WO2013001077A1 - Composition based on compounds containing carbamoylsulfonate groups - Google Patents

Abstract

A composition has been found, comprising a) at least one compound containing carbamoylsulfonate groups and b) at least one carboxylic acid containing less than 0.001% by weight, based on the composition, of emulsifier, the compounds containing carbamoylsulfonate groups in component a) being a reaction product of at least one organic polyisocyanate and at least one bisulfite and/or disulfite, characterized in that the organic polyisocyanate has a molecular weight of less than 400 g/mol and NCO groups bonded to aliphatic or cycloaliphatic systems.

Description

 Composition based on carbamoylsulfonate group-containing compounds

The invention relates to a composition based on carbamoylsulfonate-containing compounds, a process for their preparation and their use as a reaction component for amino-containing compounds, for example as leather auxiliaries, there in particular as Vorgerbstoff, tanning, retanning

Polyisocyanates having a functionality greater than 2 are useful as crosslinkers for polymeric materials and have been used successfully for example for a long time in the coating of, for example, metallic surfaces. Polyisocyanates can be used according to the field of application in unmodified form for purely organic coating compositions. Due to the great demand for solvent-free systems, coating agents have been developed which are solvent-free or low-solvent systems. For the crosslinking of the polymeric binders contained in such coating compositions, polyisocyanates are desired which can be dispersed in water. However, the crosslinkers must be dispersed in water directly before use, since the NCO groups are not stable in water and thus have a limited pot life. It is also known to use water-dispersible polyisocyanates as auxiliaries in the production of leather (tanning, retanning, dressing and coating), of paper (agents for increasing wet strength and dry strength, paper coating) and of textile (finishing such as anti-crease in cotton, shrinkage resistant finishing of wool ). In addition, polyisocyanates can be used for crosslinking polymers containing amino groups, for example copolymers based on monomers such as isobutene, butadiene, acrylonitrile, isoprene, styrene and acrylic monomers, where the amino groups can be introduced by subsequent reaction of a copolymer or by copolymerization. Suitable amino-containing polymers are also polycondensates or polyaddition products. For certain applications, it is advantageous or even essential to use crosslinkers which are used in

Water clear solutions and in this form, ie before the addition of the amino group-containing reaction component, are sufficiently stable. It is also particularly advantageous if such crosslinkers react quickly and completely at low temperatures with the amino functions of the binder. Furthermore, it has long been known to crosslink amino-containing polymers with polyisocyanates. This procedure is used, for example, in solventborne two-component reversal coating systems based on polyesterurethanes containing isocyanate end groups or prepolymers and polyamines for flexible substrates such as textile and leather applied. Due to the high reactivity of the amino groups, the components are mixed directly in the application unit. A prior mixing of the components reacting with each other into a 1-component reactive system would be possible, for example, by using polyisocyanates in blocked form. In use, higher reaction temperatures are typically required, with the blocking agent being released from the coating. There are also formulations in which the blocking agent becomes part of the finished coating and is incorporated into the network.

On the other hand, there are also applications in which a prior formulation of isocyanate-containing crosslinkers and amino group-containing polymers in a solvent-free aqueous system is required and still a rapid reaction of blocked polyisocyanates at low temperatures, in particular room temperature, optionally also in the presence of water, is required. This is the case, for example, when using natural amino-containing polymers such as collagen, gelatin or chitosan. In such applications, for example, aliphatic aldehydes such as formaldehyde or glutaraldehyde are used as crosslinking agents.

In particular, in applications with biological material (in vitro and in vivo), it is necessary to meet further requirements on the purity of the accompanying substances or on the processability, the known products still having disadvantages.

US3984365 already describes bisulfite adducts for the finish of leather, paper or textile, all of which are based on NCO prepolymers. For textile applications, such NCO prepolymer-based adducts are also already used in GB2003521. The same applies to GB1491437 and US3989458 in which such products are used for operations outside the leather area.

