DE10355402A1 - 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 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 im Bereich von 300 bis 5000 g/mol aufweist oder durch Oligomerisierung von mindestens 3 Äquivalenten C₃-C₁₀-Alken erhältlich ist,
• (C) optional mindestens einem von (A) verschiedenen ethylenisch ungesättigten Comonomer,

und optional Umsetzung mit

• (D) mindestens einer Verbindung der allgemeinen Formel Ia oder Ib
  

und anschließendes Versetzen mit Wasser,
wobei in Formel Ia und Ib 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 wobei der Wassergehalt im Bereich von 30 bis 99,5 Gew.-% liegt, bezogen auf wässrige Dispersion.The present invention relates to aqueous dispersions of copolymers obtainable by 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,
• (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 in the range from 300 to 5000 g / mol or by oligomerization of at least 3 equivalents of C ₃ -C ₁₀ - Alkene is available,
• (C) optionally at least one ethylenically unsaturated comonomer other than (A),

and optional implementation with

• (D) at least one compound of general formula Ia or Ib
  

and then adding water,
wherein in formulas Ia and Ib 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 wherein the water content is in the range of 30 to 99.5 wt .-%, based on aqueous dispersion.

Farther The present invention relates to a process for the preparation the aqueous according to the invention Dispersions and their use for the treatment of fibrous substrates.

• (A) mindestens einem ethylenisch ungesättigten Dicarbonsäureanhydrid, abgeleiet von mindestens einer Dicarbonsäure mit 4 bis 8 C-Atomen,
• (B) mindestens einem Oligomer von verzweigtem oder unverzweigtem C₃-C₁₀-Alken, wobei mindestens ein Oligomer ein mittleres Molekulargewicht M_n im Bereich von 300 bis 5000 g/mol aufweist oder durch Oligomerisierung von mindestens 3 Äquivalenten C₃-C₁₀-Alken erhältlich ist,
• (C) optional mindestens einem von (A) verschiedenen ethylenisch ungesättigten Comonomer,

und optional Umsetzung mit

• (D) mindestens einer Verbindung der allgemeinen Formel Ia oder Ib
  

wobei in den Formeln Ia und Ib die Variablen wie oben stehend definiert sind.Furthermore, the present invention relates to copolymers obtainable by 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,
• (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 in the range of 300 to 5000 g / mol or by oligomerization of at least 3 equivalents of C ₃ -C ₁₀ - Alkene is available,
• (C) optionally at least one ethylenically unsaturated comonomer other than (A),

and optional implementation with

• (D) at least one compound of general formula Ia or Ib
  

wherein in formulas Ia and Ib the variables are defined as above.

In The production of leather plays beside use characteristics like Softness and fullness the hydrophobing to protect the leather or a leather article against moisture and dirt an important role. Also more Usage characteristics of the leather such as the handle become influenced by the way of hydrophobing. But also at other fibrous substrates such as textile, paper, Cardboard, artificial leather and wood, the hydrophobing plays an important role Role. Even with flat Substrates, for example made of concrete or bricks is the impregnation an important field of work.

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 1 to 50 mol% of at least one monoethylenic unsaturated compound which is polymerizable with the aforementioned monomers such as vinyl and Alkylallylethern known and their use for the preparation of oil-soluble reaction products which are useful as an additive for lubricants and fuels.

From WO 90/03359 and EP-A 0 657 475 are known alternating copolymers of maleic anhydride and polyisobutene, which can be used after modification with amines or polyamines as an additive in lubricants and fuels.

Out WO 01/55059 are terpolymers of maleic anhydride, one or more Olefin with more than 40 C-atoms, for example polyisobutene, and a vinyl ester of carboxylic acids with 2 to 12 carbon atoms, as well as the use of terpolymers as Emulsifiers for Explosives known.

Out WO 03/23070 fatliquors for skins are known, for example Contain polyisobutene or products that are characterized by ene reaction Polyisobutene and suitable enophiles are produced (page 6, line 29 ff.)

It The task was to provide water repellents for fibrous substrates To put that a good protection against moisture at the same time allow comfortable grip of hydrophobic substrates. Farther the task was a process for the preparation of water repellents to provide, and it was the task of a procedure for Hydrophobization of fibrous substrates using new water repellents to provide.

Accordingly, were the initially defined aqueous Dispersions of copolymers found.

Under Dispersions of copolymers are hereinafter emulsions, Suspensions and also clear-looking solutions of copolymers Understood.

• (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 im Bereich von 300 bis 5000 g/mol aufweist oder durch Oligomerisierung von mindestens 3 Äquivalenten C₃-C₁₀-Alken erhältlich ist,

und

• (C) optional mindestens ein von (A) verschiedenes ethylenisch ungesättigtes Comonomer,

die man optional mit

• (D) mindestens einer Verbindung der allgemeinen Formel Ia oder Ib, vorzugsweise Ia
  

umsetzt, in der die Variablen wie folgt definiert sind:
A¹ C₂-C₂₀-Alkylen, beispielsweise -(CH₂)₂-, -CH₂-CH(CH₃)-, -(CH₂)₃-, -CH₂-CH(C₂H₅)-, -CH₂-CH(iso-C₃H₇)-, -CH₂-CH(n-C₄H₉)-, -(CH₂)₄-, -(CH₂)₄-, -(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 50;Aqueous dispersions of the invention comprise copolymer which is obtainable by 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, where at least one oligomer has an average molecular weight M _n in the range from 300 to 5000 g / mol or by oligomerization of at least 3 equivalents of C ₃ -C ₁₀ - Alkene is available,

and

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

which one is optional with

• (D) at least one compound of general formula Ia or Ib, preferably Ia
  

implements the variables 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 -CH (iso-C ₃ H ₇ ) -, -CH ₂ -CH (nC ₄ H ₉ ) -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₄ -, - (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 50;

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 (D) are used.

In one embodiment of the present invention, mixtures of different components (D), for example of the formula Ia, are used. In particular, it is possible to use those mixtures of compounds of the formula Ia 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 is 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, after the free-radical copolymerization and, if appropriate, the reaction with (D), water is added, in which case the water may also 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 hydrogen carbonate 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 radical copolymerization add water.

Inventive dispersions have a water content in the range of 30 to 99.5 wt .-%, based on the total weight of the dispersion according to the invention, preferably in Range of 60 to 90 wt .-%.

