DE10353557A1 - Producing aqueous copolymer dispersions, e.g. useful for treating leather, comprises copolymerizing an ethylenically unsaturated dicarboxylic acid anhydride and an alkene oligomer and adding water - Google Patents

Abstract

Producing aqueous copolymer dispersions with a water content of 30-99.5 wt.% comprises radical copolymerization of an ethylenically unsaturated dicarboxylic acid anhydride having 4-8 carbon atoms, an oligomer of an alkene having 3-10 carbon atoms and optionally an ethylenically unsaturated comonomer, optionally reacting the product with an alkoxylated alcohol (Ia) or alkoxylated amine (Ib), and adding water. Producing aqueous copolymer dispersions with a water content of 30-99.5 wt.% comprises radical copolymerization of an ethylenically unsaturated dicarboxylic acid anhydride having 4-8 carbon atoms, an oligomer of an alkene having 3-10 carbon atoms, where the oligomer has a molecular weight of 300-5000 or is produced by oligomerising at least 3 equivalents of the alkene, and optionally an ethylenically unsaturated comonomer, optionally reacting the product with an alkoxylated alcohol of formula (Ia) or alkoxylated amine of formula (Ib), and adding water. HO(A 1>O) nR 1> (Ia) H 2N(A 1>O) nR 1> (Ib) A 1>2-20C alkylene; R 1>1-30C alkyl, phenyl or H; n : 1-200. Independent claims are also included for: (1) aqueous copolymer dispersions produced as above; (2) treatment of fibrous substrates using the dispersions; (3) fibrous substrates treated as above; (4) copolymers produced by radical copolymerization of an anhydride, oligomer and optional comonomer as above, reaction with (Ia) or (Ib) and optional hydrolysis; (5) impregnating flat substrates with dispersions or copolymers as above.

Description

• (a) mindestens einem Oligomer von verzweigtem oder unverzweigtem C₃-C₁₀-Alken mit einem mittleren Molekulargewicht M_n bis zu 1200 g/mol,
• (b) mindestens einem Emulgator, der erhältlich ist durch Copolymerisation von (A) mindestens einem ethylenisch ungesättigtes Dicarbonsäureanhydrid, abgeleitet von mindestens einer Dicarbonsäure mit 4 bis 8 C-Atomen, (B) mindestens einem Oligomeren von verzweigtem oder unverzweigtem C₃-C₁₀-Alken, wobei mindestens ein Oligomer ein mittleres Molekulargewicht M_n bis zu 1200 g/mol aufweist, (C) mindestens einem α-Olefin mit bis zu 16 C-Atomen, und (D) optional mindestens einem weiteren ethylenisch ungesättigten Comonomer, und optional Umsetzung mit (E) mindestens einer Verbindung der allgemeinen Formel I a, I b, I c oder I b
  
  und gegebenenfalls anschließendes Kontaktieren mit Wasser, wobei in den Formeln I a bis I d die Variablen wie folgt definiert sind: A¹ C₂-C₂₀-Alkylen, gleich oder verschieden R¹ C₁-C₃₀-Alkyl, linear oder verzweigt, Phenyl oder Wasserstoff, n eine ganze Zahl von 1 bis 200.

The present invention relates to a process for the treatment of fibrous substrates, characterized in that they are treated with

• (a) at least one oligomer of branched or unbranched C ₃ -C ₁₀ -alkene having an average molecular weight M _{n of} up to 1200 g / mol,
• (B) at least one emulsifier obtainable by copolymerization of (A) at least one ethylenically unsaturated dicarboxylic acid anhydride derived from at least one dicarboxylic acid having 4 to 8 C atoms, (B) at least one oligomer of branched or unbranched C ₃ -C ₁₀ Wherein at least one oligomer has an average molecular weight M _n up to 1200 g / mol, (C) at least one α-olefin having up to 16 C atoms, and (D) optionally at least one further ethylenically unsaturated comonomer, and optionally Reaction with (E) at least one compound of the general formula I a, I b, I c or I b
  
  and optionally subsequent contact with water, where in the formulas Ia to Id the variables are defined as follows: A ¹ C ₂ -C ₂₀ -alkylene, identical or different, R ^{1 is} C ₁ -C ₃₀ -alkyl, linear or branched, Phenyl or hydrogen, n is an integer from 1 to 200.

Farther For example, the present invention relates to adjuvants for the treatment of fibrous substrates. Furthermore, the present invention relates fibrous substrates prepared by the process of the invention. Furthermore, the present invention relates to copolymers which are particularly suitable for the preparation of auxiliaries according to the invention.

In In the production of leather, hydrophobing plays an important role Role. To protect the leather or a leather article against moisture and dirt. Also other usage characteristics of the leather like For example, the handle will be by way of water repellency affected. But also with other fibrous substrates such as Textile, paper, cardboard, artificial leather plays the hydrophobing one important role.

From WO 95/07944 are copolymers of 20 to 60 mol% monoethylenically unsaturated C ₄ -C ₆ dicarboxylic acids or their anhydrides with 10 to 70 mol% of at least one oligomer of propene or a branched 1-olefin, for example isobutene, and From 1 to 50 mol% of at least one monoethylenically unsaturated compound which is polymerizable with the abovementioned monomers, for example vinyl ethers and alkyl allyl ethers, and their use for producing oil-soluble reaction products which are suitable as additives for lubricants and fuels.

Out EP-A 1 316 564 are copolymers of maleic anhydride or derivatives of maleic anhydride with polyisobutene having a degree of polymerization of 2 to 8 known. The disclosed copolymers are suitable, for example, as dispersants in lubricant compositions and as a gasoline additive, ie in non-aqueous Media.

From WO 03/23070 fatliquoring agents for skins are known, for example, the polyisobutene with a Molecular weight of 1000 g / mol or products which are prepared by En-reaction of polyisobutene preferably having a molecular weight of about 1000 g / mol and suitable enophiles such as maleic anhydride (Examples 1 to 3). The disclosed polyisobutenes, when used with conventional emulsifiers for the treatment of hides or leathers, are suitable for producing leather with a lumpy handle. Leathers with a lardy handle are desirable for many applications, but the leathers produced according to WO 03/23070 are not uniformly greased over the entire cross section, but only on the surface, in particular on the meat side. Such hydrophobing is undesirable, for example, for shoe upper leather.

It It was therefore the object of a method for the treatment of fibrous Provide substrates that provide good protection against moisture at the same time pleasant grip and as evenly as possible over the Cross-section distributed greasing of the hydrophobized substrates allows. Furthermore, there was the task to provide tools with which fibrous substrates can be treated well. Furthermore, the Task, a method for the preparation of tools ready to and the task was to treat fibrous substrates to provide.

Accordingly, became Found the initially defined method.

• – Textil, worunter im Rahmen der vorliegenden Erfindung Textilfasern, textile Flächengebilde, textile Halb- und Fertigfabrikate und daraus hergestellte Fertigwaren zu verstehen sind, die neben Textilien für die Bekleidungsindustrie beispielsweise auch Teppiche und andere Heimtextilien sowie technischen Zwecken dienende textile Gebilde umfassen. Dazu gehören auch ungeformte Gebilde wie beispielsweise Flocken, linienförmige Gebilde wie Bindfäden, Fäden, Garne, Leinen, Schnüre, Seile, Zwirne sowie Körpergebilde wie beispielsweise Filze, Gewebe, Vliesstoffe und Watten. Erfindungsgemäß zu behandelnde Textilien können natürlichen Ursprungs sein, beispielsweise Wolle, Flachs oder insbesondere Baumwolle, oder synthetisch, beispielsweise Polyamid und Polyester,
• – Papier, Pappe, Kartonagen,
• – Non-Wovens, beispielsweise als Zusatz für Lack- und Bodenpolituren,
• – Holz- und Holzverbundwerkstoffe wie beispielsweise Spanplatten,
• – Kunstleder, Alcantara, Lefa, das sind Lederfaserwerkstoffe aus Lederabfällen, die mit einem Binder oder Harz zu einem künstlich erzeugten Fasergefüge verarbeitet worden sind,

und besonders bevorzugt

• – Leder, wobei unter Leder mit Hilfe von wahlweise Chromgerbstoffen oder Chrom-frei, beispielsweise mit mineralischen Gerbstoffen, Polymergerbstoffen, synthetischen Gerbstoffen, vegetabilen Gerbstoffen, Harzgerbstoffen oder Kombinationen von mindestens zwei der vorgenannten Gerbstoffe vorgegerbte und vorzugsweise gegerbte Tierhäute oder Halbzeuge zu verstehen sind.

The inventive method is based on fibrous substrates. Among fibrous substrates in the context of the present invention are, for example:

• - Textile, which in the context of the present invention, textile fibers, textile fabrics, semi-finished and finished semi-finished products and finished goods are understood to include, in addition to textiles for the clothing industry, for example, carpets and other home textiles and technical purposes serving textile structures. These include unshaped structures such as flakes, linear structures such as twine, threads, yarns, linen, cords, ropes, threads and body structures such as felts, fabrics, nonwovens and wadding. Textiles to be treated according to the invention may be of natural origin, for example wool, flax or, in particular, cotton, or synthetic, for example polyamide and polyester,
• - paper, cardboard, cardboard boxes,
• - non-wovens, for example as an additive for paint and floor polishes,
• - wood and wood composites such as chipboard,
• - artificial leather, Alcantara, Lefa, which are leather fiber materials made of waste leather, which have been processed with a binder or resin to an artificially produced fiber structure,

and especially preferred

• Leather, leather being understood to be pre-tanned and preferably tanned hides or semi-finished products with the aid of optional chrome tanning or chromium-free, for example with mineral tannins, polymer tanning agents, synthetic tanning agents, vegetable tanning agents, resin tanning agents or combinations of at least two of the aforementioned tanning agents.

In an embodiment The present invention is leather with the help animal skin tanned or pre-tanned by chrome tanning agents (wet blue) or semi-finished products.

In a preferred embodiment In the present invention, leather is chromium-free Tanned or pretanned animal skin or semi-finished products (wet white).

• (a) mindestens einem Oligomeren von verzweigtem oder unverzweigtem C₃-C₁₀-Alken, wobei mindestens ein Oligomer ein mittleres Molekulargewicht M_n bis zu 1200 g/mol aufweist, und
• (b) mindestens einem Emulgator.