DE-B 10 2006 056 479 discloses bisulfite-blocked polyisocyanates which can be prepared in the presence of solvents. Also known from US4413997 blocked isocyanates. The use of internal or external emulsifiers as auxiliaries for the synthesis of aqueous bisulfite-blocked polyisocyanates is also known from EP-A 0 690 135, EP-A 0 814 168 and EP-A-1647563.

In US4413997 IPDI based bisulfite adducts are used for tanning, but have the disadvantage that their Schrampftemperatur is not optimal.

It is an object of the present invention to provide water-soluble polyisocyanate-based crosslinkers for aqueous systems which meet the abovementioned criteria for stability in the case of Formulation, reactivity to amino-containing polymers at room temperature and in an aqueous medium and at the same time meet the high requirements for use as reaction components for the reaction with biological materials.

Surprisingly, a composition has now been found which comprises a) at least one carbamoylsulfonate-containing compound and b) at least one carboxylic acid containing less than 0.001% by weight, based on the composition of emulsifier, wherein the compounds containing carbamoylsulfonate groups of component a) a reaction product of at least one organic polyisocyanate and at least one bisulfite and / or disulfite, characterized in that the organic polyisocyanate has a molecular weight of less than 400 g / mol and NCO groups bound to aliphatics or cycloaliphatic, in particular 1, 4-diisocyanatobutane , 1, 6-diisocyanatohexane (HDI), l, 5-diisocyanato-2,2-dimethylpentane, 2,2,4- and 2,4,4-trimethyl-l, 6-diisocyanatohexane (TMHI), 1, 3 - And 1, 4-diisocyanatohexane, 1, 3- and 1, 4-diisocyanato-cyclohexane (CHDI) and any mixtures of these isomers, 1-isocyanato-2-isocyanatomethyl-cyclopentane, 1, 2, 1, 3 and 1 , 4-bis (isocyanatomethyl) Cyclohexane and any mixtures of isomers, 1, 2, 1, 3 and 1, 4-bis (isocyanatoethyl) cyclohexane and any mixtures of these isomers, 1, 2, 1, 3 and 1, 4 bis ( isocyanato-n-propyl) -cyclohexane and any desired mixtures of these isomers, isocyanatopropyl-4-isocyanatomethylcyclohexane and isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 1-isocyanato -l-methyl-4-isocyanatomethylcyclohexane (IMCI), 2,4'- and 4,4'-diisocyanatodicyclohexylmethane (Hi ₂ MDI) and isomers, dimeryl diisocyanate (DDI), bis (isocyanatomethyl) bicyclo [ 2.2.1] heptane (NBDI), bis (isocyanatomethyl) tricyclo [5.2.1.0 ² ' ⁶ ] decane (TCDDI) and isomers and any mixtures of such diisocyanates and xylylene diisocyanates of the formulas

Component a)

Carbamoylsulfonate-containing compounds are understood as meaning those having the following structural unit:

-NH-CO-S0 ₃ ^" K ⁺ wherein K ^{+ is} a cation equivalent.

Preference is given to using the above diisocyanates. However, it is also possible to use monofunctional aliphatic isocyanates, such as, for example, butyl isocyanate, hexyl isocyanate, cyclohexyl isocyanate, stearyl isocyanate or dodecyl isocyanate and / or polyisocyanates having an average NCO functionality of 2.2 to 4.2. The higher-functionality polyisocyanates are preferably trimeric 1,6-diisocyanatohexane, trimeric 1,2-, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, trimeric 1, 2-, 1, 3. or 1,4-bis (isocyanatoethyl) cyclohexane, trimeric 1,2-, 1,3- or 1,4-bis (isocyanato-n-propyl) -cyclohexane, trimeric 1-isocyanatopropyl-4-isocyanatomethyl-cyclohexane and isomers or trimeric 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and optionally dimeric 1,6-diisocyanatohexane, dimeric 1,2-, 1, 3- or 1,4-bis (isocyanatomethyl) cyclohexane, dimeric 1,2-, 1,3- or 1,4-bis (isocyanatoethyl) cyclohexane, dimeric 1,2-, 1,3- or 1,4-bis (isocyanato-n-propyl) -cyclohexane, dimeric l Isocyanatopropyl-4-isocyanatomethylcyclohexane and isomers, or dimeric 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and the correspondingly higher homologs of isocyanurate groups and optionally uretdione-containing polyisocyanate mixtures with an NCO content of 19 to 24% by weight, as determined by catalytic trimerization known per se and with isocyanurate formation of 1,6-diisocyanatohexane, 1,2-, 1, 3 or 1, 4-bis ( isocyanatomethyl) cyclohexane, 1,2-, 1, 3- or 1,4-bis (isocyanatoethyl) cyclohexane, 1, 2-, 1, 3- or 1,4-bis (isocyanato-n-propyl) -cyclohexane, 1-isocyanatopropyl-4-isocyanatomethylcyclohexane and isomers, or obtained from 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and which preferably has an (average) NCO-