Suitable comonomers (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 in the range from 300 to 5000 g / mol or by oligomerization of at least 3, preferably at least 4 equivalents of C ₃ -C ₁₀ -alkene is available. Examples which may be mentioned are oligomers of propylene, isobutene, 1-pentene, 2-methylbutene-1, 1-hexene, 2-methylpentene-1, 2-methylhexene-1, 2-ethylpentene-1, 2-ethylhexene-1 and 2-propylheptane 1,1-octene and 1-decene, very particularly preferred is isobutene. Comonomers (B) 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 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 come into question.

Particularly preferred comonomers (B) are oligopropylene and oligoisobutenes having an average molecular weight M _n in the range from 300 to 5000 g / mol, preferably from 400 to 3000 g / mol, particularly preferably from 500 to 2300 g / mol, very particularly preferably from 550 to 1200, in particular to 1000 g / mol, for example determined by gel permeation chromatography (GPC). Particularly preferred oligoisobutenes and oligopropylenes are furthermore those which are obtainable by oligomerization of at least 3, preferably at least 4, equivalents of C ₃ -C ₁₀ -alkene.

In an embodiment In the present invention, comonomers (B) have a polydispersity in the range from 1.1 to 10, preferably to 3, and more preferably from 1.5 up to 1.8.

In one embodiment of the present invention, comonomers (B) have a polydispersity M _w / M _n in the range of 1.1 to 3, preferably 1.5 to 1.8.

In a specific embodiment of the present invention, oligomer (B) has a bimsdale molecular weight distribution with a maximum of M _n in the range from 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 boron trifluoride catalyst, see, for example DE-A 27 02 604 , Suitable isobutene-containing starting materials are both isobutene itself and also isobutene-containing C ₄ hydrocarbon streams, for example C ₄ raffinates, C ₄ cuts from isobutene dehydrogenation, C ₄ cuts Steam crackers or so-called FCC (Fluid Catalysed Cracking) crackers, insofar as relevant C ₄ cuts are substantially freed 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 (B) is known per se; regulations can be found, for example, in WO 96/23751 and in WO 99/67347, example Third

• – 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,
• – C₁₂-C₁₄-Fettalkoholethoxylate mit 3 bis 30 Ethylenoxideinheiten,
• – C₁₀-Oxoalkoholethoxylate mit 3 bis 30 Ethylenoxideinheiten,
• - C₁₀-Guerbetalkoholethoxylate mit 3 bis 30 Ethylenoxideinheiten,
• – C₄-C₂₀-Alkoholethoxylate mit 2 bis 20 Ethylenoxideinheiten, 2 bis 20 Propylenoxideinheiten und/oder 1 bis 5 Butylenoxideinheiten;
• – C₉-C₁₁-Oxoalkoholalkoxylate mit 2 bis 20 Ethylenoxideinheiten, 2 bis 20 Propylenoxideinheiten und/oder 1 bis 5 Butylenoxideinheiten;
• – C₁₃-C₁₅-Oxoalkoholalkoxylate mit 2 bis 20 Ethylenoxideinheiten, 2 bis 20 Propylenoxideinheiten und/oder 1 bis 5 Butylenoxideinheiten;
• - C₄-C₂₀-Alkoholethoxylate mit 2 bis 20 Ethylenoxideinheiten.

Particular 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 ₄ -C ₂₀ -alcohol ethoxylates having 2 to 20 ethylene oxide units, 2 to 20 propylene oxide units and / or 1 to 5 butylene 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 2 to 20 ethylene oxide units, 2 to 20 propylene oxide units and / or 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-end-capped polyethylene glycol amines 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.

Carbonsäureamide der Formel III,

nicht-cyclische Amide der allgemeinen Formel IVa und cyclische Amide der allgemeinen Formel IVb

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

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 3 bis 40 Kohlenstoffatomen, bevorzugt mit 4 bis 24 Kohlenstoffatomen, insbesondere Isobuten, Diisobuten, 1-Decen, 1-Dodecen, 1-Okta-decen, 1-Eicosan, α-C₂₂H₄₄, α-C₂₄H₄₈, und Gemische der vorstehend genannten α-Olefine;
vinylaromatische Verbindungen, beispielsweise der allgemeinen Formel VIII

wobei die Variablen wie folgt definiert sind:
A², A³ gleich oder verschieden und C₂-C₂₀-Alkylen, beispielsweise -(CH₂)₂-, -CH₂-CH(CH₃)-, -(CH₂)₃-, -CH₂-CH(C₂H₅)-, -CH₂-CH(iso-C₃H₇)-, -CH₂-CH(n-C₄H₉)-, -(CH₂)₄-, -(CH₂)₅-, -(CH₂)₆-, vorzugsweise C₂-C₄-Alkylen; insbesondere -(CH₂)₂-, -CH₂-CH(CH₃)- und -CH₂-CH(C₂H₅)-;
R², R³ gleich oder verschieden und gewählt aus unverzweigten oder verzweigten C₁-C₅-Alkyl, 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, besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
und insbesondere Wasserstoff;
R⁴ gleich oder verschieden und C₁-C₂₂-Alkyl, verzweigt oder unverzweigt, 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-Eicosyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl; oder besonders bevorzugt Wasserstoff;
R⁵ Wasserstoff oder Methyl,
x eine ganze Zahl im Bereich von 2 bis 6, vorzugsweise 3 bis 5;
y eine ganze Zahl, ausgewählt aus 0 oder 1, vorzugsweise 1;
a eine ganze Zahl im Bereich von 0 bis 6, vorzugsweise im Bereich von 0 bis 2;
b eine ganze Zahl von 1 bis 200, bevorzugt 4 bis 50;
R⁶, R⁷ gleich oder verschieden und gewählt aus Wasserstoff unverzweigten oder verzweigten C₁-C₁₀-Alkyl und wobei unverzweigtes und verzweigtes C₁-C₁₀-Alkyl wie oben stehend definiert ist;
X Sauerstoff oder N-R⁴;
R⁸ [A³-O]_b-R⁴,
R⁹ gewählt aus unverzweigten oder verzweigten C₁-C₂₀-Alkyl, 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-Tetradecyl, n-Hexadecyl, n-Octadecyl, n-Eicosyl; bevorzugt C₁-C₁₄-Alkyl 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-Tetradecyl,
und insbesondere Wasserstoff oder Methyl;
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.The one or more monomers (C) which may optionally be copolymerized in the copolymers contained in the dispersions of the invention are different from (A). Preferred monomers (C) are:
C ₃ -C ₈ carboxylic acid derivatives of the general formula II