According to the invention, fibrous substrates are treated with

• (A) at least one oligomer of branched or unbranched C ₃ -C ₁₀ alkene, wherein at least one oligomer has an average molecular weight M _n up to 1200 g / mol, and
• (b) at least one emulsifier.

Suitable oligomers (a) are oligomers of propylene or unbranched or preferably branched C ₄ -C ₁₀ -olefins, where at least one oligomer has an average molecular weight M _n of up to 1200 g / mol. Examples which may be mentioned are oligomers of propylene, isobutene, 1-pentene, 2-methylbutene-1, 1-hexene, 2-methylpentene-1, 2-methylhexene-1, 2,4-dimethyl-1-hexene, diisobutene (mixture of 2, 4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene), 2-ethyl-pentene-1, 2-ethylhexene-1 and 2-propylhepten-1, 1-octene, 1-decene and 1 Dodecene, very particularly preferred are isobutene, diisobutene and 1-dodecene. Oligomers (a) have an ethylenically unsaturated group which may be in the form of a vinyl, vinylidene or alkylvinylidene group.

Co-oligomers of the abovementioned olefins with one another or with up to 20% by weight, based on (a), of vinylaromatics such as styrene and α-methylstyrene, C ₁ -C ₄ -alkylstyrene such as, for example, 2, 3 and 4 Methylstyrene and 4-tert-butylstyrene are suitable.

Particularly preferred oligomers (a) are oligopropylene and oligoisobutenes having an average molecular weight M _n up to 1200 g / mol, preferably in the range from 300 to 1000 g / mol, more preferably at least 400 g / mol, very particularly preferably at least 500 g / mol, for example as determined by gel permeation chromatography (GPC).

In one embodiment of the present invention, oligomers (a) have a polydispersity M _w / M _n in the range from 1.1 to 10, preferably to 3 and more preferably from 1.5 to 1.8.

In one embodiment of the present invention, oligomers (a) have a bimodal molecular weight distribution with a maximum of M _n in the range of 500 to 1200 g / mol and a local maximum of M _n in the range of 2000 to 5000 g / mol.

Oligopropylene and oligoisobutenes are known as such, oligoisobutenes are obtainable for example by oligomerization of isobutene in the presence of a Lewis acid catalyst such as a boron trifluoride catalyst, see, for example, DE-A 27 02 604. As isobutene-containing starting materials are both isobutene itself also isobutene-containing C ₄ hydrocarbon streams, for example C ₄ raffinates, C ₄ cuts from isobutane dehydrogenation, C ₄ cuts from steam crackers or so-called FCC crackers (FCC: fluid catalyzed crackers), if relevant C ₄ - Sections are largely exempt from 1,3-butadiene contained therein. Typically, the concentration of isobutene in C ₄ hydrocarbon streams is in the range of 40 to 60 weight percent. Suitable C ₄ hydrocarbon streams should generally contain less than 500 ppm, preferably less than 200 ppm of 1,3-butadiene.

The Preparation of further oligomers (a) is known per se; regulations can be found, for example, in WO 96/23751 and in WO 99/67347, example Third

• (A) mindestens einem ethylenisch ungesättigten Dicarbonsäureanhydrid, abgeleitet von mindestens einer Dicarbonsäure mit 4 bis 8 C-Atomen, beispielsweise Maleinsäureanhydrid, Itaconsäureanhydrid, Citraconsäureanhydrid, Methylenmalonsäureanydrid, bevorzugt Itaconsäureanhydrid und Maleinsäureanhydrid und ganz besonders bevorzugt Maleinsäureanhydrid;
• (B) mindestens einem Oligomeren von verzweigtem oder unverzweigtem C₃-C₁₀-Alken, wobei mindestens ein Oligomer ein mittleres Molekulargewicht M_n bis zu 1200 g/mol aufweist, oder
• (C) mindestens einem α-Olefin mit bis zu 16 C-Atomen,

und

• (D) optional mindestens einem weiteren von (A) und (C) verschiedenen ethylenisch ungesättigten Comonomer,

und

• (E) optional Umsetzung mit mindestens eine Verbindung I a, I b, I c oder I d,

dessen Carboxylgruppen zumindest partiell verestert oder amidiert sein können, und optional Kontaktieren mit Wasser.According to the invention, fibrous substrate is also treated with at least one emulsifier (b) which is obtainable by preferably free-radical copolymerization of

• (A) at least one ethylenically unsaturated dicarboxylic acid anhydride derived from at least one dicarboxylic acid having 4 to 8 C atoms, for example maleic anhydride, itaconic anhydride, citraconic anhydride, methylenemalonic anhydride, preferably itaconic anhydride and maleic anhydride and most preferably maleic anhydride;
• (B) at least one oligomer of branched or unbranched C ₃ -C ₁₀ alkene, wherein at least one oligomer has an average molecular weight M _n up to 1200 g / mol, or
• (C) at least one α-olefin having up to 16 C atoms,

and

• (D) optionally at least one further ethylenically unsaturated comonomer other than (A) and (C),

and

• (E) optionally reaction with at least one compound I a, I b, I c or I d,

whose carboxyl groups may be at least partially esterified or amidated, and optionally contacting with water.

Suitable oligomers (B) are oligomers of propylene or unbranched or preferably branched C ₄ -C ₁₀ -olefins, where at least one oligomer has an average molecular weight M _n of up to 1200 g / mol. Examples which may be mentioned are oligomers of propylene, isobutene, 1-pentene, 2-methylbutene-1, 1-hexene, 2-methylpentene-1, 2-methylhexene-1, 2,4-dimethyl-1-hexene, diisobutene (mixture of 2, 4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene), 2-ethyl-pentene-1, 2-ethylhexene-1 and 2-propylhepten-1, 1-octene, 1-decene and 1 Called dodecene, very particularly preferred are oligomers of isobutene, diisobutene and 1-dodecene. Oligomers (B) have an ethylenically unsaturated group which may be in the form of a vinyl, vinylidene or alkylvinylidene group.

Also, co-oligomers of the aforementioned olefins with each other or with up to 20 wt .-%, based on (B), vinylaromatics such as styrene and α-methylstyrene, C ₁ -C ₄ -alkylstyrene such as 2-, 3- and 4-methylstyrene and 4-tert-butylstyrene are suitable.

Particularly preferred oligomers (B) are oligopropylene and oligoisobutenes having an average molecular weight M _n up to 1200 g / mol, preferably in the range from 300 to 1000 g / mol, more preferably at least 400 g / mol, very particularly preferably at least 500 g / mol, for example as determined by gel permeation chromatography (GPC).

In one embodiment of the present invention, oligomers (B) have a polydispersity M _w / M _n in the range from 1.1 to 10, preferably to 5 and more preferably from 1.5 to 1.8.

In one embodiment of the present invention, oligomers (B) have a bimodal molecular weight distribution with a maximum of M _n in the range of 500 to 1200 g / mol and a local maximum of M _n in the range of 2000 to 5000 g / mol.

oligomer (B) may be the same or different from oligomer (a).

In an embodiment In the present invention, oligomer (B) and oligomer (a) are the same.

When Comonomer (C) used α-olefins with up to 16 carbon atoms are chosen propylene, 1-butene, isobutene, 1-pentene, 4-methylbut-1-ene, 1-hexene, Diisobutene (mixture of 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene), 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and 1-hexadecene; particularly preferred are isobutene, diisobutene and 1-dodecene.

you can be used for the preparation of emulsifier (b) used according to the invention (A), (B) and (C) copolymerize with each other. You can also go to Production of emulsifier according to the invention (b) (A), (B) and (C) copolymerize with each other and react with (E) or (A), (B) and (C) and another comonomer (D) with each other copoly merisieren, or you can (A) and (B) and (C) and another Copolymerize comonomer (D) with each other and react with (E).

wobei die Variablen wie folgt definiert sind:
A¹ C₂-C₂₀-Alkylen, beispielsweise -(CH₂)₂-, -CH₂-CH(CH₃)-, -(CH₂)₃-, -CH₂-CH(C₂H₅)-, -(CH₂)₄-, -(CH₂)₅-, -(CH₂)₆-, vorzugsweise C₂-C₄-Alkylen; insbesondere -(CH₂)₂-, -CH₂-CH(CH₃)- und -CH₂-CH(C₂H₅)-;
R¹ Phenyl,
Wasserstoff
oder vorzugsweise C₁-C₃₀-Alkyl, linear oder verzweigt, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl, n-Dodecyl, n-Hexadecyl, n-Octadecyl, n-Eicosyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl, ganz besonders bevorzugt Methyl.
n eine ganze Zahl im Bereich von 1 bis 200, bevorzugt 4 bis 20.If it is desired to use emulsifier (b) whose carboxyl groups are at least partially esterified or amidated, the compound (E) selected is at least one compound of general formula I a to I d, preferably I a,

where the variables are defined as follows:
A ¹ C ₂ -C ₂₀ -alkylene, for example - (CH ₂ ) ₂ -, -CH ₂ -CH (CH ₃ ) -, - (CH ₂ ) ₃ -, -CH ₂ -CH (C ₂ H ₅ ) - , - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ -, preferably C ₂ -C ₄ alkylene; in particular - (CH ₂ ) ₂ -, -CH ₂ -CH (CH ₃ ) - and -CH ₂ -CH (C ₂ H ₅ ) -;
R ^{1 is} phenyl,
hydrogen
or preferably C ₁ -C ₃₀ -alkyl, linear or branched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso -Pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl , n-dodecyl, n-hexadecyl, n-octadecyl, n-eicosyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, very particularly preferably methyl.
n is an integer in the range of 1 to 200, preferably 4 to 20.

Of course, the groups A ¹ can only be different if n is a number greater than 1 or if different compounds of the general formula I a to I d are used.

