DE4240274A1 - Polysiloxanes with fluoroaliphatic and carboxyl-containing terminal groups, their preparation and their use in the treatment of fibrous substrates - Google Patents

Description

This invention relates to polysiloxanes with fluoroalipha ten- and carboxyl-containing terminal groups, their Her position and their use to fiber substrates such as Leather water-, oil-, dirt-repellent and soft-grip too as well as the resulting treated substrates.

Over the last few years, the leather fashion has all common to the natural grain leathers, which are soft to feel, d. h., "soft-grip" are. Natural grain leather is not protected by an impregnation. The care of natural grain leather is more difficult than the care of Finishing or impregnated leather. To make things easier the care of natural scars as well as suede can a fluorochemical treatment can be applied.

Typically, the fluorochemical is in the form of a Spray treatment or wet treatment [so-called Drum treatment ("drum treatment")] in the last  Steps of Ledergerbprozesses applied. Frequently the drum application method is preferred because the Durability of fluorochemical protection a drum treatment is better than a spray treatment. A big disadvantage of the known fluorine chemical drum treatment is the one that grip or softness of the leather are impaired; the Fluorochemical treatment gives the leather a rough texture dry handle. For such a treatment was a series of fluorochemical compositions and some become commercial for this purpose used, such as those under the trade name "Scotch gard Leather Protector ".

Various patents and publications disclose one Variety of such fluorochemical compositions for different applications, eg. For example, US Pat. 3,462,296 (Raynolds et al.), 3,484,281 (Guenthner et al.), 3,816,167 (Schultz et al.), 3,944,527 (McCown), 4,024,178 (Landucci), 4,190,545 (Marshall et al.), 4,215,205 (Landucci) and 4,426,476 (Chang), the Japanese published patent application (Kokai) No. 81-49081, and Banks, R.E., Eds., "Organofluorine Chemi cals and Their Industrial Applications ", pp. 226-230 (Ellis Harwood, Ltd., West Sussex, England, 1979). Ver Various patents also disclose compositions for Carpet treatment, including various fluorine contain chemicals, eg. See, for example, U.S. Patent Nos. 3,923,715 (Dettre et al.), 4,043,964 (Sherman et al.), 4,107,055 (Sukornick et al.), 4,264,484 (Patel), Re. 30,337 (Loudas), 4,388,372 (Champaneria) and 4,325,857 (Cham paneria). Various patents also disclose the Ver use of fluorochemical compositions for leather, z. See, for example, U.S. Patent Nos. 4,525,305 (Patel), 4,920,190 (Lina et al.), 4,782,175 (Wehowsky et al.), 4,778,915  (Lina et al.), 4 539 006 (Langford), 3 923 715 (Dettre et al.), 4,709,074 (Bathelt et al.) and L. Schlösser "Properties of fluoroorganic compounds and their Application in the leather field ", THE LEATHER, 41 vintage August 1990, p. 149-153.

Silicones or polymeric siloxanes such as those industrial available polyorganosiloxanes, e.g. Polymethylsiloxanes, are also known to be leather, textiles and make paper water repellent. See for example "Chemistry and Technology of Silicones" by Walter Noll, Academic Press, New York, p. 585-603 (1968).

European Patent Application 299 596 A2 describes a fiber treatment composition based on a microemulsion of carboxyl-modified organo polysiloxane each having at least two carboxyl groups in the molecule as well as the use of the composition the treatment of natural fibers such as wool, silk or cotton. The carboxyl-modified organopoly siloxane has the general formula

A (R ₂ SiO ₂ ) _x (RASiO ₂ ) _y R ₂ SiA

wherein R is a monovalent hydrocarbon group, A may be, inter alia, a substituted alkyl group such as 3,3,3-trifluoropropyl or a carboxyl group of the formula R'COOH, where R 'is a divalent organic Group is x = 0 to 2000, y is 0 to 200, x + y = 350 until 2000. This organopolysiloxane should so that it gives fiber materials lasting softness, Smoothness, wrinkle resistance and pressure insensitivity without formation of oil stains.

European Patent Application 298 364 A2 describes Fluoro- and polysiloxane-containing urethanes and their Ver Use for leather to make it oil and water repellent like  also soft to handle. The urethanes are made provided by reaction of the fluoroalcohol / isocyanate Adduct with a polysiloxane in a ratio of 1 to 2 mol at a temperature of 30 to 130 ° C. by fluoroaliphatic group-containing polyurethanes with Similar properties are also in DE-38 02 633 A1 described.

U.S. Patent No. 4,625,010 teaches the use of organo polysiloxanes having SiC-bonded epoxy groups on can be brought to a fiber with a polymer, having perfluoroalkyl groups.

U.S. Patent No. 4,098,742 (Mueller) teaches a method for the preparation of certain polyurethanes which are at least contain a section derived from one Perfluoroalkyl-substituted diol, and at least one Section that is derived from a reactive Hydrogen-containing polysiloxane that synthesized be by copolycondensation with an organic Diisocyanate. These polyurethanes are described as Impregnations on glass ceramics, masonry, wood, Paper, metal, leather and in particular textiles containing they have a high level of oil and water repellency to lend.