Have functionality of 3.2 to 4.2.

The use of monofunctional and of more than difunctional isocyanates in both cases is preferably limited to amounts of not more than 10 mol%, based on all polyisocyanates. However, very particular preference is given to the abovementioned aliphatic, cycloaliphatic and araliphatic diisocyanates. Particularly preferred are hexamethylene diisocyanate (HDI), Diisocyanato-cyclohexane, 1,2-, 1, 3- and 1,4-bis (isocyanatomethyl) -cyclohexane and any mixtures of isomers, 1, 2-, 1, 3- and 1,4-bis (isocyanatoethyl) cyclohexane and any mixtures of these isomers, 1,2-, 1, 3- and 1,4-bis (isocyanato-n-propyl) -cyclohexane and any mixtures of these isomers, 2,4'- and 4,4'-diisocyanato-dicyclohexylmethane , 1-isocyanatopropyl-4-isocyanatomethylcyclohexane and 1-somere and 1-isocyanato-3,3,5-trimethyl-5-

Isocyanatomethylcyclohexane (IPDI). From this latter group are especially preferred hexamethylene diisocyanate (HDI), 1, 2-, 1, 3- and 1,4-bis (isocyanatomethyl) cyclohexane and mixtures of these isomers.

Preferred bisulphites and / or disulphites are their alkali metal or ammonium salts, in particular the sodium salts of sulphurous or disulphurous acid, i. Sodium hydrogen sulfite (NaHSC> 3) or sodium disulfite (Na2S2Ü5) in question.

Advantageously, the other alkali and ammonium salts of these acids, namely potassium bisulfite, potassium bisulfite, lithium bisulfite, lithium disulfite, ammonium bisulfite, Ammoniumdisulf t and simple tetraalkylammonium salts of these acids such as tetramethylammonium bisulfite, tetraethylammonium bisulfite, etc. For blocking the

Salts are preferably used as aqueous solutions with solids contents of 5 to 40% by weight.

In a preferred embodiment of the invention, the compounds containing carbamoyl groups are based on aliphatic polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, bis (isocyanato) cyclohexane, 1,2,2,1,3- and 1,4-bis (isocyanatomethyl) cyclohexane and also any desired mixtures of isomers, 1, 2-, 1, 3- and 1,4-bis (isocyanatoethyl) cyclohexane and any mixtures of these isomers, 1,2-, 1, 3- and 1,4-bis (isocyanato-n-propyl cyclohexane and any desired mixtures of these isomers, isocyanatopropyl-4-isocyanatomethylcyclohexane and isomers, 2,4 'and 4,4'-diisocyanato-dicyclohexylmethane or nonyltriisocyanate, and mixtures thereof, but in particular hexamethylene diisocyanate 1, 2-, 1, 3- and 1,4-bis (isocyanatomethyl) cyclohexane and any mixtures of isomers, 1,2-, 1, 3- and 1,4-bis (isocyanatoethyl) cyclohexane and any desired mixtures of these isomers, 1,2-, 1, 3- and 1,4-bis (isocyanato-n-propyl) -cyclohexane and any mixtures of these isomers and / or isophorone diisocyanate, particularly preferably hexamethylene diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane and 2,4'- and 4,4'-diisocyanato-dicyclohexylmethane. For this last-mentioned group, the carbamoyl-containing compounds are particularly preferably based on hexamethylene diisocyanate (HDI), 1, 2-, 1, 3- and 1, 4-bis (isocyanatomethyl) cyclohexane and mixtures of these isomers. Component a) preferably has the following structural units in the case of diisocyanates as raw materials:

K ⁺ S0 ₃ ^" - [CO-NH-Q-NH] _n -CO-S0 ₃ ^" K ⁺ wherein K ^{+ is} a cation equivalent,

Q is any divalent hydrocarbon radical which may be interrupted or substituted by one or more identical or different heteroatoms, and n is a number from 1 to 50, preferably from 1 to 30. More preferably K ^{+ is} an ammonium radical NR (R = H, Ci-C pAlkyl), or a

Alkali metal cation such as sodium, potassium or lithium.

Very particularly preferred radicals Q are, for example, tetramethylene, pentamethylene, hexamethylene, trimethylhexamethylene, octamethylene, decamethylene or dodecamethylene, which may be by one or more identical or different heteroatoms or 1,2-, 1, 3 or 1,4-cyclohexylene, and 1, 2, 1, 3, and 1, 4-cyclohexylene dimethylene or 3,3,5-trimethyl-1, 5-cyclohexylene-5-methylene.

More preferably n has the meaning of 1 to 5, very particularly preferably n has the value 1.

The abovementioned carbamoylsulfonate groups may also be present as end groups in polyurethane or polyurethane-urea dispersions. In the case of diisocyanates, component a) can also have as raw materials the following structural units:

X - [CO-NH-Q-NH] _n -CO-S0 ₃ ^"in the K

X is a group of the formula -NH-CO-SO ₃ K or a bivalent, optionally, preferably carboxyl-substituted bridge member which is different from Q, and

K ⁺ , Q, and n have the meaning given above.

In the case of higher-functionality polyisocyanates, the same applies accordingly.

Particular preference is given to compounds containing carbamoylsulfonate groups, in which X is the alkoxy radical of a hydroxycarboxylic acid (citric acid) which is obtained by removal of a

Atoms of the hydroxyl group of the hydroxycarboxylic acid results.

Component b)

Suitable compounds of component b) are in particular mono- or polycarboxylic acids, preferably hydroxypolycarboxylic acids. Examples which may be mentioned are: formic acid, acetic acid, oxalic acid, glyoxylic acid, malonic acid, lactic acid, tartaric acid, maleic acid, glutaric acid,

Phthalic acid, adipic acid, malic acid, succinic acid, citric acid, or polycarboxylic acids such as (co) polymers of (meth) acrylic acid, maleic acid, crotonic acid or itaconic acid or derivatives thereof with optionally further monomers such as ethene, propene, styrene, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, Hydroxypropyl acry l at, 4-hydroxybutyl vinyl ether, in particular those having an average molecular weight (weight average MW) of 500 to 100000 g / mol, in particular 500 to 30,000 g / mol.

Particularly preferred as component b) at least one carboxylic acid, preferably oxalic acid, succinic acid, glutaric acid, or adipic acid, in particular at least one hydroxy-polycarboxylic acid, preferably citric acid, tartaric acid or lactic acid or mixtures thereof. Suitable components b) are also aminocarboxylic acids such as glycine, alanine, lysine,

Aspartic acid, glutamic acid, leucine, isoleucine, tyrosine, proline, tryptophan, etc. but also peptides, proteins or protein hydrolysates based on vegetable and animal proteins or collagen-containing materials such as soy protein hydrolysates, hydrolyzates of skin, hair and pumice Waste, white waste, leather waste, hydrolyzates of keratinous materials, polyaspartic acid, polyglutamic acid, and products obtained by polycondensation of

Maleic acid amide with elimination of water, optionally subsequent derivatization of the polysuccinimide with amino compounds, and subsequent hydrolysis of the remaining succinimide units are obtained under ring opening, in particular the polyaspartic acid amides from WO97 / 06279 which are hereby incorporated as incorporated.