• – Methylendgruppenverschlossene Polyethylenglykole der Formel HO-(CH₂CH₂O)_m-CH₃ mit m = 1 bis 200, vorzugsweise 4 bis 100, besonders bevorzugt 4-50
• – Methylendgruppenverschlossene Blockcopolymere aus Ethylenoxid, Propylenoxid und/oder Butylenoxid mit einem Molekulargewicht M_n von 300 bis 5000 g/mol
• – Methylendgruppenverschlossene statistische Copolymere aus Ethylenoxid, Propylenoxid und/oder Butylenoxid mit einem Molekulargewicht M_n von 300 bis 5000 g/mol
• – Alkoxylierte C₂- bis C₃₀-Alkohole, insbesondere Fettalkoholalkoxylate, Oxoalkoholalkoxylate oder Guerbet-Alkoholalkoxylate, wobei die Alkoxylierung mit Ethylenoxid, Propylenoxid und/oder Butylenoxid durchgeführt werden kann, Beispiele sind
• – C₁₃-C₁₅-Oxoalkoholethoxylate mit 3 bis 30 Ethylenoxideinheiten
• – C₁₃-Oxoalkoholethoxylate mit 3 bis 30 Ethylenoxideinheiten,
• – C₁₂C₁₄-Fettalkoholethoxylate mit 3 bis 30 Ethylenoxideinheiten,
• – C₁₀-Oxoalkoholethoxylate mit 3 bis 30 Ethylenoxideinheiten,
• – C₁₀-Guerbetalkoholethoxylate mit 3 bis 30 Ethylenoxideinheiten,
• – C₉-C₁₁-Oxoalkoholalkoxylate mit 2 bis 20 Ethylenoxideinheiten, 2 bis 20 Propylenoxideinheiten und/oder 1-5 Butylenoxideinheiten;
• – C₁₃-C₁₅-Oxoalkoholalkoxylate mit 2 bis 20 Ethylenoxideinheiten, 2 bis 20 Propylenoxideinheiten und/oder 1-5 Butylenoxideinheiten;
• – C₄-C₂₀-Alkoholethoxylate mit 2 bis 20 Ethylenoxideinheiten.

Specific examples of compounds of general formula Ia are

• - Methylendgruppenverschlossene polyethylene glycols of the formula HO- (CH ₂ CH ₂ O) _m -CH ₃ with m = 1 to 200, preferably 4 to 100, particularly preferably 4-50
• - Methylendgruppenverschlossene block copolymers of ethylene oxide, propylene oxide and / or butylene oxide having a molecular weight M _n of 300 to 5000 g / mol
• - Methylendgruppenver closed statistical copolymers of ethylene oxide, propylene oxide and / or butylene oxide having a molecular weight M _n of 300 to 5000 g / mol
• - Alkoxylierte C ₂ - to C ₃₀ alcohols, in particular fatty alcohol alkoxylates, Oxoalkoholalkoxylate or Guerbet alcohol alkoxylates, wherein the alkoxylation can be carried out with ethylene oxide, propylene oxide and / or butylene oxide, examples are
• - C ₁₃ -C ₁₅ -Oxoalkoholethoxylate with 3 to 30 ethylene oxide units
• C ₁₃ -oxo alcohol ethoxylates with 3 to 30 ethylene oxide units,
• C ₁₂ -C ₁₄ -fatty alcohol ethoxylates with 3 to 30 ethylene oxide units,
• C ₁₀ oxo alcohol ethoxylates with 3 to 30 ethylene oxide units,
• C ₁₀ -guerbet alcohol ethoxylates having from 3 to 30 ethylene oxide units,
• C ₉ -C ₁₁ oxo alcohol alkoxylates having 2 to 20 ethylene oxide units, 2 to 20 propylene oxide units and / or 1 to 5 butylene oxide units;
• C ₁₃ -C ₁₅ oxo alcohol alkoxylates having from 2 to 20 ethylene oxide units, from 2 to 20 propylene oxide units and / or from 1 to 5 butylene oxide units;
• - C ₄ -C ₂₀ -alcohol ethoxylates with 2 to 20 ethylene oxide units.

Preferred examples of compounds of the formula Ib are methylene-terminated polyethyleneglycolamines of the formula H ₂ N- (CH ₂ CH ₂ O) _m -CH ₃ where m = 1 to 200, preferably 4 to 100, particularly preferably 4 to 50.

If it is desired to react with compound I d, compound I c can be reacted with alkylating agents such as, for example, halides or sulfates of the formula R ¹ -Y with Y selected from Cl, Br and I or (R ¹ ) ₂ SO ₄ . Depending on the use of the alkylating agent or compounds I d with Y, SO ₄ ^2- or R ¹ -SO ₄ ^{- obtained} as a counterion.

In one embodiment of the present invention, mixtures of different components (E), for example of the formula Ia, are used. In particular, mixtures of compounds of the formula Ia can be used in which, based in each case on the mixture, at least 95 mol%, preferably at least 98 mol%, up to a maximum of 99.8 mol% R ¹ for C ₁ -C ₃₀ -Alkyl and at least 0.2 mol% and at most 5 mol%, preferably at most 2 mol% of hydrogen.

In one embodiment of the present invention, for the preparation of the emulsifier (b) used according to the invention, the reaction mixture is contacted after the preferably free-radical copolymerization and, if appropriate, the reaction with (E) with water, the water still being Brønsted acid or preferably Brønsted acid. Base may contain. Examples of Brønsted acids are sulfuric acid, hydrochloric acid, tartaric acid and citric acid. Examples of Brønsted base are alkali metal hydroxide such as NaOH and KOH, alkali metal carbonate such as Na ₂ CO ₃ and K ₂ CO ₃ , alkali metal bicarbonate such as NaHCO ₃ and KHCO ₃ , ammonia, amines such as trimethylamine, triethylamine, diethylamine, ethanolamine, N, N-diethanolamine, N, N, N-triethanolamine, N-methylethanolamine.

In another embodiment The present invention can be already during the preferably free radical Contact copolymerization with water.

In another embodiment In the present invention, emulsifier (b) is contacted only during the Treatment according to the invention of fibrous substrate with water.

Carbonsäureamide der Formel III,

nicht-cyclische Amide der allgemeinen Formel IV a und cyclische Amide der allgemeinen Formel IV b

C₁-C₂₀-Alkyl-vinylether wie Methyl-vinylether, Ethyl-vinylether, n-Propyl-vinylether, iso-Propyl-vinylether, n-Butyl-vinylether, iso-Butyl-vinylether, 2-Ethylhexyl-vinylether oder n-Octadecyl-vinylether;
N-Vinyl-derivate von stickstoffhaltigen aromatischen Verbindungen, bevorzugt N-Vinylimidazol, 2-Methyl-1-vinylimidazol, N-Vinyloxazolidon, N-Vinyltriazol, 2-Vinylpyridin, 4-Vinylpyridin, 4-Vinylpyridin-N-oxid, N-Vinylimidazolin, N-Vinyl-2-methylimidazolin,
α,β-ungesättigte Nitrile wie beispielsweise Acrylnitril, Methacrylnitril;
alkoxylierte ungesättigte Ether der allgemeinen Formel V,

Ester und Amide der allgemeinen Formel VI,

ungesättigte Ester der allgemeinen Formel VII

vinylaromatischen Verbindungen der allgemeinen Formel VIII

Phosphat-, phosphonat-, sulfat-, und sulfonathaltige Comonomere wie beispielsweise [2-{(Meth)acryloyloxy}-ethyl]-phosphat, 2-(Meth)acrylamido-2-methyl-1-propansulfonsäure;
α-Olefine, linear oder verzweigt, mit 18 bis 40 Kohlenstoffatomen, bevorzugt mit bis 24 Kohlenstoffatomen, beispielsweise 1-Oktadecen, 1-Eicosen, α-C₂₂H₄₄, α-C₂₄H₄₈ und Gemische der vorstehend genannten α-Olefine.The one or more monomers (D) which can optionally be used to prepare emulsifiers (b) used in the invention are different from (A), (B) and (C). Preferred monomers (D) are:
C ₃ -C ₈ carboxylic acids or carboxylic acid derivatives of the general formula III

Carboxylic acid amides of the formula III,

non-cyclic amides of the general formula IV a and cyclic amides of the general formula IV b

C ₁ -C ₂₀ -alkyl-vinyl ethers such as methyl-vinyl ether, ethyl-vinyl ether, n-propyl-vinyl ether, iso-propyl-vinyl ether, n-butyl-vinyl ether, isobutyl-vinyl ether, 2-ethylhexyl-vinyl ether or n- octadecyl vinyl ether;
N-vinyl derivatives of nitrogen-containing aromatic compounds, preferably N-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, 2-vinylpyridine, 4-vinylpyridine, 4-vinylpyridine-N-oxide, N-vinylimidazoline , N-vinyl-2-methylimidazoline,
α, β-unsaturated nitriles such as acrylonitrile, methacrylonitrile;
alkoxylated unsaturated ethers of the general formula V,

Esters and amides of the general formula VI,

unsaturated esters of general formula VII

vinylaromatic compounds of the general formula VIII

Phosphate, phosphonate, sulfate, and sulfonate-containing comonomers such as [2- {(meth) acryloylo xy} -ethyl] -phosphate, 2- (meth) acrylamido-2-methyl-1-propanesulfonic acid;
α-olefins, linear or branched, having 18 to 40 carbon atoms, preferably having up to 24 carbon atoms, for example 1-octadecene, 1-eicosene, α-C ₂₂ H ₄₄ , α-C ₂₄ H ₄₈ and mixtures of the aforementioned α-olefins ,

The variables are defined as follows:
R ² , R ^{3 are} identical or different and selected from unbranched or branched C ₁ -C ₅ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert. Butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, more preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, iso- Propyl, n-butyl, iso-butyl, sec-butyl and tert -butyl;
and especially hydrogen;
R ^{4 is} identical or different and C ₁ -C ₂₂ -alkyl, branched or unbranched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n -Pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl , n-decyl, n-dodecyl, n-eicosyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
or more preferably hydrogen;
R ^{5 is} hydrogen or methyl,
x is an integer in the range of 2 to 6, preferably 3 to 5;
y is an integer selected from 0 or 1, preferably 1;
a is an integer in the range of 0 to 6, preferably in the range of 0 to 2;
R ⁶ , R ^{7 are} identical or different and selected from hydrogen, unbranched or branched C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert Butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n- Octyl, n-nonyl, n-decyl, preferably C ₁ -C ₄ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, all particularly preferably methyl;
X is oxygen or NR ⁴ ;
R ⁸ [A ³ -O] _n -R ⁴ ,
R ^{9 is} selected from unbranched or branched C ₁ -C ₂₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n- Decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl; preferably C ₁ -C ₁₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n -Tetradecyl,
and in particular hydrogen or methyl;
R ¹⁰ , R ¹¹ are each independently hydrogen, methyl or ethyl, preferably R ¹⁰ and R ^{11 are} each hydrogen;
R ^{12 is} methyl or ethyl;
k is an integer in the range from 0 to 2, preferably k = 0,
A ² , A ^{3 are} identical or different and C ₂ -C ₂₀ -alkylene, for example - (CH ₂ ) ₂ -, -CH ₂ -CH (CH ₃ ) -, - (CH ₂ ) ₃ -, -CH ₂ -CH (C ₂ H ₅ ) -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ -, preferably C ₂ -C ₄ -alkylene; in particular - (CH ₂ ) ₂ -, -CH ₂ -CH (CH ₃ ) - and - (CH ₂ ) ₃ -;
A ⁴ C ₁ -C ₂₀ -alkylene, for example -CH ₂ -, -CH (CH ₃ ) -, -CH (C ₆ H ₅ ) -, -C (CH ₃ ) ₂ -, - (CH ₂ ) ₂ - , -CH ₂ -CH (CH ₃ ) -, - (CH ₂ ) ₃ -, -CH ₂ -CH (C ₂ H ₅ ) -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ -, preferably C ₂ -C ₄ alkylene; in particular - (CH ₂ ) ₂ -, -CH ₂ -CH (CH ₃ ) - and - (CH ₂ ) ₃ -,
or especially a single bond.