European Patent Application 0 324 345 A1 relates a procedure to leather, leather substitute and furs with a Carboxyl-containing polysiloxane hydrophobic too whose carboxyl groups are in neutralized form available. Preference is given to those polysiloxanes which contain terminal carboxylic acid anhydride groups. The Anhydride groups of polysiloxanes can with amines or Alcohols are reacted to form esters or partial esters.  

European Patent Application 0 415 204 A2 describes certain anhydride-functional organo (poly) siloxanes, For example, as a hardener for epoxy resin materials are usable.

This invention makes a new class in one respect accessible from functional polysiloxanes containing a fluoroaliphatic radicals and carboxyl termi nale unit attached to a diorganosiloxy group on and either another such terminal one unit attached to another diorganosiloxy group, or a cyclic carboxylic anhydride containing terminal unit, tied to another diorgano possess siloxy group, as well as carboxylic acid derivatives these polysiloxanes.

In another aspect, the invention makes polyorgano siloxanes which contain one unit containing α, ω-bis (fluoroaliphatic radical and carboxyl) and derivatives thereof. These polysiloxanes can ver are used to prepare treatment Substances that are beneficial in the treatment of sub straten like leather are to this water and Ölab to impart a sense of detachment and softness.

In a preferred embodiment, it is the fluoroaliphatic and carboxy polyorganosiloxanes of this invention to α, ω-bis (polydialkylsiloxane) dicarbon acid esters, thioesters or amides of fluoroaliphatic (eg perfluoroalkyl) groups containing mono functional alcohols, mercaptans or amines. The free carboxyl group of the amide according to the invention, thio esters or esters can be with a base such. B. ammonia be reacted to form a salt that is in water can be dispersed to form an aqueous  Solution that is beneficial in the treatment of Fiber substrates such as leather, to this water and Oil repellency and soft grip to give hen. Especially preferred fluoroaliphatic and carb oxylpolyorganosiloxanes of this invention, such as the the above-mentioned esters, thioesters or amides those according to formulas I and II:

wherein

• R _{f represents} a fluoroaliphatic group;
• Q represents a covalent bond or a linking group;
• R ₁ and R ₂ are each independently a linear, branched or cyclic aliphatic group or an aromatic group;
• n is an integer greater than 1, and preferably 10 to 100;
• - MH, Na, K, Li, NR ₃ R ₄ R ₅ R ₆ , where R ₃ , R ₄ , R ₅ , R _{6 are} H, linear, branched or cyclic saturated aliphatic groups or aromatic groups, and R ₃ - R ₆ may contain functional groups such as hydroxy groups.

The fluoro aliphatic group represented as R _f in formulas I and II is a stable, inert, non-polar, preferably saturated, monovalent moiety that is both oleophobic and hydrophobic, preferably containing at least about 3 carbon atoms, more preferably 4 to about 20 Carbon atoms, and most preferably about 6 to 12 carbon atoms, may be linear, branched, or cyclic, is preferably free of polymerizable olefinically unsaturated sites, and may optionally contain chain forming heteroatoms such as oxygen, divalent or hexavalent sulfur, or nitrogen. It is preferred that each fluoroaliphatic group holds about 40 to about 78 wt.% Fluorine. The terminal part of the fluoroaliphatic group contains a fully fluorinated terminal group. This terminal group preferably contains at least 7 fluorine atoms, e.g. CF ₃ CF ₂ CF ₂ -, (CF ₃ ) ₂ CF-, -CF ₂ SF ₅ , or the like. Perfluorinated aliphatic groups, eg. Those of formula C _x F _{(2x + 1} ) are the most preferred embodiments of the fluoroaliphatic group wherein x is at least 3, preferably 4 or greater and even 20.

The linking group Q can be a covalent bond or a unit that has at least one carbon Contains atom, preferably a unit, which is 1 to about 20 carbon atoms and optionally oxygen, Contains nitrogen and sulfur heteroatoms and before is preferably free of active hydrogen atoms. To the examples of structures that are linked Group Q are suitable, include linear chain, branched ketti  saturated or cyclic alkylene, arylene, aralkylene, oxy, Oxo, thio, sulfonyl, sulfinyl, imino, sulfonamido, carb oxamido, carbonyloxy, iminocarboxymethylene, ureylenedi and combinations thereof, such as sulfonamidoalkylene.

Preferred linking groups Q can be selected be after the ease of their manufacture and the Availability in trade. Below is a representative given a list of suitable organic Q groups. In this list, k is independently an integer from 1 to about 20, g is an integer from 0 to about 10, h is an integer from 1 to about 20, R 'is Is hydrogen, phenyl or an alkyl of 1 to about 4 Carbon atoms (and is preferably methyl), and R "is alkyl of 1 to about 20 carbon atoms.