Carboxylic acid amides of the formula III,

non-cyclic amides of the general formula IVa and cyclic amides of the general formula IVb

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

Phosphate-, phosphonate-, sulphate- and sulphonate-containing comonomers such as [2- {(meth) acryloyloxy} -ethyl] -phosphate, 2- (meth) acrylamido-2-methyl-1-propanesulfonic acid;
α-olefins, linear or branched, having 3 to 40 carbon atoms, preferably having 4 to 24 carbon atoms, in particular isobutene, diisobutene, 1-decene, 1-dodecene, 1-octa-decene, 1-eicosane, α-C ₂₂ H ₄₄ , α-C ₂₄ H ₄₈ , and mixtures of the aforementioned α-olefins;
vinylaromatic compounds, for example of the general formula VIII

where the variables are defined as follows:
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 -CH (iso-C ₃ H ₇ ) -, -CH ₂ -CH (nC ₄ H ₉ ) -, - (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 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, iso-pentyl, 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;
b is an integer from 1 to 200, preferably from 4 to 50;
R ⁶ , R ^{7 are} identical or different and selected from hydrogen, unbranched or branched C ₁ -C ₁₀ -alkyl and wherein unbranched and branched C ₁ -C ₁₀ -alkyl is as defined above;
X is oxygen or NR ⁴ ;
R ⁸ [A ³ -O] _b -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 of 0 to 2, preferably k = 0.

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 IVa 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 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-di-ethylaminopropyl 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.

Very particular preference is given to using comonomer (C): styrene, acrylic acid, diisobutene, 1-dodecene, 1-eicosene, α-C ₂₂ H ₄₄ , α-C ₂₂ H ₄₈ , methacrylic acid, methyl acrylate, methyl methacrylate, acrylamide, vinyl-n butyl ether, vinyl isobutyl ether, N-vinylformamide, N-vinylpyrrolidone, 1-vinylimidazole and 4-vinylpyridine.

In the dispersions of the invention contained copolymers can concerning (A), (B) and optionally (C) block copolymers, be alternating copolymers or random copolymers, wherein alternating copolymers are preferred.

In an embodiment The present invention provides the anhydride groups of the copolymer the polymerization completely or partially hydrolyzed and optionally neutralized before.

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

In one embodiment of the present invention, the molar ratios of copolymer dispersed in aqueous dispersions 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 10 to 60 mol%,
• (C) 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) and (C) gives 100 mol%, and
• (D) in the range of 0 to 50 mol%, preferably 1 to 30 mol%, particularly preferably 2 to 20 wt .-%, based on all carboxyl groups of copolymer.

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

In one embodiment of the present invention, copolymers dispersed in aqueous dispersions according to the invention have an average molecular weight M _w in the range from 1000 g / mol to 50,000 g / mol, preferably 1100 to 25,000 g / mol, determined, for example, by size exclusion chromatography chromatography) with, for example, tetrahydrofuran or dimethylacetamide as solvent and polymethyl methacrylate or polystyrene as standard.

In one embodiment of the present invention, the polydispersity M _w / M _n of copolymer dispersed in dispersions according to the invention is generally in the range from 1.1 to 20, preferably from 1.5 to 10.

In an embodiment of the present invention aqueous dispersions according to the invention unpolymerized comonomer (B), for example in proportions of from 1 to 30% by weight, based on the total weight at inventive aqueous Dispersion.

One Another object of the present invention is a method for the production of aqueous according to the invention Dispersions, also referred to below according to the invention manufacturing method.

to exercise the production process according to the invention starting from (A), (B) and optionally (C), which is radically copolymerized with each other. While or preferably after copolymerization, water is added, in such a way that the water content of the dispersion according to the invention in the range of 30 to 99.5 wt .-% water.

In an embodiment the present invention is based on (A), (B) and optionally (C), which is radically copolymerized with each other and reacted with (D). While or preferably after copolymerization, water is added, in such a way that the water content of the dispersion according to the invention in the range of 30 to 99.5 wt .-% water.

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

In another special embodiment of the present invention the radical copolymerization of (A), (B) and optionally (C) in the presence of the entire amount or proportions of the used Compound (D) by.

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

If it is desired to react the copolymer with (D) or to carry out a free-radical copolymerization in the presence of (D), then the total amount of (D) is calculated as based on a complete reaction of (D) and up to 50 mol%, preferably 1 to 30 mol%, particularly preferably 2 to 20 mol% (D), 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 (C) 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 the Generally, initiator will be in amounts of from 0.1% to 20% by weight, preferably 0.2 to 15 wt .-%, calculated on the mass of all comonomers used.

you can the manufacturing process of the invention in the presence or 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. As precipitant For example, toluene, ortho-xylene, meta-xylene and aliphatic ones are suitable 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 wt .-%, based on total weight of comonomers (A), (B) and optionally (C). As a solvent are under the conditions of copolymerization and esterification or to understand amide formation inert substances, in particular aliphatic and aromatic hydrocarbons such as Cyclohexane, n-heptane, isododecane, benzene, toluene, ethylbenzene, xylene as isomer mixture, meta-xylene, ortho-xylene. Do you work at the Reaction with (D) without acid catalyst or omitted the reaction with (D), so you can the radical copolymerization and if appropriate, reaction with (D) also in solvents selected from Ketones such as acetone, methyl ethyl ketone, or cyclic ones or non-cyclic ethers such as tetrahydrofuran or di-n-butyl ether.

The The preparation process according to the invention 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 production process according to the invention can usual equipment be used, for. As autoclave and boiler.

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

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

In an embodiment In the present invention, a mixture of (D) and (A) is added. before and gives initiator and at the same time (B) and optionally (C) in the manner of a feed process, wherein initiator, (B) and optionally (C) each dissolved in (D) are.

In an embodiment In the present invention, a mixture of (D) and (A) is added. before and gives initiator and (B) and (C) in the manner of a feed process to, wherein the feed rates of (B) and (C) are different chosen become.

In another embodiment In the present invention, a mixture of (D) and (A) is provided and gives initiator and (B) and (C) in the manner of a feed process to, wherein the feed rates of (B) and (C) are chosen to be equal.

In another embodiment In the present invention, (B) and optionally (C) are presented and gives initiator and (A) in the manner of a feed process to and then sets optionally with (D) um.