The remaining variables are defined as above.

exemplary selected Compounds of the formula III are (meth) acrylamides, such as acrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, N-undecylacrylamide or the corresponding methacrylamides.

exemplary selected Compounds of the formula IV a are N-vinylcarboxamides, such as N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide or N-vinyl-N-methylacetamide; exemplary selected Representative for Compounds of the formula IVb are N-vinylpyrrolidone, N-vinyl-4-piperidone and N-vinyl-ε-caprolactam.

Exemplary selected compounds of formula VI are (meth) acrylic acid esters and amides such as N, N-dialkylaminoalkyl (meth) acrylates or N, N-dialkylaminoalkyl (meth) acrylamides; Examples are N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminopropyl acrylate, N, N-dimethylaminopropyl methacrylate, N, N-diethylamino propyl acrylate, N, N-diethylaminopropyl methacrylate, 2- (N, N-dimethylamino) ethylacrylamide, 2- (N, N-dimethylamino) ethylmethacrylamide, 2- (N, N-diethylamino) ethylacrylamide, 2- (N, N-diethylamino) ethylmethacrylamide, 3- (N, N-dimethylamino) propylacrylamide and 3- (N, N-dimethylamino) propylmethacrylamide.

exemplary selected Compounds of the formula VII are vinyl acetate, allyl acetate, vinyl propionate, Vinyl butyrate, vinyl 2-ethylhexanoate or vinyl laurate.

exemplary selected vinylaromatic compounds of the general formula VIII are α-methylstyrene, para-methylstyrene and especially styrene.

All is particularly preferably used as comonomer (D): acrylic acid, 1-octadecene, methacrylic acid, methyl acrylate, Methyl methacrylate, acrylamide, vinyl n-butyl ether, vinyl isobutyl ether, Styrene, N-vinylformamide, N-vinylpyrrolidone, 1-vinylimidazole and 4-vinylpyridine.

The As emulsifiers (b) used copolymers can concerning (A), (B), (C) and optionally (D) block copolymers, alternating Copolymers or random copolymers, with alternating Copolymers are preferred.

In an embodiment of the present invention the process according to the invention in water Fleet out.

In an embodiment According to the present invention, the anhydride groups are used as emulsifier (b) completely used copolymer after the polymerization or partially hydrolyzed and optionally neutralized before.

In an embodiment According to the present invention, the anhydride groups are used as emulsifier (b) copolymer used after the copolymerization as anhydride groups in front.

In an embodiment you choose a weight ratio from oligomer (a) to emulsifier (b) in the range of 1: 1 to 100: 1, preferably from 10: 1 to 50: 1.

• (A) im Bereich von 5 bis 60 mol-%, bevorzugt 10 bis 55 mol-%,
• (B) im Bereich von 1 bis 95 mol-%, bevorzugt 5 bis 70 mol-%,
• (C) im Bereich von 1 bis 60 mol-%, bevorzugt 10 bis 55 mol-%,
• (D) 0 bis 70 mol-%, bevorzugt 1 bis 50 mol-%, jeweils bezogen auf Copolymerisat, wobei die Summe aus (A), (B), (C) und (D) 100 mol-% ergibt, und
• (E) im Bereich von 0 bis 50 mol-%, bevorzugt 1 bis 30 mol-%, besonders bevorzugt 2 bis 20 mol-%, bezogen auf alle Carboxylgruppen von Copolymerisat.

In one embodiment of the present invention, the molar ratios of emulsifiers used in accordance with the invention are (b)

• (A) in the range of 5 to 60 mol%, preferably 10 to 55 mol%,
• (B) in the range of 1 to 95 mol%, preferably 5 to 70 mol%,
• (C) in the range of 1 to 60 mol%, preferably 10 to 55 mol%,
• (D) 0 to 70 mol%, preferably 1 to 50 mol%, in each case based on copolymer, wherein the sum of (A), (B), (C) and (D) gives 100 mol%, and
• (E) in the range of 0 to 50 mol%, preferably 1 to 30 mol%, particularly preferably 2 to 20 mol%, based on all carboxyl groups of copolymer.

The inventive method can be carried out as tanning or preferably as retanning, in The following tanning method according to the invention or retanning process according to the invention called. However, one can the method of the invention as a separate Exercise treatment procedures.

The Tanning process according to the invention is practiced in Generally speaking so that the dispersion according to the invention or copolymer of the invention in one portion or in several portions immediately before or but during of the tanning. The tanning process according to the invention is preferably carried out at a pH of 2.5 to 5, which is often observed that the pH during the implementation the tanning process according to the invention increases by about 0.3 to three units. You can also change the pH by adding blunting agents by about 0.3 to three units increase.

The Tanning process according to the invention you lead generally at temperatures of 10 to 45 ° C, preferably at 20 to 30 ° C by. proven has a duration of 10 minutes to 12 hours, preferably a duration from one to three hours. The tanning process according to the invention can be found in any tannery usual Carry out vessels, for example by walking in barrels or in twisted drums.

For the execution of the tanning process (a) and (b) according to the invention, it is possible to meter together or separately. Preferably, one doses (a) and (b) together. Particular preference is given to metering (a) and (b) in the form of an aqueous dispersion, where, in the case of dispersions below, aqueous emulsions, Sus pensions and also clear-looking aqueous solutions of (a) and (b).

In a variant of the tanning process according to the invention one puts (a) and (b) together with one or more conventional ones Tannins, for example, with chrome tannins, mineral Tannins, preferably with syntans, polymer tanning or vegetable Tannins, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Volume A15, pages 259-282 and in particular Page 268 ff., 5th edition, (1990), Verlag Chemie Weinheim.

you can the inventive method for the treatment of leather, preferably as a retanning method of leather using (a) and (b). The Nachgerbverfahren invention is based on conventional, i. for example with chrome tanning agents, mineral tannins, preferably with polymer tanning agents, aldehydes, Syntanen or resin tannins tanned semi-finished or according to the invention Use of (a) and (b) produced semifinished products. To carry out the retanning according to the invention you leave According to the invention (a) and (b) act on semi-finished products.

you can for execution the Nachgerbverfahrens invention (a) and (b) dosed together or separately. Preferably dosed Man (a) and (b) together. Particular preference is given to metering (a) and (b) in the form of an aqueous Dispersion.

The Nachgerbverfahren invention can be done under otherwise tannery conditions. you expediently chooses one or more, i. 2 to 6 action steps and can be between the Flush the reaction steps with water. The temperature at the individual action steps is in each case in the range of 5 to 60 ° C, preferably 20 to 45 ° C.

you may be in the range from 0.5 to 10% by weight of the sum of oligomer (a) and emulsifier (b), wherein wt .-% are based on the Gap weight of the invention treated Leather or treated according to the invention Semi-finished products.

Of course you can one to carry the tanning process according to the invention or Nachgerbverfahrens during tanning or retanning usually used, for example, fatliquors, polymer tanning agents, Acrylate- and / or methacrylate-based fatliquor or on the Base of silicones, retanning agents based on resin and vegetable tanning agents, fillers, Leather dyes or emulsifiers or combinations of at least two of the aforementioned substances.

In an embodiment the Nachgerbverfahrens invention you can use other fatliquoring and water repellents.

In another embodiment the Nachgerbverfahrens invention one waives the use of further fatliquoring and hydrophobing agents.

In an embodiment The present invention dispenses with the addition of further Hydrophobic or fatliquoring agents based on silicones.

In another embodiment spray of the present invention one watery Dispersion of (a) and (b) on fibrous substrate, in particular Paper, cardboard, cardboard.

In another embodiment In the present invention, fibrous substrates are treated, in particular Textile, with (a) and (b), for example, by the exhaust process.

By the treatment according to the invention fibrous substrate is rendered hydrophobic.

One Another object of the present invention are fibrous substrates, preferably leather, for example based on wet-blue and in particular Leather based on wet-white, produced by the treatment method according to the invention. You have a particularly good water repellency by a uniform lubrication over the entire cross-section of the fibrous substrate according to the invention characterized is.

A further subject matter of the present invention is leather produced by the tanning process according to the invention or the retanning process according to the invention or by a combination of inventive tanning process and retanning process according to the invention. Leather according to the invention NEN through an overall advantageous quality, for example, they have a particularly pleasant handle. The leathers according to the invention contain a copolymer described above which penetrates particularly well into the micro-region of the elementary fibers.

One Another aspect of the present invention is the use of fibrous material according to the invention Substrates, for example for the production of auto parts or packaging.

One Another aspect of the present invention is the use of the leather according to the invention for the manufacture of clothing, furniture or car parts. Under clothing are for the purposes of the present invention, for example jackets, Pants, shoes, especially shoe soles, belts or suspenders to call. Under furniture are all such in the context of the present invention To name furniture containing the ingredients of leather. By way of example, seating is called such as armchairs, chairs, sofas. Car parts are exemplified by car seats.

One Another aspect of the present invention are garments containing or prepared from substrates according to the invention, in particular made of leather according to the invention or textile according to the invention. Another aspect of the present invention is furniture comprising or made of leather according to the invention. Another aspect The present invention relates to car parts containing or manufactured made of leather according to the invention.