-SO ₂ N (R ') (CH ₂ ) -
-CON (R ') (CH ₂ ) _k -
- (CH ₂ ) _k -
-CH ₂ CH (OH) CH ₂ -
-CH ₂ CH (OR '') CH ₂ -
- (CH ₂ ) _k S-
- (CH ₂ ) _k O (CH ₂ ) _k -
- (CH ₂ ) _k S (CH ₂ ) _k -
- (CH ₂ ) _k (OCH ₂ CH ₂ ) _k -
- (CH ₂ ) _k SO ₂ (CH ₂ ) _k -
-SO ₂ N (R ') (CH ₂ ) _k O (CH ₂ CH ₂ ) _k -
-SO ₂ N (R ') CH ₂ CH (OH) CH ₂ -
- (CH ₂ ) _k SO ₂ N (R ') (CH ₂ ) _k -
- (CH ₂ ) _k SO ₂ -
-OC ₆ H ₄ CH ₂ -

Q is preferably alkylene, sulfonamido, or sulfone amidoalkylen.

In a preferred embodiment of the invention, the organic linking group Q is -R'- or -SO ₂ N (R) R'-, wherein R is hydrogen or an alkyl group such as an alkyl having, for example, 1 to 6 carbon atoms, and R 'is an alkylene group having, for example, 1 to 15 carbon atoms.

In a preferred embodiment, R _{1 is} a branched, linear or cyclic aliphatic group having, for example, 2 to 10 carbon atoms.

The silicon-bonded R ₂ in the formulas I and II are, for example, methyl, ethyl, n-propyl, iso-propyl or phenyl groups. The index n in formulas I and II is most preferably 20-60.

In a preferred embodiment, the inventions polyorganosiloxanes according to the invention

wherein n is 20 to 60, M is as described in formulas I and II, and x is 6 to 14.
Preferably, x is 8.

The Fluoraliphaten- and Carboxylpoly invention Organosiloxanes can be prepared by reaction a polyorganosiloxane-substituted dicarboxylic acid anhydride with a fluoroaliphatic group ent holding alcohol, mercaptan or amine.

In the process of this invention, the reaction between polyorganosiloxane-substituted dicarboxylic acid anhydride and a fluoroaliphatic group enthal alcohol without solvent, in the melt or be carried out in a solvent against is inert via reactants and catalyst and the Reactant and catalyst at the Reaktionstempe solubility. A useful solvent is for example, toluene.

In the process of this invention, the reaction be carried out without catalyst in the presence  any catalyst capable of reacting tion between the dicarboxylic anhydride and the one fluoroaliphatic group-containing alcohol, amine or To promote mercaptan. Examples of such Kataly These are pyridine or 4- (dimethylamino) pyridine.

The inventive method for producing the spe ziellen Polyorganosiloxane can at any tempera and pressing are performed in which the Reaction between the dicarboxylic anhydride and the Al K, amine or mercaptan expires. Preferably the process at temperatures of 50 to 150 ° C and Atmospheric pressure carried out.

The minimum amount of a fluoroaliphatic group containing alcohol, mercaptans or amines required is to be substituted with the polyorganosiloxane Dicarboxylic anhydride is selected in Ab dependence of the desired rejection properties and Grip of the final product. Preferably, little at least 50% of the dicarboxylic anhydride groups with the one fluoroaliphatic group containing reactants implemented.

Once the reaction is complete, the solvent, if used, preferably evaporated.

In a preferred embodiment, the structures th Fluoraliphaten- and carboxyl-containing polyorgano siloxanes partially or completely with an alkali substance, preferably ammonia neutralized to To form salts.

The monofunctional fluoroaliphatic alcohols useful in the above-described reaction with the anhydride to produce the polysiloxanes of this invention include the N-alkanol perfluoroalkane sulfonamides described in U.S. Patent No. 2,803,656 (Ahlbrecht et al.) Having the general formula R _f SO ₂ N (R) R ₁ CH ₂ OH, wherein R _{f is} a perfluoroalkyl group (including perfluorocycloalkyl) having 4 to 10 carbon atoms, R _{1 is} an alkylene radical having 1 to 12 carbon atoms and R is a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, and is preferably methyl. These monofunctional alcohols can be prepared by reacting an acetate ester or halohydrin with a sodium or potassium salt of the corresponding perfluoro alkanesulfonamide.

Exemplary of the fluoroaliphatic alcohols are the following:
N-ethyl-N- (2-hydroxyethyl) -perfluoroctansulfonamid,
N-propyl-N- (2-hydroxyethyl) -perfluoroctansulfonamid,
N-ethyl-N- (2-hydroxyethyl) -perfluordecansulfonamid,
N-ethyl-N- (2-hydroxyethyl) -perfluordodecansulfonamid,
N-ethyl-N- (2-hydroxyethyl) perfluorocyclohexylethanesulfonamide,
N-propyl-N- (2-hydroxyethyl) -perfluorobutylcyclohexane sulfonamide,
N-ethyl-N- (2-hydroxyethyl) perfluoro-4-dodecylcyclohexane sulfonamide,
N-ethyl-N- (2-hydroxyethyl) perfluoro-2-methylcyclohexane sulfonamide,
N-ethyl-N- (6-hydroxyhexyl) -perfluoroctansulfonamid,
N-methyl-N- (11-hydroxyundecyl) -perfluoroctansulfonamid,
N-methyl-N- (4-hydroxybutyl) -perfluorbutansulfonamid,
N- (2-hydroxyethyl) -perfluoroctansulfonamid,
N-methyl-N- (2-hydroxyethyl) perfluorooctanesulfonamide.