In another embodiment of the present invention, (B) and initiator, (A) and optionally (C) in the manner of a feed process to and then sets optionally with (D) um.

In another embodiment in the present invention, (A), (B) and optionally (D) before and gives initiator and (C) in the manner of a feed process. (A), (B) and optionally (D) may also be in a solvent be submitted. In one embodiment of the present invention are added during the addition of (B) and optionally (C) further initiator too.

In an embodiment the present invention is temperature for the copolymerization of (A), (B) and optionally (C) is in the range of 80 to 300 ° C, preferably 100 to 200 ° C.

Of the Pressure is for example in the range of 1 to 10 bar, preferably 1 to 5 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 weight of the comonomers used. Preference is given to working without the use of controllers.

you can while the copolymerization one or more polymerization inhibitor in small amounts, for example, hydroquinone monomethyl ether. Polymerization inhibitor can be advantageously with (B) and optionally (C) 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) and (B), optionally (C), if appropriate (D) 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 (D) can be 1 to 12 hours, preferably 2 to 9 hours, more preferably 3 to 6 hours.

Leading the production process according to the invention by reacting (A), (B) and optionally (C) in the presence the total amount of (D) is copolymerized, for example 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 (D) 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.

Becomes the reaction with (D) carried out in the presence of catalysts, so the duration of the reaction can be 0.5 to 2 hours.

In Another variant of the method described leads you the reaction with (D) 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 (D) or to some extent with the carboxyl groups of the anhydrides (A) and optionally the carboxyl groups of (C). In general less than 40 mol% remain as unreacted (D).

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

In an embodiment one can look at the further step of separating unreacted (D) from the inventively prepared Dispense copolymers.

In this embodiment one sets polymers together with a certain percentage of not abreacted (D) for the treatment of fibrous substrates.

By the copolymerization described above is obtained copolymers. The Copolymers obtained can be a cleaning according to conventional Methods such as reprecipitation or extractive removal unreacted monomers. If a solvent or precipitant was used, so it is possible to remove this after completion of the copolymerization, for example by distilling off.

in the The present invention is as described above copolymer prepared with water, and that is calculated the Amount of added water so that dispersion of the invention gets which has a water content in the range from 30 to 99.5% by weight to the total mass of inventive dispersion.

In one embodiment of the present invention, after the free-radical copolymerization and, if appropriate, the reaction with (D), water is added, in which case the water may also 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 hydrogen carbonate 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 (D) in the presence of solvent carried out, so it is preferred, first solvent to remove, for example by distilling off and only afterwards with water.

In a special embodiment In the present invention, the solvent is removed after the reaction with water by, for example, steam distillation.

By the addition of water, optionally containing Brønsted acid or preferably Brønsted base can, can the present in the copolymer carboxylic anhydride partially or completely be hydrolyzed.

To water, optionally containing Brønsted acid or preferably Brønsted base can, at temperatures in the range of 20 to 100 ° C, preferably up to 90 ° C postreacted, for a period of 10 minutes to 4 hours.

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

In a further embodiment The present invention sets copolymer at 50 to 100 ° C before and gives, if necessary, to 50 bis in the manner of a feed process 100 ° C heated water to, the water is still brønsted acid or prefers 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 optionally to 50 to 100 ° C heated copolymer to. Suitable nonionic surfactants are for example multiply, preferably 3 to 30 times alkoxylated C ₁₂ -C ₃₀ alkanols.

In a further embodiment of the present invention, the copolymer is initially introduced at from 50 to 100.degree. C. and, in the manner of a feed process, gives the mixture of water which may be heated to from 50 to 100.degree. C., whereby the water may still contain Brønsted acid or preferably Brønsted base , and nonionic surfactant too. As a non-ionic surfactant is, for example, multiple, preferably 3 to 30-fold alkoxylated C ₁₂ -C ₃₀ alkanol in question.

One Another object of the present invention is the use the aqueous according to the invention Dispersions for the treatment of fibrous substrates. Another The subject of the present invention is a method of treatment of fibrous substrates, hereinafter also treatment method according to the invention called, using aqueous dispersions of the invention.

• – 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. Die Textilien können natürlichen Ursprungs sein, beispielsweise Wolle, Flachs oder insbesondere Baumwolle, oder synthetisch, beispielsweise Polyamid und Polyester;
• – Papier, Pappe, Kartonagen,
• – Holz und Holzverbundwerkstoffe wie beispielsweise Spanplatten,
• – Kunstleder, Alcantara oder Lefa, das sind Lederfaserwerkstoffe aus Lederabfällen, welche mit einem Binder oder Harz zu einem synthetisch erzeugten Fasergefüge verarbeitet werden

und besonders bevorzugt

• – Leder, wobei unter Leder mit Hilfe von wahlweise Chromgerbstoffen, mineralischen Gerbstoffen, Polymergerbstoffen, synthetischen Gerbstoffen, vegetabilen Gerbstoffen, Harzgerbstoffen oder Kombinationen von mindestens zwei der vor genannten Gerbstoffen vorgegerbte und vorzugsweise gegerbte Tierhäute zu verstehen sind.

Among fibrous substrates in the context of the present invention may be mentioned:

• - 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. The textiles may be of natural origin, for example wool, flax or in particular cotton, or synthetic, for example polyamide and polyester;
• - paper, cardboard, cardboard boxes,
• - wood and wood composites such as chipboard,
• - Synthetic leather, Alcantara or Lefa, which are leather fiber materials from leather waste, which are processed with a binder or resin to a synthetically produced fiber structure

and especially preferred

• Leather, leather being understood to mean pretreated and preferably tanned animal skins by means of optional chrome tanning agents, mineral tannins, polymer tanning agents, synthetic tanning agents, vegetable tanning agents, resin tanning agents or combinations of at least two of the aforesaid tanning agents.

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

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

Inventive dispersions can be used in tanning and preferably in retanning, in the following, tanning process according to the invention or retanning process according to the invention called. You can dispersions of the invention in a separate treatment step

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 at a pH of 2.5 to 8, preferably from 3 to 5.5, where you often observed that the pH during the implementation the tanning process according to the invention increases by about 0.3 to three units.

In an embodiment In the present invention, the pH can be reduced by blunting Increase funds by about 0.3 to three units.

In another embodiment The present invention can be the tanning process according to the invention at a pH in the range of 4 to 8 begin inventive copolymer by adding an acidic component such as formic acid fix a pH in the range of 3 to 5.5.

