene glycol or dipropylene glycol and/or 1 to 5% by weight of isopropanol, glycol and/or glycerol.
- Aqueous anionic dispersion according to one or more of Claims 1 to 5, characterized in that it additionally contains 5 to 25% by weight of at least one anionic dispersion of a (meth)acrylic ester polymer or copolymer, preferably a copolymer of methyl methacrylate and isobutyl methacrylate.
- Aqueous anionic dispersion according to Claim 6, characterized in that the anionic dispersion of the (meth)acrylic ester polymer contains as emulsifier a compound of the formula III
YCF₂(CF₂)q-CH₂CH₂O-CO-NH-CH₂CH₂-SSO₃X (III)
where Y denotes -H or -F, q denotes 5 to 15 and X denotes a cation. - Product which contains at least one bis-(2-fluoroalkylethoxy-carbonylamino)-toluene of the formula I
YCF₂-(CF₂)n-CH₂CH₂OH (II)
where n and Y have the previously mentioned meanings, with tolylene diisocyanate in a molar ratio of (1.8 to 2) : 1 in the presence of 2 to 5%, preferably 2 to 3.5%, of N-methylpyrrolidone, relative to the compound of the formula II. - Process for preparing aqueous anionic dispersions of one or more of Claims 1 to 7, characterized in thatA) a product which contains at least one bis-(2-fluoroalkylethoxy-carbonylamino)-toluene of the formula I
YCF₂-(CF₂)n-CH₂CH₂OH (II)
where n and y have the previously mentioned meanings, with tolylene diisocyanate in a molar ratio of (1.8 to 2) : 1 in the presence of 2 to 5%, preferably 2 to 3.5%, of N-methylpyrrolidone, relative to the compound of the formula II, is dissolved in an organic solvent or solvent mixture and dispersed withB) at least one emulsifier of the formula III
YCF₂(CF₂)p-CH₂CH₂O-CO-NH-CH₂CH₂-SSO₃X (III)
where p denotes a number from 5 to 15, Y denotes -H or -F and X denotes a monovalent cation andC) at least one nonionic emulsifier of the formula IV
YCF₂-(CF₂)q-CH₂CH₂-(OCH₂CH₂)r-OH (IV
)
where Y denotes -H or -F, q denotes a number from 5 to 15, r denotes a number from 0 to 10 and where appropriate a further organic solvent in water, the mixing ratios being chosen to be such that dispersions in accordance with one or more of Claims 1 to 7 are formed. - Use of the aqueous anionic dispersion of one or more of Claims 1 to 7, for oleophobizing and hydrophobizing textiles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT86105191T ATE65809T1 (en) | 1985-04-20 | 1986-04-15 | AQUEOUS ANIONIC DISPERSION. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3514373 | 1985-04-20 | ||
| DE19853514373 DE3514373A1 (en) | 1985-04-20 | 1985-04-20 | AQUEOUS ANIONIC DISPERSION |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0202471A2 EP0202471A2 (en) | 1986-11-26 |
| EP0202471A3 EP0202471A3 (en) | 1988-10-12 |
| EP0202471B1 true EP0202471B1 (en) | 1991-07-31 |
Family
ID=6268725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86105191A Expired - Lifetime EP0202471B1 (en) | 1985-04-20 | 1986-04-15 | Aqueous anionic dispersion |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US4775488A (en) |
| EP (1) | EP0202471B1 (en) |
| JP (1) | JPH06104192B2 (en) |
| KR (1) | KR860008334A (en) |
| AT (1) | ATE65809T1 (en) |
| AU (1) | AU582229B2 (en) |
| BR (1) | BR8601773A (en) |
| DD (1) | DD248383A5 (en) |
| DE (2) | DE3514373A1 (en) |
| ES (1) | ES8802404A1 (en) |
| NZ (1) | NZ215882A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3672718D1 (en) * | 1985-08-30 | 1990-08-23 | Hoechst Ag | PERFLUORALKYL AND EPICHLORHYDRINE GROUPS CONTAINING URETHANS, THIS URETHANE CONTAINING AQUEOUS DISPERSIONS AND THEIR USE. |
| US5242487A (en) * | 1988-11-11 | 1993-09-07 | Daikin Industries Ltd. | Water- and oil-repellant composition |
Family Cites Families (4)
| 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 (en) * | 1979-02-16 | 1985-04-16 | John E. Bacino | Fluorocarbon compositions and method of spray coating |
| JPS5994621A (en) * | 1982-11-12 | 1984-05-31 | Unitika Ltd | Production of antistaining fiber |
-
1985
- 1985-04-20 DE DE19853514373 patent/DE3514373A1/en not_active Withdrawn
-
1986
- 1986-04-11 US US06/850,592 patent/US4775488A/en not_active Expired - Fee Related
- 1986-04-15 AT AT86105191T patent/ATE65809T1/en not_active IP Right Cessation
- 1986-04-15 EP EP86105191A patent/EP0202471B1/en not_active Expired - Lifetime
- 1986-04-15 DE DE8686105191T patent/DE3680580D1/en not_active Expired - Fee Related
- 1986-04-18 JP JP61088441A patent/JPH06104192B2/en not_active Expired - Lifetime
- 1986-04-18 AU AU56389/86A patent/AU582229B2/en not_active Ceased
- 1986-04-18 DD DD86289369A patent/DD248383A5/en unknown
- 1986-04-18 NZ NZ215882A patent/NZ215882A/en unknown
- 1986-04-18 ES ES554146A patent/ES8802404A1/en not_active Expired
- 1986-04-18 BR BR8601773A patent/BR8601773A/en unknown
- 1986-04-19 KR KR1019860003042A patent/KR860008334A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DD248383A5 (en) | 1987-08-05 |
| KR860008334A (en) | 1986-11-14 |
| ES554146A0 (en) | 1988-05-16 |
| NZ215882A (en) | 1988-09-29 |
| AU5638986A (en) | 1986-10-23 |
| DE3514373A1 (en) | 1986-10-23 |
| EP0202471A3 (en) | 1988-10-12 |
| DE3680580D1 (en) | 1991-09-05 |
| ES8802404A1 (en) | 1988-05-16 |
| JPH06104192B2 (en) | 1994-12-21 |
| BR8601773A (en) | 1986-12-23 |
| EP0202471A2 (en) | 1986-11-26 |
| JPS61249538A (en) | 1986-11-06 |
| AU582229B2 (en) | 1989-03-16 |
| US4775488A (en) | 1988-10-04 |
| ATE65809T1 (en) | 1991-08-15 |
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