Other alcohols useful in the reaction with anhydride to make the polyoxanes of this invention include the perfluoroalkyl substituted alkanols of the formula C _n F _{2n + 1} CH ₂ OH wherein n is 4 to 10 (e.g., C ₄ F ₉ CH ₂ OH) described, for example, in U.S. Patent No. 2,666,797 (Husted et al.) And those of the formula R _f (CH ₂ ) _m OH wherein R _{f is} a perfluoroalkyl radical with 4 to 10 carbon atoms and m is an integer from 1 to 4, z. B.

Also, perfluoroalkyl-substituted alkanols, z. B. C _n F _{2n + 1} (C _m H _2m-2 OH, wherein n is 4 to 10 and m is 1 to 4, z. B. C ₈ F ₁₇ CH = CHCH ₂ OH, may be used for the preparation of the polysiloxanes to the invention OF INVENTION Other useful monofunctional alcohols include the N- [hydroxypoly (oxyalkylene)] perfluoroalkanesulfonamides of U.S. Patent No. 2,915,554 (Ahlbrecht et al.) such as US Pat

Other alcohols which are useful in the reaction with anhydride for the preparation of the polysiloxanes of the invention are, for. Those of the formula (R _f CH ₂ CH ₂ S) ₂ C (CH ₃ ) CH ₂ CH ₂ OH described in U.S. Patent No. 4,419,298 (Falk et al.), And e.g. HO-CH ₂ C- (CH ₂ SCH ₂ CH ₂ R _f ) ₂ CH ₂ OH described in U.S. Patent No. 4,898,981 (Falk et al.). Other alcohols that can be used to prepare the polysiloxanes of the invention are, for. For example those of the formula:

US Pat. No. 3,935,277 and US Pat. 4,158,672.

Exemplary perfluoroalkyl mercaptans useful in the above-described reaction with the polysiloxane-substituted acid anhydride for the preparation of the polysiloxanes of the invention include, for example, the mercaptans of the formula R _f -R ₁ -SH described in a number of U.S. patents No. 2,894,991, 2,961,470, 2,965,677, 3,088,849, 3,172,190, 3,544,663 and 3,655,732; the latter patent discloses mercaptans wherein R _{f is} perfluoroalkyl and R _{1 is} alkylene of 1 to 16 carbon atoms.

Exemplary fluoroaliphatic amines which are useful in the reaction with the anhydride for the preparation of the inventions to the invention polysiloxanes include fluoroalkylamines z. Having the general formula R _f (CH ₂ ) ₂ NH ₂ as described in U.S. Patent No. 5,026,910 (Bollens et al.).

Polysiloxane-substituted dicarboxylic anhydrides, the with the above-mentioned fluoroaliphatic Alkoho len, mercaptans and amines can be reacted to to produce the polysiloxanes of the invention are  For example, in the European patent application 0 415 204 A2.

Preferred polydialkylsiloxane-substituted dicarboxylic acid acid anhydrides have the following structure:

where n is an integer greater than 1 and preferably 10-100 is.

Other typical examples of anhydride-substituted Polydialkylsiloxanes are described in European patent no. 415 204 described.

Useful bases for the preparation of the treatment compositions according to the invention are, for example, NaOH, KOH, LiOH, NH ₄ OH and amines such as

NH ₂ CH ₂ CH ₂ OH
NH (CH ₂ CH ₂ OH) ₂
N (CH ₂ CH ₂ OH) ₃
N (CH ₂ CH ₃ ) ₃
NH (CH ₂ CH ₃ ) ₂
N (CH ₂ CH ₂ CH ₂ CH ₃ ) ₃

Other useful bases that can be used are, for example, in European Patent No. 73 732 be wrote.

The polysiloxanes of this invention are preferably as concentrated aqueous solutions or aqueous emulsions produced. In general, the aqueous Polysiloxane solutions or dispersions of this invention about 5 to 50% by weight of the active composition. In this form, the polysiloxanes of the invention be easily diluted with water before they Tanning drum are added.

For the preparation of the concentrated Polysiloxane solutions can be environmentally friendly, with what miscible organic solvents are used, such as As solvents that are less dangerous or have low toxicity, such as solvents, the in Germany in class II or class III of the TA Luft get ranked. Useful organic solvents, for preparing the aqueous poly according to the invention siloxane solutions can be used are those which are at least partially miscible with water, such as Alcohols, ketones or water-miscible ethers (eg. Diethylene glycol diethyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether), mixed with water glycol ethers (eg, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol mono butyl ether, dipropylene glycol monomethyl ether, dipropylene glycoldimethyl ether, diethylene glycol monobutyl ether), lower esters of monoalkyl ethers of ethylene glycol or Propylene glycol (eg, propylene glycol monomethyl ether acetate), many of which are commercially available.  