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 one up 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.

In a variant of the tanning process according to the invention, dispersion according to the invention or copolymer according to the invention is used together with one or more conventional tanning agents, for example with tannins of mineral tannins, preferably with syntans, polymer tanning agents or vegetable tanning agents, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, volume A15, pages 259 to 282 and in particular page 268 ff., 5th edition, (1990), Verlag Chemie Weinheim.

In a variant of the tanning process according to the invention if the dispersion according to the invention or Inventive copolymer together with fatliquoring agents such as native triglycerides, white oil, paraffin, Wax, silicone oil, also emulsifiers.

In a variant of the tanning process according to the invention if the dispersion according to the invention or Inventive copolymer along with conventional Tanning and fatliquoring, but without silicone oil.

you can in the tanning process according to the invention 0.5 to 40 wt .-%, preferably 2 to 20 wt .-% dispersion of the invention or copolymer of the invention use, based on the pelt weight.

you can the inventive method for the treatment of leather, preferably as a retanning method of leather using dispersion or copolymer of the invention carry out. The retanning process according to the invention is based on conventional, i. for example with chrome tanning agents, mineral tanning agents based on Al, Ti, Zr, Fe and Si, preferably with Polymer tanning agents, aldehydes, vegetable tannins, syntans or resin tannins tanned semi-finished or according to the invention as above described semi-finished products. For carrying out the retanning according to the invention you leave Inventive copolymer to act on semi-finished products.

The Nachgerbverfahren invention one can under otherwise usual Perform conditions. You choose appropriate 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 can in Nachgerbverfahren invention 0.5 to 40 wt .-%, preferably 2 to 20 wt .-% dispersion of the invention or copolymer of the invention use, based on the shaved weight.

Of course you can one inventive dispersion or inventive copolymer in the tanning process according to the invention or Nachgerbverfahren during the retannation usually used, for example, fatliquors, polymer tanning agents, Acrylate- and / or methacrylate-based or based on fatliquor of silicones, retanning agents based on resin and vegetable tanning agents, fillers, Leather dyes or emulsifiers or combinations of at least 2 of the aforementioned substances.

In one embodiment of the present invention, the treatment process according to the invention and preferably the retanning process according to the invention are carried out using at least one oligomer of branched or unbranched C ₃ -C ₁₀ alkene having an average molecular weight M _n in the range from 300 to 5000 g / mol or of oligomer which is obtainable by oligomerization of at least 3 equivalents of C ₃ -C ₁₀ alkanes. Preferably, at least one oligomer corresponds to the comonomer (B) used to prepare the dispersion or copolymer of the invention. The ratio of copolymerized (B) to additional oligomer may range from 1: 0.1 to 1:10.

In one embodiment of the present invention, the retanning process according to the invention is carried out in the presence of emulsifier, for example in the presence of nonionic emulsifiers such as multiply, preferably 3 to 30 times, alkoxylated C ₇ -C ₃₀ -alkanols. If it is desired to use emulsifier, it is possible to use, for example, from 1 to 30% by weight of emulsifier, based on copolymer of the invention.

In an embodiment the present invention is omitted in the retanning process according to the invention based on the addition of water repellents or fatliquoring agents of silicones.

By the treatment according to the invention fibrous substrate is hydrophobed or greased.

Another object of the present invention are fibrous substrates, preferably leather, for example, leather based on wet-white or wet-blue and more preferably leather on the basis of wet-white, prepared by the treatment process according to the invention. You assign a special comfortable grip on.

One Another aspect of the present invention are leather by the tanning process according to the invention or the retanning process according to the invention or by a combination of tanning process according to the invention and retanning process according to the invention. The leathers of the invention are characterized by an overall advantageous quality, for example have a particularly pleasant grip and are very soft and full. The leathers of the invention contain above-described copolymer particularly well in microspheres penetrates the elementary fibers.

One Another aspect of the present invention is the use of leather, For example, leather according to the invention based on wet-white or wet-blue, preferably leather according to the invention based on wet-white and in particular leather according to the invention based on wet-white, made using vegetable tanning agents manufactured for the manufacture of clothing, furniture or car parts. Another aspect of the present invention is a method for the manufacture of clothing, furniture or car parts Use of leather according to the invention, For example, leather according to the invention based on wet-white or wet-blue, preferably leather according to the invention based on wet-white. Under garments 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 Furniture too which contain components of leather, for example as seat or on armrests. Examples include seating furniture such as chairs, Chairs, sofas. Car parts are exemplified by car seats.

One Another aspect of the present invention are garments containing or made of leather according to the invention. Another aspect The present invention relates to furniture containing or manufactured from leathers according to the invention. Another aspect of the present invention are automotive parts containing the or made of leather according to the invention.

• (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 im Bereich von 300 bis 5000 g/mol aufweist oder durch Oligomerisierung von mindestens 3 Äquivalenten C₃-C₁₀-Alken erhältlich ist,
• (C) optional mindestens einem von (A) verschiedenen ethylenisch ungesättigten Comonomer,

und Umsetzung mit

• (D) mindestens einer Verbindung der allgemeinen Formel Ia oder Ib,
  

wobei in Formel Ia und Ib 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 invention are copolymers obtainable by 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,
• (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 in the range from 300 to 5000 g / mol or by oligomerization of at least 3 equivalents of C ₃ -C ₁₀ - Alkene is available,
• (C) optionally at least one ethylenically unsaturated comonomer other than (A),

and implementation with

• (D) at least one compound of general formula Ia or Ib,
  

wherein in formulas Ia and Ib 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.

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 Ia and / or Ib are used.

In one embodiment of the present invention, mixtures of different components (D), for example of the formula Ia, are used. In particular, it is possible to use those mixtures of compounds of the formula Ia 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 is 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, copolymers according to the invention or dicarboxylic acid anhydrides (A) copolymerized in copolymers according to the invention are partial or complete dig in hydrolyzed and optionally neutralized form.