• (a) mindestens ein Oligomer von verzweigtem oder unverzweigtem C₃-C₁₀-Alken mit einem mittleren Molekulargewicht M_n bis zu 1200 g/mol,
• (b) mindestens einen Emulgator, der erhältlich ist durch Copolymerisation von (A) mindestens einem ethylenisch ungesättigtes Dicarbonsäureanhydrid, abgeleitet von mindestens einer Dicarbonsäure mit 4 bis 8 C-Atomen, (B) mindestens einem Oligomeren von verzweigtem oder unverzweigtem C₃-C₁₀-Alken, wobei mindestens ein Oligomer ein mittleres Molekulargewicht M_n bis zu 1200 g/mol aufweist, (C) mindestens einem α-Olefin mit bis zu 16 C-Atomen, und (D) optional mindestens einem weiteren ethylenisch ungesättigten Comonomer, und optional Umsetzung mit (E) mindestens einer Verbindung der allgemeinen Formel I a, I b, I c oder I b,
  
  wobei in Formel I a und I d die Variablen wie folgt definiert sind: A¹ C₂-C₂₀-Alkylen, gleich oder verschieden R¹ C₁-C₃₀-Alkyl, linear oder verzweigt, Phenyl oder Wasserstoff, n eine ganze Zahl von 1 bis 200 und gegebenenfalls anschließendes Kontaktieren mit Wasser.

Another object of the present invention are adjuvants containing

• (a) at least one oligomer of branched or unbranched C ₃ -C ₁₀ -alkene having an average molecular weight M _{n of} up to 1200 g / mol,
• (B) at least one emulsifier obtainable by copolymerization of (A) at least one ethylenically unsaturated dicarboxylic anhydride derived from at least one dicarboxylic acid having 4 to 8 carbon atoms, (B) at least one oligomer of branched or unbranched C ₃ -C ₁₀ Wherein at least one oligomer has an average molecular weight M _n up to 1200 g / mol, (C) at least one α-olefin having up to 16 C atoms, and (D) optionally at least one further ethylenically unsaturated comonomer, and optionally Reaction with (E) at least one compound of the general formula I a, I b, I c or I b,
  
  where in formulas Ia and Id the variables are defined as follows: A ¹ C ₂ -C ₂₀ -alkylene, identical or different, R ^{1 is} C ₁ -C ₃₀ -alkyl, linear or branched, phenyl or hydrogen, n is an integer from 1 to 200 and optionally subsequent contact with water.

The variables are defined as above. Of course, the groups A ¹ can only be different if n is a number greater than 1 or if different compounds of the general formula I a and / or I b are used.

By Use of the aid according to the invention let yourself the inventive method especially easy to treat fibrous substrates. The Dosage is particularly convenient, and the greasing of treated according to the invention fibrous substrates are particularly uniform.

One Another object of the present invention is a method for the preparation of auxiliaries according to the invention, in the following also inventive production process called. The production process according to the invention can be carried out in such a way that one oligomer (a) and emulsifier (b) mixed together. If for the production of (b) has added water, the added remains Water preferably in the emulsifier (b), so that the aid according to the invention preferably in the form of aqueous Dispersions incurred.

In a special embodiment the production process according to the invention mixed oligomer (a) and emulsifier (b) together and passes the mixture through a homogenizer, for example a gap homogenizer. You get especially stable aqueous Dispersions, which are also the subject of the present invention are.

In an embodiment the present invention is added to so much water that the Water content of the dispersion according to the invention of (a) and (b) ranges from 30 to 99.5% by weight of water to aid according to the invention.

In an embodiment According to the present invention, adjuvants according to the invention have a pH in the range of 3 to 10, preferably 5 to 8.

Of course you can one aids according to the invention add further substances, for example, further emulsifiers, preferably However, if you use adjuvants according to the invention no further emulsifiers too.

• (A) mindestens einem ethylenisch ungesättigten Dicarbonsäureanhydrid, abgeleitet von mindestens einer Dicarbonsäure mit 4 bis 8 C-Atomen
• (B) mindestens einem Oligomeren von verzweigtem oder unverzweigtem C₃-C₁₀-Alken, wobei mindestens ein Oligomer ein mittleres Molekulargewicht M_n bis zu 1200 g/mol aufweist,
• (C) mindestens einem α-Olefin mit bis zu 16 C-Atomen, und
• (D) optional mindestens einem weiteren ethylenisch ungesättigten Comonomer, und optional Umsetzung mit
• (E) mindestens einer Verbindung der allgemeinen Formel I a, I b, I c oder I b,
  
  wobei in Formel I a bis I d die Variablen wie folgt definiert sind: A¹ C₂-C₂₀-Alkylen, gleich oder verschieden, R¹ C₁-C₃₀-Alkyl, linear oder verzweigt, Phenyl oder Wasserstoff, n eine ganze Zahl von 1 bis 200 und gegebenenfalls anschließendes Kontaktieren mit Wasser.

Emulsifiers (b) can be prepared by copolymerization, preferably free-radical copolymerization of

• (A) at least one ethylenically unsaturated dicarboxylic anhydride derived from at least one dicarboxylic acid having 4 to 8 carbon atoms
• (B) at least one oligomer of branched or unbranched C ₃ -C ₁₀ -alkene, where at least one oligomer has an average molecular weight M _{n of} up to 1200 g / mol,
• (C) at least one α-olefin having up to 16 carbon atoms, and
• (D) optionally at least one further ethylenically unsaturated comonomer, and optionally reaction with
• (E) at least one compound of the general formula I a, I b, I c or I b,
  
  wherein in formula Ia to Id the variables are defined as follows: A ¹ C ₂ -C ₂₀ -alkylene, identical or different, R ^{1 is} C ₁ -C ₃₀ -alkyl, linear or branched, phenyl or hydrogen, n is an integer Number of 1 to 200 and optionally subsequent contact with water.

to Representation of the invention as an emulsifier (b) Substances used can be used appropriately as follows.

In an embodiment of the present invention is prepared by copolymerization of (A), (B), (C) and optionally (D) copolymers which are obtained after the copolymerization with (E) partially esterified or amidated and which is used according to the invention as emulsifier (b).

In another embodiment of the present invention is prepared by copolymerization of (A), (B), (C) and optionally (D) in the presence of (E) partially esterified or amidated copolymers prepared according to the invention as an emulsifier (b) uses.

In one embodiment of the present invention, mixtures of different components (E), for example of the formula Ia, are used. In particular, mixtures of compounds of the formula Ia can be used in which, based in each case on the mixture, at least 95 mol%, preferably at least 98 mol%, up to a maximum of 99.8 mol% R ¹ for C ₁ -C ₃₀ -Alkyl and at least 0.2 mol% and at most 5 mol%, preferably at most 2 mol% of hydrogen.

If it is desired to react with compound I d, compound I c can be reacted with alkylating agents such as, for example, halides or sulfates of the formula R ¹ -Y with Y selected from Cl, Br and I or (R ¹ ) ₂ SO ₄ . Depending on the use of the alkylating agent or compounds I d with Y, SO ₄ ^2- or R ¹ -SO ₄ ^{- obtained} as a counterion.

Instead of With compound I d implement, one can in the context of the present Implement invention also with I c and following the copolymerization and optionally contacting with water with alkylating agent implement.

In an embodiment The present invention is used in accordance with the invention Emulsifiers (b) copolymerized dicarboxylic anhydrides (A) partially or Completely in hydrolyzed and optionally neutralized form.

Carbonsäureamiden der Formel III,

nicht-cyclischen Amiden der allgemeinen Formel IV a oder cyclischen Amiden der allgemeinen Formel IV b

C₁-C₂₀-Alkyl-Vinylethern,
N-Vinyl-Derivaten von stickstoffhaltigen aromatischen Verbindungen,
α,β-ungesättigten Nitrilen,
alkoxylierten ungesättigten Ethern der allgemeinen Formel V

Estern oder Amiden der allgemeinen Formel VI

ungesättigten Estern der allgemeinen Formel VII

vinylaromatischen Verbindungen der allgemeinen Formel VIII

Phosphat-, Phosphonat-, Sulfat- und Sulfonatgruppen-haltige Comonomere,
α-Olefine, linear oder verzweigt, mit 18 bis 40 Kohlenstoffatomen, bevorzugt mit bis 24 Kohlenstoffatomen, insbesondere 1-Oktadecen, 1-Eicosen, α-C₂₂H₄₄, α-C₂₄H₄₈ und Gemische der vorstehend genannten α-Olefine;
wobei in den allgemeinen Formeln die Variablen wie folgt definiert sind:
R², R³ gleich oder verschieden und gewählt aus Wasserstoff, unverzweigten oder verzweigten C₁-C₅-Alkyl und COOR⁴,
R⁴ gleich oder verschieden und gewählt aus Wasserstoff oder C₁-C₂₂-Alkyl, verzweigt oder unverzweigt,
R⁵ Wasserstoff oder Methyl,
x eine ganze Zahl im Bereich von 2 bis 6,
y eine ganze Zahl, ausgewählt aus 0 oder 1,
a eine ganze Zahl im Bereich von 0 bis 6,
R⁶, R⁷ gleich oder verschieden und gewählt aus Wasserstoff, unverzweigten oder verzweigten C₁-C₁₀-Alkyl,
X Sauerstoff oder N-R⁴
R⁸ [A³-O]_n-R⁴,
R⁹ gleich oder verschieden und gewählt aus Wasserstoff, unverzweigten oder verzweigten C₁-C₁₀-Alkyl,
R¹⁰, R¹¹ unabhängig voneinander jeweils Wasserstoff, Methyl oder Ethyl, bevorzugt sind R¹⁰ und R¹¹ jeweils Wasserstoff;
R¹² Methyl oder Ethyl;
k eine ganze Zahl im Bereich von 0 bis 2 bedeutet, bevorzugt gilt k = 0
A², A³ C₂-C₂₀-Alkylen,
A⁴ C₁-C₂₀-Alkylen oder eine Einfachbindung
und die übrigen Variablen wie oben stehend definiert sind.In one embodiment of the present invention, emulsifiers (b) employed in accordance with the invention comprise at least one comonomer (D) in copolymerized form which is selected
ethylenically unsaturated C ₃ -C ₈ -carboxylic acids or carboxylic acid derivatives of the general

Carboxylic acid amides of the formula III,

non-cyclic amides of the general formula IV a or cyclic amides of the general formula IV b

C ₁ -C ₂₀ -alkyl-vinyl ethers,
N-vinyl derivatives of nitrogen-containing aromatic compounds,
α, β-unsaturated nitriles,
alkoxylated unsaturated ethers of the general formula V

Esters or amides of the general formula VI

unsaturated esters of the general formula VII

vinylaromatic compounds of the general formula VIII

Phosphate, phosphonate, sulfate and sulfonate group-containing comonomers,
α-olefins, linear or branched, having 18 to 40 carbon atoms, preferably having up to 24 carbon atoms, in particular 1-octadecene, 1-eicosene, α-C ₂₂ H ₄₄ , α-C ₂₄ H ₄₈ and mixtures of the abovementioned α-olefins ;
where in the general formulas the variables are defined as follows:
R ² , R ^{3 are} identical or different and selected from hydrogen, unbranched or branched C ₁ -C ₅ -alkyl and COOR ⁴ ,
R ^{4 is} identical or different and selected from hydrogen or C ₁ -C ₂₂ -alkyl, branched or unbranched,
R ^{5 is} hydrogen or methyl,
x is an integer in the range of 2 to 6,
y is an integer selected from 0 or 1,
a is an integer in the range of 0 to 6,
R ⁶ , R ^{7 are} identical or different and selected from hydrogen, unbranched or branched C ₁ -C ₁₀ -alkyl,
X oxygen or NR ⁴
R ⁸ [A ³ -O] _n -R ⁴ ,
R ^{9 is} identical or different and selected from hydrogen, unbranched or branched C ₁ -C ₁₀ -alkyl,
R ¹⁰ , R ¹¹ are each independently hydrogen, methyl or ethyl, preferably R ¹⁰ and R ^{11 are} each hydrogen;
R ^{12 is} methyl or ethyl;
k is an integer in the range of 0 to 2, preferably k = 0
A ² , A ³ C ₂ -C ₂₀ -alkylene,
A ⁴ C ₁ -C ₂₀ alkylene or a single bond
and the remaining variables are defined as above.