It can mixtures of organic solvents to Her position of the aqueous polysiloxane according to the invention Solutions are used.

The amount of polysiloxane according to the invention, which on the Substrate is applied according to this invention is chosen so that the substrate surface sufficiently high or desirable water and oil repellency be lent, this amount usually like that is that 0.01 to 5 wt .-%, preferably 0.05 to 2 wt .-% fluorine present on the treated substrate are. The amount that is sufficient to the desired rejection ability or desired softness can lend, can be determined empirically and depending on the needs ability or desire to be increased.

The fluoroaliphatic and carboxyl-containing polysiloxanes of this invention are particularly advantageous to leather water-, oil-, dirt-repellent and soft-grip too make, and these properties can through a Drum treatment of the leather during leather tanning process.

Various adjuvants may be in the invention Polysiloxanes are introduced to this particular To give properties. For example, coals Hydrogen Extender for dirt resistance and Water repellency can be added; also can Fatliquor or synthetic tanning agent added become. Also other oil and water repellent fluorine Chemical substances may be added to the composition ben, so that the composition of the invention better is capable of treating the treated fibrous porous Substra th the desired surface properties ver lend.

In the following non-limiting examples Objectives and advantages of this invention are explained, wherein all parts and percentages are by weight, unless otherwise noted. At those Bei play, in which the polysiloxanes of the invention be applied to different substrates the following test methods were used for evaluation.

spray rating

The spray rating (SR) of a treated Substrate is a value of dynamic repulsion assets of the treated substrate to water which impinges on the treated substrate as it does about the clothes in a heavy downpour experiences. The rating is determined using the standard test Number 22, published in the Technical Manual and Yearbook of the American Association of Textile Chemists and Colorists (AATCC) of 1977, and is expressed as "Spray rating" of the treated substrate. The spray Rating is obtained by spraying water on the substrate and is determined using a Scale from 0 to 100, with 100 being the highest possible tion is. In general, a spray rating of 70 or more desirable.

Oil repellency

The oil repellency (OR) of a treated substrate is determined using Standard Test Method No. 118-1983 of the American Association of Textile Chemists and Colorists (AATCC); This test is based on the resistance of a treated substrate to the penetration of oils of different surface tension. Treated substrates that resist only Nujol ^™ mineral oil (the least penetrating test oils) are rated 1, whereas treated substrates which resist heptane (the most penetrating of the test oils) are rated 8 be considered. Further intermediate values are determined using other pure oils or mixtures of oils as shown in the following table.

Standard Test Liquids Evaluation number of oil repellency according to AATCC composition 1 Nujol ^TM mineral oil 2 65:35 Nujol ^™ / hexadecane (v / v) b. 21 ° C (70 ° F) 3 n-hexadecane 4 n-tetradecane 5 n-dodecane 6 n-decane 7 n-octane 8th n-heptane

The evaluated oil repellency corresponds to the am strongest penetrating oil (or mixture of oils), which after 30 s contact time not in the tested sub strat penetrates or wets this. Higher numbers indicate better oil repellency.

In general, an oil repellency of minde 1 is desirable.

Water repellency

The water repellency (WR) is measured using a water / isopropyl alcohol  Test fluid and is expressed as "WR" rating of the treated substrate. Treated substrates in the only a liquid of 100% water / 0% isopropyl Alcohol - the weakest penetrating test liquid ability - to penetrate or to resist this will be with us a rating of 0, whereas treated sub strate of a test fluid of 0% water / 100% Isopropyl alcohol - the most penetrating of the Test mixes - resist, with a rating of 10 be considered. Further intermediate values are determined by using another water / isopropyl alcohol Test liquid in which the percentages of Water and isopropyl alcohol in each case multiples of 10 are. The WR rating is the strongest one urgent test fluid, which after 15 s contact time does not penetrate or wet the substrate. in the general is a water repellency of 2 or more desirable.

Bally penetrometer

For testing upper leather on Wasserabweisungsver like was a Bally penetrometer model 5023 (a standardized dynamic testing machine for shoe upper leather) used. In this test, the test piece became alternately curved and stretched by the machine, like upper leather in actual use while it is on One side was in contact with water. The at measured values of this test are:

• 1. the time to water first from one side of the test piece of treated leather to the other side penetrates (this period is unbehan deltem leather typically less than 15 minutes), and  
• 2. the percentage increase in weight of the test piece, caused by ingestion of water during the Tests (this weight gain amounts to un treated leather is typically more than 100% after one hour).