Carbonsäureamiden der Formel III,

nicht-cyclischen Amiden der allgemeinen Formel IVa oder cyclischen Amiden der allgemeinen Formel IVb

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

Phosphat-, Phosphonat-, Sulfat- und Sulfonatgruppen-haltige Comonomere,
α-Olefine, linear oder verzweigt, mit 3 bis 40 Kohlenstoffatomen, bevorzugt mit 4 bis 24 Kohlenstoffatomen, insbesondere Isobuten, Diisobuten, 1-Decen, 1-Dodecen, 1-Oktadecen, 1-Eicosan, α-C₂₂H₄₄, α-C₂₄H₄₈, und Gemische der vorstehend genannten α-Olefine;
vinylaromatischen Verbindungen der allgemeinen Formel VIII

wobei in den allgemeinen Formeln die Variablen wie folgt definiert sind:
A², A³ gleich oder verschieden und C₂-C₂₀-Alkylen,
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,
b eine ganze Zahl von 1 bis 200,
R⁶, R⁷ gleich oder verschieden und gewählt aus Wasserstoff, unverzweigten oder verzweigten C₁-C₁₀-Alkyl,
X Sauerstoff oder N-R⁴
R⁸ [A³-O]_b-R⁴,
R⁹ gleich oder verschieden und gewählt aus Wasserstoff, unverzweigten oder verzweigten C₁-C₁₀-Alkyl,
R¹⁰, R¹¹ unabhängig voneinander Wasserstoff, Methyl oder Ethyl,
R¹² ausgewählt aus Methyl und Ethyl,
k eine ganze Zahl im Bereich von 0 bis 2
und die übrigen Variablen wie oben stehend definiert sind.In one embodiment of the present invention, copolymers according to the invention comprise at least one comonomer (C) in copolymerized form which is selected
ethylenically unsaturated C ₃ -C ₈ -carboxylic acid derivatives of the general formula II

Carboxylic acid amides of the formula III,

non-cyclic amides of the general formula IVa or cyclic amides of the general formula IVb

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

Phosphate, phosphonate, sulfate and sulfonate group-containing comonomers,
α-olefins, linear or branched, having 3 to 40 carbon atoms, preferably having 4 to 24 carbon atoms, in particular isobutene, diisobutene, 1-decene, 1-dodecene, 1-octadecene, 1-eicosane, α-C ₂₂ H ₄₄ , α-C ₂₄ H ₄₈ , and mixtures of the aforementioned α-olefins;
vinylaromatic compounds of the general formula VIII

where in the general formulas the variables are defined as follows:
A ² , A ^{3 are} identical or different and C ₂ -C ₂₀ -alkylene,
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,
b is an integer from 1 to 200,
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] _b -R ⁴ ,
R ^{9 is} 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 of 0 to 2
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 10 bis 60 mol-%,
• (C) im Bereich von 0 bis 70 mol-%, bevorzugt 1 bis 50 mol-%, jeweils bezogen auf erfindungsgemäßes Copolymerisat, wobei die Summe aus (A), (B) und (C) 100 mol-% ergibt, und
• (D) im Bereich von 1 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 comonomer 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 10 to 60 mol%,
• (C) in the range of 0 to 70 mol%, preferably 1 to 50 mol%, in each case based on inventive copolymer, wherein the sum of (A), (B) and (C) gives 100 mol%, and
• (D) in the range of 1 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.

In one embodiment of the present invention, copolymers according to the invention have an average molecular weight M _n in the range from 1000 g / mol to 50,000 g / mol, preferably 1100 g / mol to 25,000 g / mol, determined for example by gel permeation chromatography with, for example, tetrahydrofuran or dimethylacetamide as solvent and Polymethyl methacrylate or polystyrene as standard.

Copolymers of the invention can concerning (A), (B) and optionally (C) block copolymers, be alternating copolymers or random copolymers, wherein alternating copolymers are preferred.

The polydispersity M _w / M _{n of} copolymers according to the invention is generally in the range from 1.1 to 20, preferably from 1.5 to 10.

One Another object of the present invention is a method for the preparation of copolymers according to the invention.

One Another object of the present invention is a method for the production of aqueous according to the invention Dispersions, also referred to below according to the invention manufacturing method.

To carry out the preparation process according to the invention starting from (A), (B) and optionally (C), which is copolymerized with each other radically and with (D). The reaction with (D) may take place during and after the copolymerization.

In one embodiment of the present invention, hydrolyzed after the radical copolymerization and the reaction with (D) with water, wherein 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 KNCO ₃ , ammonia, amines such as trimethylamine, triethylamine, diethylamine, ethanolamine, N, N-diethanolamine, N, N, N-triethanolamine, N-methylethanolamine.

Copolymers of the invention usually fall in the form of aqueous Dispersions or aqueous solutions or in bulk. From aqueous dispersions 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.

One Another aspect of the present invention is the use of inventive copolymer for the treatment of fibrous substrates.

One Another object of the present invention is the use of aqueous according to the invention Dispersions or of copolymers according to the invention for impregnation of flat Substrates. Another object of the present invention is a method of impregnation of flat substrates using dispersions of the invention or copolymer of the invention, hereinafter also impregnation method according to the invention called. The impregnation process according to the invention For example, can you do that that one flat Substrates with at least one aqueous dispersion according to the invention or at least a copolymer of the invention treated.

at flat Substrates in the context of the present invention may be, for example to trade concrete or bricks.

The Invention will be explained by working examples.

1. Synthesis Code for copolymerization and esterification

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

The average molar mass M _{w of} the copolymers according to the invention was determined by the method of size exclusion chromatography using dimethylacetamide as solvent and polymethyl methacrylate as standard.

General Preparation Method

comonomer (B) and optionally (C) according to the table 1 were placed in a 2-liter kettle and in a gentle stream of nitrogen to 150 ° C heated. After reaching this temperature was within 5 hours the monomer (A) in liquid Form as a melt of about 70 ° C. and according to the table 1 optionally (C) and within 5.5 hours the indicated Amount of di-tert-butyl peroxide added. The type of addition of optionally of added Comonomer (C) or comonomer (C) is shown in Table 1. Subsequently was one hour at 150 ° C reheated.

Subsequently was optionally (D) added. In the experiments in which (D) was added, the resulting mixture is heated under nitrogen for three Hours to a temperature of 150 ° C.

After that the resulting reaction mixture in each case to inventive dispersion further processed.

The resulting reaction mixture was cooled to 90 ° C, treated with aqueous sodium hydroxide solution, wherein the molar ratio of NaOH / maleic anhydride each 0.6: 1.0 was. The mixture was then stirred for 4 hours at 90 ° C and then cooled to room temperature. Dispersions according to the invention were obtained which each had a pH of 5.5 to 6.5.

Further details on the preparation of dispersions according to the invention can be found in Table 1.