• (A) im Bereich von 5 bis 60 mol-%, bevorzugt 10 bis 55 mol-%,
• (B) im Bereich von 1 bis 95 mol-%, bevorzugt 5 bis 70 mol-%,
• (C) im Bereich von 1 bis 60 mol-%, bevorzugt 10 bis 55 mol-%
• (D) im Bereich von 0 bis 70 mol-%, bevorzugt 1 bis 50 mol-%, jeweils bezogen auf Copolymerisat, wobei die Summe aus (A), (B), (C) und (D) 100 mol-% ergibt, und
• (E) im Bereich von 0 bis 50 mol-%, bevorzugt 1 bis 30 mol-%, besonders bevorzugt 2 bis 20 mol-%, bezogen auf alle Carboxylgruppen des Copolymerisats.

In one embodiment of the present invention, the molar ratios of comonomers copolymerized in emulsifier (b) according to the invention are

• (A) in the range of 5 to 60 mol%, preferably 10 to 55 mol%,
• (B) in the range of 1 to 95 mol%, preferably 5 to 70 mol%,
• (C) in the range of 1 to 60 mol%, preferably 10 to 55 mol%
• (D) in the range of 0 to 70 mol%, preferably 1 to 50 mol%, in each case based on copolymer, wherein the sum of (A), (B), (C) and (D) gives 100 mol% , and
• (E) in the range of 0 to 50 mol%, preferably 1 to 30 mol%, particularly preferably 2 to 20 mol%, based on all carboxyl groups of the copolymer.

In one embodiment of the present invention ver as emulsifier (b) ver used copolymers of (A), (B), (C) and optionally (D) has an average molecular weight M _w in the range of 1000 g / mol to 50,000 g / mol, preferably 1500 g / mol to 25,000 g / mol, determined, for example by gel permeation chromatography with dimethylacetamide as solvent and polymethyl methacrylate as standard.

According to the invention as an emulsifier (b) Copolymers of (A), (B), (C) and optionally (D) used and (E) can concerning (A), (B), (C) and optionally (D) block copolymers, be alternating copolymers or random copolymers, wherein alternating copolymers are preferred.

The polydispersity M _w / M _n of copolymers of (A), (B), (C) and optionally (D) and (E) used according to the invention as emulsifier (b) is generally in the range from 1.1 to 20, preferably from 2 to 10.

In an embodiment of the present invention have used as emulsifier (b) according to the invention Copolymers of (A), (B), (C) and optionally (D) and (E) Fikentscher K values in the range from 5 to 100, preferably 8 to 30 (measured according to H. Fikentscher at 25 ° C in cyclohexanone and a Polymer concentration of 2% by weight).

In an embodiment of the present invention used according to the invention Emulsifiers (b) contain unpolymerized comonomer (B), for example in proportions of 1 to 50 wt .-%, based on the Total weight of emulsifier.

to Production of according to the invention as an emulsifier (B) used copolymers of (A), (B), (C) and optionally (D) and (E) starting from (A), (B), (C) and optionally (D), which are preferably copolymerized with each other radically and optionally with (E) implements. The reaction with (E) can, if she wanted will, before, during and after the copolymerization. During or preferably after the copolymerization can be contacted with water. One can but for the production according to the invention as emulsifier (b) used Copolymer also renounce to contact with water.

In a special embodiment of the present invention you first a radical copolymerization of (A), (B), (C) and optionally (D) by and then sets with (E) um.

In another special embodiment The present invention is the radical copolymerization of (A), (B), (C) and optionally (D) in the presence of the whole Amount or proportions of the compound (E) to be used.

In another special embodiment The present invention is first (A) and optionally (D) with (E) and then copolymerizes radically with (B) and (C).

If a reaction of copolymer of (A), (B), (C) and optionally (D) with (E) or a free-radical copolymerization in the presence of (E) is desired, then the total amount of (E) is calculated such that starting from a complete reaction of (E) and up to 50 mol%, preferably 1 to 30 mol%, particularly preferably 2 to 20 mol% (E), based on all carboxyl groups of the copolymer used. In the context of the present invention, the term "all carboxyl groups contained in the polymer" is understood as meaning those carboxyl groups of copolymerized comonomers (A) and optionally (D) which are present as anhydride, as C ₁ -C ₄ -alkyl ester or as carboxylic acid.

The free-radical copolymerization is advantageously started by initiators, for example peroxides or hydroperoxides. Suitable peroxides or hydroperoxides are di-tert-butyl peroxide, tert-butyl peroctoate, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, tert-butyl permaleinate, tert-butyl perisobutyrate, benzoyl peroxide, diacetyl peroxide, succinyl peroxide, p-butyl peroxide. Chlorobenzoyl peroxide, Dicyclohexylperoxiddicarbonat, exemplified. The use of redox initiators is also suitable, for example combinations of hydrogen peroxide or sodium peroxodisulfate or one of the abovementioned peroxides with a reducing agent. Suitable reducing agents are, for example, ascorbic acid, tartaric acid, Fe (II) salts such as FeSO ₄ , sodium bisulfite, potassium bisulfite.

suitable Initiators are also Azo compounds such as 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylpropion-amidine) dihydrochloride and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile).

In general, initiator in amounts of 0.1 to 20 wt .-%, preferably 0.2 to 15 wt .-%, be counts on the mass of all comonomers used.

you the copolymerization can be carried out in the presence or in the absence of solvents and precipitants carry out. As a solvent for the radical copolymerization come polar, compared to acid anhydride inert solvents considering such as e.g. Acetone, tetrahydrofuran and dioxane. Suitable precipitants For example, toluene, ortho-xylene, meta-xylene and aliphatic Hydrocarbons.

In a preferred embodiment you work without solvent or in the presence of only minor amounts of solvent, i. 0.1 to maximum 10% by weight, based on the total mass of comonomers (A), (B), (C) and optionally (D). As solvents are among the Conditions of copolymerization and esterification or Amide formation inerfe substances to understand, especially aliphatic and aromatic hydrocarbons such as cyclohexane, n-heptane, isododecane, Benzene, toluene, ethylbenzene, xylene as mixture of isomers, meta-xylene, ortho-xylene. If one works in the reaction with (E) without acidic catalyst or If one waives the reaction with (E), then one can the radical copolymerization and optionally reaction with (E) also in solvents selected from Ketones such as acetone, methyl ethyl ketone, or cyclic ones or noncyclic ethers such as tetrahydrofuran or Perform di-n-butyl ether.

The Copolymerization and optionally the reaction with (E) is preferably carried out with the exclusion of oxygen, for example in a nitrogen or argon atmosphere, preferably in a stream of nitrogen.

For the radical Copolymerization and, if appropriate, the reaction with (E) may be customary apparatuses be used, for. As autoclave and boiler.

The Order of addition of the comonomers can be different Make way.

In an embodiment put a mixture of (E) and (A) before and gives initiator and at the same time (B), (C) and optionally (D) too. It is preferred (B) and (C) and optionally (D) in the manner of a feed process admit.

In another embodiment put a mixture of (E) and (A) before and gives initiator and simultaneously (B) and (C) and optionally (D) in the manner of a feed process to, wherein initiator, (B) and (C) and optionally (D) respectively solved in (E) are.

In another embodiment if one prefers a mixture of (E) and (A) and gives initiator and (B), (C) and (D) in the manner of a feed process, wherein the feed rates of (B), (C) and (D) are chosen differently.

In another embodiment if one introduces a mixture of (E) and (A) and gives initiator and (B), (C) and (D) in the manner of a feed process, wherein the feed rates of (B), (C) and (D) are the same become.

In another embodiment one puts (A) and optionally (D) before and gives initiator and (B) and (C) in the manner of a Zulaufverahrens and then sets if necessary with (E) um.

In another embodiment (A) and give Initiator, (B), (C) and optionally (D) in the manner of a feed process and then sets if necessary with (E) um.

In another embodiment put (B), (C) and optionally (D) before and gives initiator and (A) in the manner of a feed process and then sets, if necessary with (E) um.

In another embodiment adding (B) and (C) and giving initiator, (A) and optionally (D) in the manner of a feed process and then sets if necessary with (E) um.

In another embodiment put (B) and optionally (D) and give initiator, (A) and optionally (C) in the manner of a feed process and sets subsequently optionally with (E) um.

In another embodiment, (A), (B), (C) and optionally (E) are added, and initiator and (D) are added in the manner of a feed process. (A), (B) and optionally (E) may also be in solution be presented.

In an embodiment one gives while the addition of (B), (C) and optionally (D) further initiator to.

In an embodiment one gives while the addition of (A) and optionally (D) further initiator.

In an embodiment is the temperature for the copolymerization of (A), (B), (C) and optionally (D) in Range from 80 to 300 ° C, preferably 90 to 200 ° C.

Of the Pressure is for example in the range of 1 to 15 bar, preferably 1 to 10 bar.