Also suitable as component b) are derivatives of cellulose, oligosaccharides or monosaccharides which contain a carboxyl group, for example carboxymethylcellulose, oxidized starch, preferably having a molecular weight of less than 100,000 g / mol, in particular less than 20,000 g / mol, gluconic acid, glucuronic acid, oxidatively degraded anionic starch, alginates, pectins, etc.

Preferred component b) is also a carboxylic acid group-containing reaction product of a hydroxypolycarboxylic acid and a polyisocyanate. Suitable hydroxypolycarboxylic acids are, in particular, those mentioned above, in particular citric acid. Suitable polyisocyanates are in particular the abovementioned, in particular the preferred diisocyanates, in particular hexamethylene diisocyanate.

A preferred component b) preferably contains 0 to 5 wt .-%, preferably 0 to 2 wt .-%, based on the composition, of a reaction product of a carboxylic acid and the polyisocyanate used.

The composition according to the invention is preferably essentially free of emulsifiers, ie compounds which reduce the interfacial tension between an organic and an aqueous phase, so that an oil-in-water emulsion can form, in particular it is emulsifier-free. Component c)

Preferred further additives of component c) may preferably comprise or not contain fatliquoring agents, dedusting agents, buffers and / or fillers. Emulsifiers are for the purposes of this invention preferably no additives.

Fatliquoring agents are preferably substances based on biological, mineral or synthetic oils which can be provided with hydrophilic groups in order to improve the usability in water, eg. B. by complete or partial sulfation, sulfitation, carboxylation or phosphating.

Suitable fillers are preferably inert inorganic salts and organic polymers, for. As sulfates such as sodium sulfate or calcium sulfate, talc, silica compounds, starch or lignosulfonates into consideration. Suitable buffers are those which can be adjusted and stabilized by addition in a sufficient amount of a pH range, in particular a pH range of 1 to 5, preferably 2.0 to 3.5. Suitable buffers for this are preferably mixtures of compounds of component c) and their salts in question. Preferred salts are in particular alkali metal salts, preferably sodium or potassium salts.

Examples of preferred dedusting agents are alkoxylates of aromatic compounds or polyethers or certain diesters. Examples which may be mentioned specifically: ethoxylates, propoxylates or mixed polyethers based on EO / PO, hydroquinone or phenol-styrene being mentioned as aromatic compounds, polyethylene glycol having an average molecular weight of from 100 to 800, polypropylene glycol having an average molar mass of from 100 to 800, EO / PO mixed polyether having an average molecular weight of 100 to 800, monoalkyl ethers or dialkyl ethers of the abovementioned polyethers, where the alkyl radical may have 1 to 4 carbon atoms. Dustproofing agents based on mineral oil are also suitable. Dedusting agents are preferably used in an amount of 0 to 5.0, preferably 0.1 to 2.0%, based on inventive solid material. The composition according to the invention may also contain or not contain further additives, the amount of these additives including that of component c) preferably being up to 30% by weight.

The inventive solid composition preferably contains

From 65 to 99.9% by weight, in particular from 78 to 99.9% by weight, of component a), from 0.1 to 15% by weight, in particular from 0.1 to 10% by weight, of component b),

0 to 15 wt .-%, in particular 0 to 10 wt .-% further of a) and b) various additives which contains less than 0.001 wt .-%, based on the composition of emulsifier.

Preferably, the solid composition contains 0 to 5 wt .-%, in particular 0 to 2 wt .-% water (residual moisture). The weight ratio of component a) to b) is preferably 1: 1 to 10: 1, in particular 1: 1 to 1000: 1.

The aqueous composition according to the invention preferably contains

From 10 to 49.9% by weight, in particular from 20 to 49.9% by weight, of component a),

0.1 to 8 wt .-%, in particular 0.1 to 5 wt .-% of component b), 0 to 7 wt .-%, in particular 0 to 5 wt .-% further of a) and b) various additives containing less than 0.001 wt .-%, based on the composition of emulsifier.