Oil and water repellency after abrasion

The repellency of a scraped treated Substrate is measured with test pieces of the treated Substrate of 5 cm by 12.5 cm, covered with sandpaper ("WETORDRY-TRI-M-ITE" No600C) in an AATCC rub checker (model CM-1) over a period of 5 s by means of 10 forward and backward drive movements were mined. With these abraded test pieces were the above-described OR and WR tests durchge leads and the ratings of repellency as Oil repellency values after abrasion (Abraded Oil repellency; AOR) and water repellency after Abrasion (Abraded Water Repellency; AWR).

Static oil intake

Static oil absorption is a test designed to measure the degree of resistance of a drum treated leather to oil absorption under static conditions. A 50 mm by 50 mm test piece was weighed and held upright in a beaker of Nujol ^™ mineral oil so that the top of the piece was 6 mm below the oil surface. After a dipping time of 10 minutes, the test piece was taken out, the surface oil was gently blotted with absorbent paper, and the test piece was weighed again.

The results were recorded as a percentage Oil intake using the formula:

where W1 is the original weight of the piece and W2 is the Weight of the piece after immersion is.

example 1

A three-neck glass reaction flask was charged with 100 g of a polydimethylsiloxane-α, ω-diyl bis succinic anhydride (0.60 milliequivalent / g anhydride, available from Wacker Chemie Co. as SLM 50240/2), 33.4 g (0.06 mol) N- Methyl N- (2-hydroxyethyl) perfluorooctanesulfonamide, 125 g of troc kenem toluene and 1 g of pyridine as catalyst. The contents of the flask were heated and kept at 100 ° C for 4 hours. Ester formation was monitored by Fourier transform infrared spectroscopy by the disappearance of anhydride absorption at 1789 cm ^-1 . Once the reaction was complete, the toluene was removed from the reaction product under reduced pressure. After cooling the reaction product to 60 ° C, 105 g of 2-butoxyethanol and 105 g of deionized water were added. Upon stirring, a milky white emulsion having a pH of 3 to 4 was obtained. This emulsion was then neutralized with ammonia to a pH of 7.5. In the course of neutralization, the milky white emulsion became a clear yellowish solution. This solution ent held 40 wt .-% of the inventive α, ω-Fluoralipha ten- and carboxyl-substituted polydimethylsiloxane of the formula

The general structure was by Fourier transforma tion infrared spectroscopy.

Examples 2-6

Five different polysiloxanes according to the invention were made using the same procedure as in Example 1, but using the in Table 1 give fluorinated alcohol derivatives and difunctional Polydimethylsiloxanes. The polysiloxanes formed are covered by the formula II.

Table I

Examples 7 to 11

Five different polysiloxane products of the invention were prepared by the method described in Example 1 method, but the 2-butoxyethanol was by other solvents replaced (compiled in Tabel II), N-methyl-N- (2-hydroxyethyl) perfluorooctanesulfone amide was used as a fluorochemical alcohol reactant used and the polydimethylsiloxane-α, ω- used di-bis-succinic anhydride had about 25 siloxy-in units.

Table II

Examples 12 to 14

Three different polysiloxane products according to the invention were prepared using the same in Example 1 described general method, but became the Neutra lisation of the carboxylic acid groups to a pH of 7.5 with the bases given in Table III instead of with Ammonia made.

Table III example Base used 12 triethylamine 13 morpholine 14 KOH

Example 15

A three-neck glass reaction flask was charged with 7.50 g of a polydimethylsiloxane-α, ω-diyl bis succinic anhydride (1.03 meq / g anhydride, available from Wacker Chemie Co. as SLM 50240/4), 4.36 g of N-ethyl-N- (2-amino ethyl) -perfluoroctansulfonamid charged. The contents of the flask were heated and kept at 65 ° C for 4 hours. After this 4 h, no residual anhydride absorption at 1789 cm ^-1 in the Fourier transform infrared spectrum was found, indicating that the reaction was complete. After cooling the reaction product to 40 ° C, 0.75 g of triethylamine was added to neutralize the carboxylic acid and the product mixture was stirred for an additional 10 minutes. The α, ω-fluoroaliphatic and carboxyl-substituted polydimethylsiloxane according to the invention was then diluted with 24.0 g of ethylene glycol monobutyl ether and 24.0 g of deionized water. This dilution gave a slightly viscous polysiloxane solution according to the invention with 20.8 wt .-%. The pH of the solution was 8.

Example 16

A glass reaction flask was charged with 15.0 g of a polydi methylsiloxane α, ω-diyl bis succinic anhydride (1.03 milliequivalent / g anhydride, available from Wacker Chemie Co. as SLM 50240/4), 9.0 g C ₁₀ F ₂₁ CH ₂ CH ₂ SH, 1.5 g of triethylamine and 10.0 g of acetone. The reaction flask was closed and the contents of the flask were heated and held at 80 ° C for 4 hours. After these 4 h, the Fourier transform infrared spectrum showed no residual anhydride absorption at 1789 cm ^-1 more, and the typical thioester absorption at 1695 cm ^-1 was found. The product mixture was cooled and diluted with 92.0 g of acetone. This gave a polysiloxane solution according to the invention with 20 wt .-%.