It is possible to use regulators, for example C ₁ to C ₄ -aldehydes, formic acid and compounds containing organic SH groups, such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, tert-butylmercaptan, n-dodecylmercaptan. Polymerization regulators are generally used in amounts of from 0.1 to 10% by weight, based on the total mass of the comonomers used. Preference is given to working without the use of controllers.

you can while the copolymerization of one or more polymerization inhibitors in small amounts, for example, hydroquinone monomethyl ether. Polymerization inhibitor can be advantageously with (B), (C) and optionally (D) dose. Suitable amounts of polymerization inhibitor are 0.01 to 1 wt .-%, preferably 0.05 to 0.5 wt .-%, calculated on the mass of all comonomers. The addition of polymerization inhibitor is particularly preferred when the copolymerization at Temperatures above 80 ° C is performed.

To Termination of the addition of (A), (B), (C), optionally (D), optionally (E) and optionally initiator can be left to react.

The Duration of radical copolymerization is generally 1 to 12 Hours, preferably 2 to 9 hours, more preferably 3 to 6 Hours.

The Duration of the reaction with (E) can be 1 to 12 hours, preferably 2 to 9 hours, more preferably 3 to 6 hours.

Leading the preparation of (b) by reacting (A), (B), (C) and optionally (D) in the presence of the total amount of (E) copolymerized, is a total reaction time of 1 to 12 hours, preferably 2 suitable for up to 10 hours, more preferably 3 to 8.

you may be the reaction with (E) in the absence or even presence of catalysts, especially acid catalysts such as e.g. Sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, n-dodecylbenzenesulfonic acid, hydrochloric acid or acidic ion exchangers.

In Another variant of the method described leads you the reaction with (E) in the presence of an entrainer, with the optionally resulting in the reaction of water Azeotrope forms.

in the Generally governed under the conditions of the above Complete steps (E) or to some extent with the carboxyl groups of the anhydrides (A) and optionally the carboxyl groups from (D). In general less than 40 mol% remain as unreacted (E).

It is possible, by methods known per se such as extraction not reacted (E) obtainable by the preparation process according to the invention Separate copolymer.

In an embodiment one can point to the further step of separating unreacted (E) dispense with the copolymers produced. In this embodiment If one sets copolymers together with a certain percentage on unreacted (E) for the treatment of fibrous substrates one.

By the above-described copolymerization of (A), (B), (C) and optionally (D) is obtained Copolymers. The resulting copolymers can be subjected to purification by conventional methods, for example reprecipitation or extractive removal of unreacted monomers. If a solvent or precipitant has been used, it is possible to remove it after completion of the copolymerization, for example by distillation.

in the The scope of the present invention may be as described above contact prepared copolymer with water, calculated the amount of added water so that dispersion according to the invention gets which has a water content in the range from 30 to 99.5% by weight have on the total mass of aids.

In one embodiment, after the radical copolymerization and, if appropriate, the reaction with (E) with water, the water may still contain Brønsted acid or preferably Brønsted base. Examples of Brønsted acids are sulfuric acid, hydrochloric acid, tartaric acid and citric acid. Examples of Brønsted base are alkali metal hydroxide such as NaOH and KOH, alkali metal carbonate such as Na ₂ CO ₃ and K ₂ CO ₃ , alkali metal bicarbonate such as NaHCO ₃ and KHCO ₃ , ammonia, amines such as trimethylamine, triethylamine, diethylamine, ethanolamine, N, N-diethanolamine, N, N, N-triethanolamine, N-methylethanolamine. The concentration of Brønsted acid or preferably Brønsted base is generally from 1 to 20% by weight, based on the sum of water and Brønsted acid or water and Brønsted base.

you can already during add water to the radical copolymerization, preferably However, it is only at the end of the radical copolymerization Water too. Has one the radical copolymerization and the reaction with (E) in the presence of solvent carried out, so it is preferred, first solvent to remove, for example by distilling off and only afterwards to contact with water.

By contacting with water, optionally Brønsted acid or preferably Brønsted base can contain the present in the copolymer carboxylic anhydride partially or completely be hydrolyzed.

To contacting with water, optionally Brønsted acid or preferably Brønsted base may be included, at temperatures in the range of 20 to 120 ° C, preferably up to 100 ° C postreacted, for a period of 10 minutes to 48 hours.

In an embodiment In the present invention, water is added, the water still being Brønsted acid or preferably Brønsted base can contain at 50 to 100 ° C before and gives way in the manner of a feed process if necessary 50 to 120 ° C heated Copolymer to.

In a further embodiment the present invention sets copolymer at 50 to 120 ° C before and gives, if necessary, to 50 bis in the manner of a feed process 100 ° C heated water to, with the water still Br⌀nsted acid or preferably Brønsted base may contain.

In one embodiment of the present invention, a mixture of water, wherein the water may still contain Brønsted acid or preferably Brønsted base and nonionic surfactant, at 50 to 100 ° C before and gives in the manner of a feed process optionally heated to 50 to 120 ° C copolymer. Suitable nonionic surfactants are for example multiply, preferably 3 to 30 times alkoxylated C ₁₂ -C ₃₀ alkanols.

In a further embodiment, the copolymer is initially introduced at 50.degree. To 120.degree. C. and, in the manner of a feed process, the mixture of water, optionally heated to 50.degree. To 100.degree. C., the water still being Brønsted acid or preferably Brønsted base Nonionic surfactant is, for example, polyhydric, preferably 3 to 30 times alkoxylated C ₁₂ -C ₂₀ -alkanol in question.

The The copolymers described above usually fall in the form of aqueous Dispersions or aqueous solutions or in bulk. aqueous Dispersions and solutions from the above-described copolymers are also subject matter of the present invention. From aqueous dispersions and solutions of the invention leave copolymers according to the invention isolate methods known per se to those skilled in the art, for example by evaporation of water or by spray drying.

• (A) mindestens einem ethylenisch ungesättigtes Dicarbonsäureanhydrid, abgeleitet von mindestens einer Dicarbonsäure mit 4 bis 8 C-Atomen,
• (B) mindestens einem Oligomeren von verzweigtem oder unverzweigtem C₃-C₁₀-Alken, wobei mindestens ein Oligomer ein mittleres Molekulargewicht M_n bis zu 1200 g/mol aufweist,
• (C) mindestens einem α-Olefin mit bis zu 16 C-Atomen, und
• (D) optional mindestens einem weiteren ethylenisch ungesättigten Comonomer, und optional Umsetzung mit
• (E) mindestens einer Verbindung der allgemeinen Formel I a, I b, I c oder I b
  
  und gegebenenfalls anschließendes Kontaktieren mit Wasser, wobei in den Formeln I bis i d die Variablen wie folgt definiert sind: A¹ C₂-C₂₀-Alkylen, gleich oder verschieden R¹ C₁-C₃₀-Alkyl, linear oder verzweigt, Phenyl oder Wasserstoff, n eine ganze Zahl von 1 bis 200.

Another object of the present application are copolymers obtainable by copolymerization of

• (A) at least one ethylenically unsaturated dicarboxylic acid anhydride derived from at least one dicarboxylic acid having 4 to 8 C atoms,
• (B) at least one oligomer of branched or unbranched C ₃ -C ₁₀ -alkene, where at least one oligomer has an average molecular weight M _{n of} up to 1200 g / mol,
• (C) at least one α-olefin having up to 16 carbon atoms, and
• (D) optionally at least one further ethylenically unsaturated comonomer, and optionally reaction with
• (E) at least one compound of the general formula I a, I b, I c or I b
  
  and optionally subsequent contacting with water, wherein in the formulas I to id the variables are defined as follows: A ¹ C ₂ -C ₂₀ -alkylene, identical or different R ¹ C ₁ -C ₃₀ -alkyl, linear or branched, phenyl or Hydrogen, n is an integer from 1 to 200.

Especially is preferred in copolymers of the invention at least one comonomer (C) chosen from isobutene, diisobutene and 1-dodecene.

• (A) im Bereich von 5 bis 60 mol-%, bevorzugt 10 bis 55 mol-%,
• (B) im Bereich von 1 bis 95 mol-%, bevorzugt 5 bis 70 mol-% und
• (C) im Bereich von 1 bis 60 mol-%, bevorzugt 5 bis 55 mol-% und
• (D) im Bereich von 1 bis 70 mol-%, bevorzugt 1 bis 50 mol-%, jeweils bezogen auf Copolymerisat, wobei die Summe aus (A), (B), (C) und (D) 100 mol-% ergibt, und
• (E) im Bereich von 0 bis 50 mol-%, bevorzugt 1 bis 30 mol-%, besonders bevorzugt 2 bis 20 mol-%, bezogen auf alle Carboxylgruppen des erfindungsgemäßen Copolymerisats.

In one embodiment of the present invention, the molar ratios of comonomers copolymerized in copolymer of the invention are

• (A) in the range of 5 to 60 mol%, preferably 10 to 55 mol%,
• (B) in the range of 1 to 95 mol%, preferably 5 to 70 mol% and
• (C) in the range of 1 to 60 mol%, preferably 5 to 55 mol% and
• (D) in the range of 1 to 70 mol%, preferably 1 to 50 mol%, in each case based on copolymer, wherein the sum of (A), (B), (C) and (D) gives 100 mol% , and
• (E) in the range of 0 to 50 mol%, preferably 1 to 30 mol%, particularly preferably 2 to 20 mol%, based on all carboxyl groups of the copolymer according to the invention.

The Invention will be explained by working examples.

1. Synthesis Code for copolymerization and partial esterification

All Reactions were - if not stated otherwise - under an atmosphere carried out by nitrogen.

The K values of the copolymers according to the invention were after H. Fikentscher, Cellulose Chemistry, Volume 13, 58-64 and 761-774 (1932) in cyclohexanone at 25 ° C and a polymer concentration determined by 2 wt .-%.

Preparation Method

206 g of polyisobutene having a molecular weight M _n of 550 g / mol and 185 g of diisobutene (mixture of 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene) in a molar ratio of 80: 20, determined by ¹ H-NMR spectroscopy) were placed in a 4-liter kettle and heated to 110 ° C in a gentle stream of nitrogen. After reaching the temperature of 110 ° C was dissolved within 5 hours 184 g of maleic anhydride in liquid form as a melt of about 70 ° C and within 5.5 hours 5.5 g Tert.-Butylperoctoat in 25 g of diisobutene (mixture of 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene). Subsequently, one hour at 120 ° C was reheated. Thereafter, the temperature was raised to 160 ° C and distilled unreacted diisobutene.