The aqueous composition according to the invention preferably contains from 35 to 90% by weight, in particular from 50 to 80% by weight, of water.

The compositions of the invention may be present as a solid, particulate material or as a liquid, in particular aqueous composition.

The composition of the invention is preferably in the form of a solid, particulate material having a melting point of greater than 20 ° C., preferably greater than 60 ° C., in particular greater than 100 ° C. "Particulate" is in particular a material having an average particle size of 0.1 μm to 1000 μm, preferably 1 to 800 μm, in particular 50 to 300 μm, the mean being based on the mass (weight average) of all particles. Volume average) can be calculated therefrom by analytical methods and vice versa The average particle size can be determined, for example, microscopically.

Preferably, the particulate solid material according to the invention has a residual moisture content of 0 to 10 wt .-%, in particular 0 to 5 wt .-%, particularly preferably 0 to 2 wt .-%, based on the material. The particulate solid material according to the invention is based on any, preferably a spherical or spherical shape-like or derived particle structure. There are also agglomerates of particles from the mentioned forms in the range specified

Particle size in question. According to the invention, the material may be present as a powder, granules or as so-called. Micro granules, as it is z. B. is obtained in the one-fluid nozzle spray drying.

Also preferred is the composition of the invention as an aqueous composition, in particular aqueous solution, preferably having a solids content of 10 to 49.9 wt .-%, preferably from 20 to 49.9 wt .-%.

In a likewise preferred embodiment, the composition according to the invention contains less than 1% by weight of organic or inorganic tannins, preferably less than 0.1% by weight, in particular the composition is essentially free of organic or inorganic tannins, with very particular preference it is free of organic or inorganic tannins. Also preferably, the solid composition according to the invention additionally contains 0 to 15% by weight, in particular 0 to 10% by weight, very particularly preferably 0.01 to 5% of component c), in each case based on the solid composition.

Also preferably, the aqueous composition according to the invention additionally contains 0 to 7.5 wt .-%, in particular 0 to 5 wt .-%, most preferably 0.005 to 2.5% of component c), each based on the aqueous composition. In the case of the aqueous composition, the formulation contains a percentage of components a) to c) which has been reduced by the proportion of water.

In a likewise particular embodiment, the material according to the invention also contains reaction products of polyisocyanates or polyisocyanate bisulphite adducts and citric acid. For example, such reaction products containing urethane groups and carbamoylsulfonate groups are obtainable by reaction of an excess of polyisocyanate with component b) and subsequent reaction with a bisulfite and / or disulfite. Examples of compounds of this type are bisurethanes of 1 mol of hexamethylene diisocyanate and 2 mol of citric acid or, for example, the monourethane of 1 mol of hexamethylene diisocyanate and 1 mol of citric acid, with residual NCO groups reacting in situ with bisulfite and / or disulfite to give the carbamoylsulfonate group.

Particularly preferred compositions are those containing compounds containing Carbamoylsulfonatgruppen- by reacting at least one organic isocyanate with at least one bisulfite and / or disulfite and at least one hydroxy-polycarboxylic acid (component b), in particular citric acid, preferably in an amount of 0.05 to 3, preferably 0.1 to 2% wt .-%, based on the composition were obtained.

The preferred materials of the present invention contain less than 5%, especially less than 1% of urea group-containing dimeric, trimeric or polymeric carbamoylsulfonates which may be by-produced by hydrolysis of the polyisocyanates in the synthesis.

The composition according to the invention preferably contains

0.1 to 49.9 wt .-%, in particular 10 to 49.9 wt .-% of the carbamoylsulfonatgruppen- containing compound of component a) and

0.1 to 10% by weight, in particular 0.1 to 5% by weight, very particularly preferably 0.1 to 3% by weight of component b), 40.1 to 99.8 wt .-%, in particular 50 to 89.9 wt .-% water, each based on the composition containing less than 0.001 wt .-%, based on the composition of emulsifier. Production The invention further relates to a process for the preparation of the invention

Composition characterized in that the component a) with component b), if appropriate, mixed with further additives.