2. Application technology exam

The Data in wt .-% refer to the shaved weight, respectively, if not stated otherwise.

2.1 Application in retannage of leather - manufacture of shoe upper leather

Two commercially available cattle Wetblue (Packer, USA) were folded to a thickness of 1.8-2.0 mm and cut into eight strips of about 1000 g each. The strips were then in a barrel (50 l) and a fleet length of 200 wt .-% at intervals of 10 minutes with 2 wt .-% sodium formate and 0.4 wt .-% NaHCO ₃ and 1 wt .-% of a naphthalenesulfonic acid -Formaldehyde condensation product prepared according to US 5,186,846 Example "Dispersant 1." After 90 minutes, the liquor was drained off and the strips were then distributed to 7 separate walk drums.

Together with 100% by weight of water, drums 1 to 7 were metered at 25 to 35 ° C. with 1% by weight of a 50% by weight (solids content) of aqueous solution of dyestuffs whose solids were composed as follows:
70 parts by weight of dye EP-B 0 970 148 , Example 2.18,
30 parts by weight Acid Brown 75 (iron complex), Color Index 1.7.16;
and drummed for 10 minutes in the barrel.

Subsequently, as indicated in Table 2, in each case 6% by weight of the inventive dispersion according to Table 1 were added and the mixtures were tumbled for 30 minutes in the drum. Subsequently, each 8 wt .-% sulfone were from EP-B 0 459 168 Example K1 added and drummed for a further 30 minutes at 15 revolutions / min in barrel. The strips were then treated for 45 minutes with 3% by weight vegetable tanning material ^Mimosa® and 1.5% each of the abovementioned solution of dyes.

Subsequently was with formic acid acidified to a pH of 3.6-3.8. After 20 minutes were the fleets evaluated by an optical process with respect to the consumption and drained. The leather 2.1.1 according to the invention was obtained. to 2.1.7. The leathers of the invention were then washed with 200 wt .-% water. Last were in 100% water at 50 ° C 2 wt .-% of a fatliquoring agent, as described under 3. was produced. After a walk time of 45 minutes was with 1% by weight of formic acid acidified.

The washed leather were dried and staked.

The leather according to the invention 2.1.1 to 2.1.7 provided excellent fullness and softness and feel Yours by coloring of the fibers. additionally show the leather a pronounced Hydrophobing on, without adding them with water repellents Has treated base of silicone compounds, wherein the hydrophobization of the invention the effect of silicone oils even better can.

Comparative Example C1

For Comparative Example C1, the procedure was as above, but instead of the copolymer in two portions, a total of 8% by weight of the fatliquoring agent from 3. were metered in, the first 4% by weight of fatliquoring agent being metered together with ^Mimosa® and dissolving dyes, while the second 4 wt% was added as above after the first acidification.

Table 2 Technical testing of leather 2.1.1 to 2.1.7 according to the invention and comparison leather V1

Remarks:

• 1: Bestimmung der Wasseraufnahme nach Kubelka gem. DIN 53330 (5.78), Das Leder 12, 36-37, 1961, Penetrationszeit: 2 h
• 2: Bestimmung des Verhaltensgegenüber Wasser bei der dynamischen Beanspruchung im Bally-Penetrometer gem. DIN 53338/Blatt 1 (4.76), Das Leder 12, 38-40, 1961, Wasserdurchtritt nach Anzahl der Knickungen.

The evaluation of fullness, grain firmness, softness and levelness of the dyeing was done according to a grading system from 1 (very good) to 5 (deficient).

• 1: Determination of water absorption according to Kubelka acc. DIN 53330 (5.78), Leather 12, 36-37, 1961, Penetration time: 2 h
• 2: Determination of the behavior against water in the dynamic load in the Bally penetrometer acc. DIN 53338 / sheet 1 (4.76), leather 12, 38-40, 1961, water penetration according to the number of buckling.

2.2 Examples: 2.2.1 to 2.2.7: retanning according to the invention of wet-white semi-finished products

The Skin of a South German Rindes was converted to a corresponding wet white semi-finished product by a standard procedure a strength folded by 1.8 mm and cut into strips of about 500 g each.

The semi-finished strips were in a barrel (50 l) and a liquor length of 150 wt .-% at intervals of 10 minutes with 2 wt .-% sodium formate and 0.4 wt .-% NaHCO ₃ and 1 wt .-% of a Naphthalinsulfonsäure- Formaldehyde condensation product prepared according to US 5,186,846 Example "Dispersant 1." After 90 minutes, the liquor was drained off and the strips were then distributed to 7 separate walk drums.

Subsequently, in each case 10% by weight of copolymer dispersion according to the invention according to Tables 1 and 3 and 8% by weight of sulfone tanning agent each EP-B 0 459 168 Example K1 was added and drummed with the leather over a period of 45 minutes. Then, 6% by weight of vegetable tanning agent Tara (BASF Aktiengesellschaft) and 2% by weight of a 50% by weight (solids content) aqueous solution of dyes were metered whose solids were composed as follows:
70 parts by weight of dye EP-B 0 970 148 , Example 2.18,
30 parts by weight Acid Brown 75 (iron complex), Color Index 1.7.16; and another 2 hours. After two hours, the pH was adjusted to 3.6 with formic acid. Finally they sat 1.5% each Lipamin ^® OK to and acidified after a drumming time of a further 60 minutes with formic acid to pH 3.2 at. Leathers 2.2.1 to 2.2.7 according to the invention were obtained.

The leather according to the invention are washed twice with 100% water, stored wet overnight and dried after tentering on tenter at 50 ° C. After the tunnel the leathers are judged as below.

The Rating was based on a grading system from 1 (very good) to 5 (inadequate). The evaluation of fleet consumption was done visually according to the criteria residual dye (extinction) and turbidity (fatliquoring agent).

In Example 2.2.6 and 2.2.7 or 1.5 wt .-% silicone emulsion were before dosing of Lipamin ^® OK in addition to 4 (see below) dosed

Table 3 Examples 2.2.1 to 2.2.7

3. Preparation of a fatliquoring agent

In a 2-liter kettle were mixed:
230 g of a polyisobutene with M _n = 1000 g / mol and M _w = 1800 g / mol,
30 g of nC ₁₈ H ₃₇ O- (CH ₂ CH ₂ O) ₂₅ -OH
5 g of nC ₁₈ H ₃₇ O- (CH ₂ CH ₂ O) ₈₀ -OH
40 g of oleic acid
230 g sulfited oxidized triolein

The mixture was heated with stirring to 60 ° C and 470 g of water and 10 g of nC ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) ₇ -OH added. The resulting emulsion was then passed through a split homogenizer. A finely divided, stable emulsion was obtained.