The resulting reaction mixture was cooled to 90 ° C and simultaneously with 2400 g of water and 140 g of 50 wt .-% aqueous Sodium hydroxide added. Subsequently was 4 hours at 90 ° C touched and then cooled to room temperature. The emulsifier according to the invention was obtained (b1) in the form of an aqueous Dispersion having a pH of 6.5 and a water content of 80 wt .-% had. The K value was 14.7.

2. Production of auxiliaries according to the invention

Emulsifier (b1) was further processed into adjuvant H1 according to the invention by mixing 90 g of polyisobutene having a molecular weight M _n of 550 g / mol with 10 g of the dispersion of emulsifier (b1) described above by stirring in a beaker.

Emulsifier (b1) was processed further to aid H2 according to the invention by mixing 90 g of polyisobutene having a molecular weight M _n of 1000 g / mol with 10 g of the dispersion of emulsifier (b1) described above by stirring in a beaker.

you received the aids according to the invention H1 and H2.

3. Production of leather

3.1. Use according to the invention of adjuvant H1 in the production of leather and comparative examples

Preamble: % By weight refers to the shaved weight, unless stated otherwise.

100 parts by weight of chromium-tanned cowhide having a folding thickness of 1.8 to 2.0 mm were produced in a rotatable barrel with flow-breaking internals at 30 ° C. with 100% by weight of water and 2% by weight of a naphthalenesulfonic acid / formaldehyde condensation product US 5,186,846 , Example "Dispersant 1", over a period of 45 minutes, followed by draining the liquor and washing the leather with 200% by weight of water.

Together with 100% by weight of water, 3% by weight of adjuvant H1 according to the invention were metered in and tumbled. After a flexing time of 30 minutes (30 ° C.) at 10 revolutions / min, a sample of the liquor was drawn and thereafter 7% by weight of sulfone tanning agent from EP-B 0 459 168, Example K1 added and another 45 minutes at 10 revolutions / min in the barrel. Thereafter, 3% by weight of vegetable tanning material Mimosa®, commercially available from BASF Aktiengesellschaft, was added and tumbled for 40 minutes. Thereafter, 2% by weight of a brown dye mixture was added, composed as follows:
70 parts by weight of dyestuff from EP-B 0 970 148, Example 2.18,
30 parts by weight of Acid Brown 75 (iron complex), Color Index 1.7.16.

To 40 minutes further Walkens with formic acid to a pH of 3.6 acidified to 3.8. After another 20 minutes, the fleet was drained and with 200 % By weight of water. The washed leather was withered, dried and according to the test criteria set out in Table 2 assessed.

3.2 Use according to the invention of resource H2

example 3.1 was repeated, but H1 was used instead of the adjuvant according to the invention the aid according to the invention H2.

3.3 Comparative Example V3 and V4

The procedure was as above, but instead of the adjuvant H1 according to the invention, a comparison aid prepared according to Table 1 was used. Table 1: Composition of aids H1 and H2 according to the invention and comparison aids VH3 and VH4

Of the Water content is in each case based on the total mass of auxiliaries or Related tools.

The stability the emulsion (liquor) was after a life of 90 minutes graded with grades from 1 to 5.

Surface roughness, meat side morphology, softness, staining and penetration were rated by subject teams for grades 1-5. Table 2: Result of the treatment of semi-finished products: performance test

Claims (22)

Process for the treatment of fibrous substrates, characterized in that they are treated with (a) at least one oligomer of branched or unbranched C ₃ -C ₁₀ alkene having an average molecular weight M _n up to 1200 g / mol, (b) at least one An emulsifier obtainable by copolymerizing (A) at least one ethylenically unsaturated dicarboxylic acid anhydride derived from at least one dicarboxylic acid having 4 to 8 carbon atoms, (B) at least one oligomer of branched or unbranched C ₃ -C ₁₀ alkanes, wherein at least an oligomer having an average molecular weight M _n up to 1200 g / mol, (C) at least one α-olefin having up to 16 C atoms, and (D) optionally at least one further ethylenically unsaturated comonomer, and optionally reaction with (E) at least one compound of general formula I a, I b, I c or I d

and optionally subsequent contact with water, where in the formulas Ia to Id the variables are defined as follows: A ¹ C ₂ -C ₂₀ -alkylene, identical or different, R ^{1 is} C ₁ -C ₃₀ -alkyl, linear or branched, Phenyl or hydrogen, n is an integer from 1 to 200. Process according to Claim 1, characterized in that branched C ₄ -C ₁₀ olefin is used to prepare oligomer (B). Process according to Claim 1 or 2, characterized in that oligomers starting with the use of branched C ₄ -C ₁₀ olefin are used to prepare emulsifier (b). Method according to one of claims 1 to 3, characterized that oligomer (a) is polyisobutene. Method according to one of claims 1 to 4, characterized that oligomers (B) are polyisobutene. Method according to one of claims 1 to 5, characterized that you have a weight ratio (a) to (b) ranges from 1 to 1 to 100 to 1. Method according to one of claims 1 to 6, characterized in (b) the comonomers are chosen as follows: (A) in the range of 5 to 60 mol%, (B) in the range of 1 to 95 mol%, (C) in the range of 1 to 60 mol%, (D) in the range of 0 to 70 mol%, in each case based on copolymer, the sum of (A), (B), (C) and (D) gives 100 mol%, and (E) in the range of 0 to 50 mol%, based on all carboxyl groups of copolymer. Method according to one of claims 1 to 7, characterized that one in watery Fleet performs. Method according to one of claims 1 to 8, characterized in that (D) is selected from ethylenically unsaturated C ₃ -C ₈ carboxylic acids and carboxylic acid derivatives of the general formula II

Carboxylic acid amides of the formula III,

non-cyclic amides of the general formula IV a or cyclic amides of the general formula IV b

C ₁ -C ₂₀ -alkyl vinyl ethers, N-vinyl derivatives of nitrogen-containing aromatic compounds, α, β-unsaturated nitriles, alkoxylated unsaturated ethers of the general formula V

Esters or amides of the general formula VI

unsaturated esters of the general formula VII

vinyl aromatic compounds of the formula VIII

Phosphorus, phosphonate, sulfate and sulfonate group-containing comonomers, α-olefins having 18 to 40 carbon atoms, where in the general formulas the variables are defined as follows: R ² , R ^{3 are} identical or different and selected from hydrogen, unbranched or branched C ₁ -C ₅ -alkyl and COOR ⁴ , R ^{4 are} identical or different and selected from hydrogen or C ₁ -C ₂₂ -alkyl, branched or unbranched, R ^{5 is} hydrogen or methyl, x is an integer in the range from 2 to 6, y is an integer selected from 0 or 1, a is an integer in the range from 0 to 6, R ⁶ , R ^{7 are} identical or different and selected from Hydrogen, unbranched or branched C ₁ -C ₁₀ -alkyl, X is oxygen or NR ⁴ R ⁸ [A ³ -O] _n -R ⁴ , R ^{9 are} identical or different and selected from hydrogen, unbranched or branched C ₁ -C ₁₀ - Alkyl, R ¹⁰ , R ¹¹ independently of one another are hydrogen, methyl or ethyl, R ^{12 is} selected from methyl and ethyl, k is an integer in the range from 0 to 2, A ² , A ^{3 is} C ₂ -C ₂₀ -alkylene A ⁴ C ₁ -C ₂₀ alkylene or a single bond and the other variables are as defined above. Method according to one of claims 1 to 9, characterized chosen fibrous substrates are made of leather, textile, paper, cardboard, imitation leather, Alcantara or Lefa. Method according to one of claims 1 to 10, characterized that it is leather based on wet-white. Method according to one of claims 1 to 11, characterized that comonomer (C) is chosen from isobutene, diisobutene and 1-dodecene. Fibrous substrates treated by a process according to claim 1 to 12. Fibrous substrates according to claim 13, characterized in that that substrates are leathers. Leather according to claim 14, characterized that it is leather based on wet-white. Use of fibrous substrates according to one of claims 13 to 15 for the manufacture of clothing or furniture or car parts. Auxiliary comprising (a) at least one oligomer of branched or unbranched C ₃ -C ₁₀ -alkene having an average molecular weight M _{n of} up to 1200 g / mol, (b) at least one emulsifier obtainable by copolymerization of (A) at least an ethylenically unsaturated dicarboxylic acid anhydride derived from at least one dicarboxylic acid having 4 to 8 C atoms, (B) at least one oligomer of branched or unbranched C ₃ -C ₁₀ alkanes, where at least one oligomer has an average molecular weight M _{n of} up to 1200 g / (C) at least one α-olefin having up to 16 C atoms, and (D) optionally at least one further ethylenically unsaturated comonomer, and optionally reacting with (E) at least one compound of general formula I a, I b, I c or I b

and optionally subsequent contact with water, where in the formulas Ia to Id the variables are defined as follows: A ¹ C ₂ -C ₂₀ -alkylene, identical or different, R ^{1 is} C ₁ -C ₃₀ -alkyl, linear or branched, phenyl or hydrogen, n is an integer Number from 1 to 200. Aid according to claim 17, characterized that comonomer (C) chosen is made up of isobutene, diisobutene and 1-dodecene. A copolymer obtained by copolymerizing (A) at least one ethylenically unsaturated dicarboxylic anhydride derived from at least one dicarboxylic acid having 4 to 8 carbon atoms, (B) at least one oligomer of branched or unbranched C ₃ -C ₁₀ alkanes, wherein at least one oligomer an average molecular weight M _n up to 1200 g / mol, (C) at least one α-olefin having up to 16 C atoms, and (D) optionally at least one further ethylenically unsaturated comonomer, and optionally reaction with (E) at least one Compound of the general formula I a, I b, I c or I b

and optionally subsequent contact with water, where in the formulas Ia to Id the variables are defined as follows: A ¹ C ₂ -C ₂₀ -alkylene, identical or different, R ^{1 is} C ₁ -C ₃₀ -alkyl, linear or branched, Phenyl or hydrogen, n is an integer from 1 to 200. Copolymer according to Claim 19, characterized that comonomer (C) chosen is made up of isobutene, diisobutene and 1-dodecene. aqueous Dispersions of copolymers according to one of claims 19 and 20th Aqueous dispersions according to claim 21, characterized in that they additionally contain (a) at least one oligomer of branched or unbranched C ₃ -C ₁₀ alkene having an average molecular weight M _n up to 1200 g / mol.