The invention further relates to a process for the preparation of the composition according to the invention which is characterized in that at least one organic polyisocyanate having a molecular weight of less than 400 g / mol with aliphatics or

Cycloaliphaten bonded NCO groups with at least one bisulfite and / or disulfite in the presence of water and with simultaneous action of shear forces, wherein the carboxylic acid of component b) and optionally further additives before, during or after the bisulfite and / or disulfite Reaction is added and the resulting reaction mixture is then optionally dried.

The invention further relates to a process for the preparation of a solid, particulate composition according to the invention, which comprises reacting at least one organic polyisocyanate with at least one bisulfite and / or disulfite in the presence of water and with the simultaneous action of shear forces, and the resulting aqueous solution then dried, wherein the carboxylic acid of component b) is added before, during or after the bisulfite reaction or only after drying.

Furthermore, it is advantageous to filter the reaction solution of the method according to the invention before drying. For this purpose, for example, known separation techniques such as filtration on per se known porous filter media such as paper, ceramic materials or porous plastics are suitable. Simple methods such as vacuum filtration via suction, pressure filtration via pressure suction filters, chamber filter presses, filter bags, or more complex separation techniques using filter cartridges, which are also used, for example, in HPLC analysis or in sterile filtration, are used. In addition, a sedimentation by centrifugation for the separation of small amounts of turbidity can be used. For the synthesis of the aqueous compositions and the solid compositions, both continuous and discontinuous process variants are suitable. To produce sufficiently high shear forces are commercially available stirrers, Schnellrührrer and dispersing machines, such as dissolvers and mixers rotor-stator type, for example, an Ultraturrax device with slotted discs, as well as ultrasonic generating apparatus, the sonotrode is immersed in the reaction medium, or high-pressure homogenizers which can be designed, for example, for high pressures (eg 10 to 1000 bar) or jet dispersers using nozzles which are operated, for example, in a pressure range in the middle range (eg 10 to 100 bar).

Furthermore, it is possible to carry out the preparation of carbamoylsulfonatgruppenhaltigen compounds continuously, wherein the reaction components are fed continuously into a plant part, which allows an intimate mixture of the components, and the reaction mixture at elevated temperatures, preferably from 20 to 100 ° C and at the Temperature-adapted short residence time, for example, is reacted in a microreactor to the final product, the resulting reaction mixture, optionally after adjusting the temperature, pH, concentration and addition of further components is fed into a drying apparatus, and after evaporation of the water, the solid, particulate material is discharged from the plant and filled in appropriate containers. Suitable microreaction systems are, for example, those from Ehrfeld BTS GmbH or GEA / Niro.

It is also possible to continuously feed the component b) and optionally further additives during the reaction to the reaction. In a continuous mode, it is possible to adjust the reaction temperature at 20 to 100 ° C. The residence time in the reaction system can be shortened by increasing the reaction temperature to a few minutes.

In a preferred embodiment, a solution of alkali bisulfite or disulfite is prepared in water. This aqueous solution and the polyisocyanate are now separated and in a stoichiometric ratio of bisulfite groups (HSO ₃ -) to NCO groups of 1.0: 1.0 to