Example 17

15 g of the prepared in Example 1, undiluted, from Toluene by evaporation liberated polysiloxane product were diluted with 22.5 g of ethyl acetate, yielding a poly 40% by weight siloxane solution ("Solution A").

55 g of deionized water was mixed with 5 g of ethylene glycol and 3.0 g of 25% NH ₄ OH to give a solution ("Solution B").

The solutions A and B were heated to 50 ° C and under vigorously stirred; then the gebil treated mixture with ultrasonic waves for 6 min and after this treatment became the ethyl acetate by vacuum distillation at 55 ° C from the mixture ent removed. After removing all the ethyl acetate obtained a storage-stable microdispersion with pH 7. This dispersion contained 20% by weight of the invention Polysiloxane.  

Examples 18-29 and Comparative Examples 1-2

There were aqueous dispersions or solutions of inventions According to the invention fluoroaliphatic-containing polysiloxanes ago and evaluated for their effectiveness in the Treatment of leather (especially advantageous for upholstery ments) in order to give it pleasant surface properties to lend. For this purpose, the polysiloxanes of Examples 1-4, 7-14 used. For comparison purposes two more compositions were prepared. The A (Comparative Example 1) is that in claim 3 of U.S. Patent No. 4,160,777 (Loud As), and U.S. Pat the other (Comparative Example 2) is the product of U.S. Patent No. 4,525,305, Formula IX, p. 7. The Treat Solutions were given in a bath extraction treatment the leather applied. The products were applied during the last stage of wet production of the leather, according to the standard steps of chrome tanning, Retannage, dyeing and fatliquoring, which are used in Ver processing of upholstery leather.

The treatment compositions became the fatliquor Bad added in sufficient quantities to a poly siloxane dry matter content of 1.6% by weight, relative to the smooth weight of the leather. The fat-pickling bath contained a liquid, which amounted to 200 wt .-% What This was relative to the smooth weight of the leather.

The bath temperature was at the moment of adding the Treatment agent at 50 ° C and the pH to 4.5. The off Drawing was continued for 30 minutes, after which the pH was lowered to 3.5 with formic acid.

After the treated leather ge in the usual way dried and finished, the OR, WR, SR,  AOR and AWR tests on the scar side of the treated Leathers performed. The results are in Table IV given.

Table IV

The above results clearly show that in Appl formation of polysiloxanes according to the invention on upholstery Leather is a leather with a soft feel and good oil and oil water repellent properties. The result The overall properties of the leather are significantly better as those produced in accordance with Comparative Examples Leather.

Examples 18-21 show that a wide variety of Siloxane chain lengths can be used. The Bei Games 22-26 show that a wide variety of auxiliary  Solvents can be used to fiction produce according to polysiloxanes. Examples 27-29 show that uses a wide variety of bases can be prepared to the polysiloxanes of the invention deliver.

Example 30 and Comparative Example 3

Using the in Examples 18-29 einschl The working method became typical shoe leather with a treated aqueous dispersion, which in Example 3 prepared polysiloxane, and for comparison was the aqueous treatment solution (Comparative Example 3) as that of Comparative Example 2 ago and also for the treatment of shoe leather ver applies. The performance results are in the following Tables V and VI are compiled.

Table V

Table VI

Compared to Comparative Example 3, Example 30 shows clearly the excellent performance of the invention Composition. Both the repellent properties produced with the polysiloxanes according to the invention leather as well as the softness of the leather is better as in the leather produced in the comparative example. Especially important for shoe leather is the lower per total water absorption after 1 h in the Bally penetrometer Test.

Example 31 and Comparative Example 4

Using the application procedure of Examples 18-29 became a suede, as it is used for clothing treated with an aqueous solution that in Bei contains 1 prepared polysiloxane product, and For comparison purposes, the solution of the method described in Ver Example 2 used. The Performance results are summarized in Table VII provides.

Table VII

The results show that the poly siloxanes can be used to high quality to create valued clothing suede. Example 31 shows that this with the product of Example 1 herge Overall, leather put in good repellency It has a good grip connection with the handle  Product of Comparative Example 2 produced leather good repellency, but bad grip on has. For this reason, the leather of comparison Example 4 Overall unacceptable properties.

Examples 32 to 34

Herge from different fluorinated alcohols were polysiloxanes of Examples 1, 5 and 6 were using the methods described in Examples 18-29 Nursing method for treating leather for game leather shoes used. The results are in table VIII given.

Table VIII

The results in Table VIII show that various Fluorochemical precursors can be used to to produce the polysiloxanes of the invention.

Examples 35 and 36 and Comparative Examples 5 and 6

"Double-sided" sheepskin leather was treated with an aq treated solution that in Examples 1 and 3 contained polysiloxanes, and for comparison with treatment agents such as those in the Comparative Examples 1 and 2 used. The performance Results are given in Table IX. The applied Application method is described in Examples 18-29.  