4. Production a silicone emulsion

als statistisches Cokondensat mit q = 3 und p = 145 (jeweils Durchschnittswerte)
130 g N-Oleylsarkosin,
15 g NaOH (fest)
153 g Paraffingatsch (36/38°C; Shell)
450 ml WasserIn a 2 l container with stirrer were mixed:
150 g of a silicone, kinematic viscosity 600 mm ² / s, the formula

as statistical cocondensate with q = 3 and p = 145 (average values)
130 g of N-oleylsarcosine,
15 g NaOH (solid)
153 g slack wax (36/38 ° C, shell)
450 ml of water

The resulting silicone emulsion had a pH of 8.5.

Claims (21)

Aqueous dispersions of copolymers obtainable by 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, (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 in the range of 300 to 5000 g / mol or obtainable by oligomerization of at least 3 equivalents of C ₃ -C ₁₀ alkene, (C) optionally at least one ethylenically unsaturated comonomer other than (A) , and optionally reacting with (D) at least one compound of general formula Ia or Ib

and subsequent addition with water, wherein in formula Ia and Ib 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 wherein the water content is in the range of 30 to 99.5 wt .-%, based on aqueous dispersion. aqueous Dispersions according to Claim 1, characterized in that the anhydride groups of the copolymer completely or after the polymerization partially with water or aqueous hydrolyzed alkaline solution become. aqueous Dispersions according to one of claims 1 or 2, characterized that the molar ratios of copolymerized copolymer in the copolymer (A) in the area from 5 to 60 mol%, (B) in the range of 1 to 95 mol%, (C) in the range from 0 to 70 mol%, in each case based on copolymer, wherein the sum of (A), (B) and (C) gives 100 mol%, and (D) in the range of 0 to 50 mol%, based on all carboxyl groups of copolymer, lie. Aqueous dispersions according to any one of claims 1 to 3, characterized in that (C) is selected from ethylenically unsaturated C ₃ -C ₈ carboxylic acid derivatives of the general formula II

Carboxylic acid amides of the formula III,

non-cyclic amides of the general formula IVa or cyclic amides of the general formula IVb

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

Phosphate, phosphonate, sulfate and sulfonate group-containing comonomers. α-olefins having 3 to 40 carbon atoms, vinyl aromatic compounds of the general formula VIII

where in the general formulas the variables are defined as follows: A ² , A ^{3 are} identical or different and C ₂ -C ₂₀ -alkylene, 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, is an integer in the range from 0 to 6, b is an integer from 1 to 200, R ⁶ , R ^{7 are} identical or different and selected from among hydrogen, unbranched or branched C ₁ -C ₁₀ -alkyl, X is oxygen or NR ⁴ R ⁸ [A ³ -O] _b -R ⁴ , R ^{9 are} identical or different and selected from hydrogen, unbranched or branched C ₁ -C ₁₀ -alkyl, R ¹⁰ and R ¹¹ independently of one another are hydrogen, methyl or Ethyl, R ¹² selected from methyl and ethyl, k is an integer in the range of 0 to 2 and the remaining variables are as defined above. Aqueous dispersions according to any one of claims 1 to 4, characterized in that they contain 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 in the range of 300 to 5000 g / mol or by oligomerization of at least 3 equivalents of C ₃ -C ₁₀ alkanes. Process for the preparation of aqueous dispersions according to the claims 1 to 5, characterized in that (A) and (B) and optionally (C) radical copolymerized with each other and then with Water is added. Method according to Claim 6, characterized that one while or after the copolymerization of (A), (B) and optionally (C) with (D) implements. Use of aqueous Dispersions according to one of claims 1 to 5 for the treatment of fibrous substrates. Process for the treatment of fibrous substrates using aqueous Dispersions according to one of claims 1 to 5. Method according to claim 9, characterized in that chosen fibrous substrates are made of leather, textile, paper, cardboard, wood, wood composites, Synthetic leather, Alcantara and Lefa. Method according to claim 10, characterized in that that leather is wet white. Fibrous substrates treated by a process according to claim 9 to 11. Fibrous substrates according to claim 12, characterized in that that substrates are leathers. Leather according to claim 13, characterized that it is leather based on wet-white. Use of fibrous substrates according to one of claims 12 to 14 for the manufacture of clothing or furniture or car parts. Copolymers obtainable by 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, at least one Oligomer has an average molecular weight M _n in the range of 300 to 5000 g / mol or is obtainable by oligomerization of at least 3 equivalents of C ₃ -C ₁₀ alkene, (C) optionally at least one of (A) different ethylenically unsaturated comonomer, and reaction with (D) at least one compound of the general formula Ia or Ib,

where in formulas Ia and Ib 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 and optionally hydrolysis. Copolymers according to Claim 16, characterized in that (C) is selected from ethylenically unsaturated C ₃ -C ₈ -carboxylic acid derivatives of the general formula II

Carboxylic acid amides of the formula III,

non-cyclic amides of the general formula IVa or cyclic amides of the general formula IVb

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

Phosphorus, phosphonate, sulfate and sulfonate group-containing comonomers, α-olefins having 3 to 40 carbon atoms, vinyl aromatic compounds of the general formula VIII

where in the general formulas the variables are defined as follows: A ² , A ^{3 are} identical or different and C ₂ -C ₂₀ -alkylene 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 of 2 to 6, y is an integer selected from 0 or 1, a is an integer in the range of 0 to 6, b is an integer from 1 to 200, 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] _b -R ⁴ , R ^{9 are} identical or different and selected from hydrogen, unbranched or branched C ₁ -C ₁₀ -alkyl, R ¹⁰ and 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 of 0 to 2 and the other variables such as o Ben standing are defined. Use of copolymers according to claim 16 or 17 for the treatment of fibrous substrates. Use of aqueous Dispersions according to one of claims 1 to 5 or copolymers according to Claim 16 or 17 for impregnation of flat Substrates. Process for the impregnation of flat substrates, characterized in that flat substrates with aqueous Dispersions according to one of claims 1 to 5 or with copolymers treated according to claim 16 or 17. Method according to claim 20, characterized in that that it is flat Substrates are about concrete or brick.