Table IX

These results show that both with the inventions polysiloxanes prepared according to the invention sheepskins as well as the products of Ver Similarly produced leather overall good Possess rejection properties, but only with the Leather produced according to the invention polysiloxanes have soft grip and thus the only leather with the desired properties are.

Examples 37 and 38 and Comparative Examples 7 and 8

"Nappa" sheepskin was treated with an aqueous solution which are those prepared in Examples 1 and 3 Contained polysiloxanes, and for comparison with Be such as those in the comparative case Play 1 and 2 used, using the in the Examples 18-29 application method described.

The performance results are given in Table X.  

Table X

The results of Table X clearly show that again produced with the polysiloxanes according to the invention leather the desired combination of properties have.

Example 39

An aqueous solution of the product prepared in Example 1 polysiloxane of the invention was applied to 100% wool fabric and applied to a 65/35% polyester / cotton fabric gene.

The order of the polysiloxane was carried out by pillows contract; after application, the fabrics were dried and Hardened at 150 ° C for 3 min. The order level was to 0.6% polysiloxane, based on the fabric mass.

The performance results are given in Table XI.  

Table XI

The results of Table XI show that the invent polysiloxanes according to the invention also textile substrates oil and Water repellency in combination with softgrip lend.

The person skilled in the art will be aware of how this invention works can be variously modified and changed, without departing from the spirit and scope of this invention.

Claims (20)

1. Polysiloxanes containing a fluoroaliphatic radicals and Car boxyl containing terminal moiety to a diorgano having bound siloxy group and either a white Such a terminal unit bound to another Diorganosiloxy group, or a cyclic carbon acid anhydride-containing terminal unit attached to have another diorganosiloxy group, as well as car Bonsäure derivatives of these polysiloxanes. 2. Polysiloxanes according to claim 1, which are two fluoroaliphatic Residues and carboxyl-containing terminal units point. 3. Polysiloxanes according to claim 1, which is a fluoroaliphatic Radicals and carboxyl-containing terminal moiety and a ter containing a cyclic carboxylic anhydride a small unit bound to another diorganosiloxy Group have. 4. polysiloxanes according to claim 1, the α, ω-bis (polydialkyl siloxane) dicarboxylic acid esters, thioesters or amides of fluoroaliphatic group-containing monofunctional len alcohols, mercaptans or amines are.   5. Polysiloxanes according to claims 1 to 4 with the formulas wherein

• R _{f represents} a fluoroaliphatic group;
• Q represents a covalent bond or a linking group;
• R ₁ and R ₂ are each independently a linear, branched or cyclic aliphatic group or an aromatic group;
• n is an integer greater than 1 and preferably 10 to 100;
• - MH, Na, K, Li, NR ₃ R ₄ R ₅ R ₆ , where R ₃ , R ₄ , R ₅ , R ₆ H, is a linear, branched or cyclic saturated or saturated aliphatic group or an aromatic group, and R ₃ - R ₆ can contain functional groups.

6. Polysiloxanes according to claim 5, wherein Q is -R'- or -SO ₂ N (R) R'-, wherein R is hydrogen or an alkyl group having 1 to 6 carbon atoms and R 'is an alkylene group 1 to 15 carbon atoms. 7. Polysiloxanes according to claims 5 or 6, wherein R _{1 is} a branched, linear or cyclic aliphatic group having 2 to 10 carbon atoms. 8. Polysiloxanes according to claims 5 to 7, wherein R _{2 is} a methyl, ethyl, n-propyl, isopropyl or phenyl group. 9. Polysiloxanes according to claims 5 to 8, wherein n 20- 60 is. 10. polysiloxanes according to claims 1 to 9 having the formula wherein n is 20 to 60 and M is as described in claim 5 ben. 11. Polysiloxanes according to claims 1 to 9 with the formula wherein n is 20 to 60, M is as described in claim 5, and x is 6 to 14. 12. Polysiloxanes according to claim 11, wherein x is 8.   13. A process for the preparation of polysiloxanes according to Claims 1 to 12, wherein polyorganosiloxane-substituted Dicarboxylic anhydrides are reacted with fluorine alcohols containing aliphatic groups, mercaptans or amines. 14. The method of claim 13, wherein the polysiloxanes the reaction of the anhydrides with alcohols, mercaptans or amines partially or completely with an alkali neutralized substance to form salts become. 15. The method of claim 14, wherein the alkaline sub is ammonia. 16. Use of the polysiloxanes according to claims 1 to 12, to leather water, oil and soil repellency and to give softness. 17. Use according to claim 16, wherein lending said Characteristics of fluorochemical drum treatment happens during the leather tanning process. 18. Fiber substrate with water, oil, Schmutzabweisungsvermö and softness on the surface effective amount of polysiloxanes according to claims 1 to 12 to give it these properties hen. 19. A fibrous substrate according to claim 18, which is on its upper surface such an amount of polysiloxanes according to the An Claims 1 to 12, that 0.01 to 5 wt .-%, before preferably 0.05 to 2 wt .-%, fluorine are present. 20. Fiber substrate according to claims 18 and 19, wherein the Substrate leather is.