1.2: 1.0, preferably 1.0: 1.0 to 1.05: 1.0 corresponding speed supplied continuously to a mixer, which is integrated into a microreaction system. For example, microreaction plants with a modular structure from Ehrfeld BTS GmbH can be used for the continuous production. The two liquid streams are preferably metered with pulsation-free working high-pressure pumps via inlet modules in the microreaction system. The liquid streams supplied to the mixer are intimately mixed by the microstructure of the mixer, passed through a heat exchanger and then in a microreactor at a temperature between 20 and 120 ° C, preferably with a residence time of a few seconds to 15 minutes, reacted to give complete conversion of the NCO groups. After leaving the reactor, the aqueous product solution is cooled by a heat exchanger and pumped via an outlet module from the microreaction system into a separate container. The solution may now be mixed continuously in this container with further additives of component b) and optionally c) and passed directly into a spray dryer. The metering rate of the raw materials in the microreaction plant is thereby advantageously adapted to the speed of discharge of the spray-dried material from the spray dryer. For spray drying, the inlet temperature is preferably set at 120 to 200 ° C, preferably at 130 ° C to 180 ° C. If the solid material has a residual moisture content of more than 2%, it may be advantageous to reduce the residual moisture to a value below 2% in a downstream, likewise continuously operated drying step, for example in a fluidized-bed dryer or paddle dryer. The material obtained is then filled continuously into corresponding containers. It may be advantageous in the continuous process, for example, before, during or after spray drying to add a dedusting agent to obtain a dust-free product that is free-flowing and can be easily dosed by the user. The resulting solid material is very soluble in water (at 20-25 ° C) and is characterized as a solid material by excellent storage stability even at high temperatures (60 ° C).

For drying the aqueous reaction mixtures, irrespective of whether intermediate isolation of the aqueous reaction mixture takes place or not, the per se known apparatuses such as spray dryers, thin film evaporators, evaporation screws, apparatus for cooling crystallization or vacuum dryers such as apparatuses for freeze drying or vacuum dryers with forced conveying. Particularly suitable are spray dryers, optionally also spray dryers with integrated fluidized bed drying. A drying of the predried material may be required, so that the maximum residual moisture content is kept as low as possible. The residual moisture is usually in the range of 0 to 5%, preferably between 0 and 2%, particularly preferably between 0 and 1%, based on solid material.

A suitable process for the drying is in particular the spray-drying, preferably single-substance spray drying by means of high-pressure or swirl chamber nozzles or spray drying by means of sputtering disks, freeze-drying with upstream or downstream granulation or dry work-up, built-up granulation, for example after the plate or drum granulation process optionally with partly pre-dried product, Fluidized bed drying and granulation, mixed agglomeration and drying optionally in combination with fluidized bed or fluidized bed drying. Furthermore, processes such as mixed agglomeration in suspension with optionally downstream fluidized bed or fluid bed drying, granulation by means of paste deformation and subsequent post-drying and come Comminution or pelletizing and steam jet agglomeration in question. Combinations of said methods are also possible. It is also possible to dry the aqueous solution by evaporating the water by depressurizing a solution subjected to high pressure with carbon dioxide, whereby fine powders are also obtained. Particularly preferred are the methods of spray drying by means of high-pressure or swirl chamber nozzles, spray drying with integrated and / or downstream fluidized-bed agglomeration and / or drying, built-up granulation by the plate method and fluidized-bed granulation and drying.

The solid carbamoylsulfonate group-containing compounds can be prepared by various methods. Three methods are briefly described below.

A process according to the invention for the preparation of the solid composition according to the invention is preferably characterized in that a precipitating agent such as acetone, ethanol, isopropanol, methyl ethyl ketone is added to the liquid reaction mixture obtained by one of the processes described above and the precipitate is dried.

For the preparation of the solid composition, there are three exemplary procedures below.

Method 1 = Precipitation of the Carbamoylsulfonatgruppen-containing compound from aqueous solution. The precipitation is carried out by mixing the aqueous solution with an excess of an at least partially water-immiscible non-solvent for component a), preferably ethanol, methanol, n-propanol, isopropanol, methoxypropanol, acetone, methyl ethyl ketone, ethyl acetate. Most preferred is acetone.

The aqueous solution to be used preferably has a concentration of from 10 to 50%, particularly preferably from 25 to 45%. Particular preference is given to aqueous solutions which are prepared by reacting the polyisocyanate with the alkali salt of bisulfite / disulfite, wherein 1.00 to 1, 10 mol of bisulfite equivalents are preferably used per 1.00 NCO equivalent. Particular preference is given to aqueous solutions which are prepared by reacting the polyisocyanate with the bisulfite / disulfite alkali salt, with 1.00 to 1.05 mol of bisulfite equivalents being preferably used per 1.00 NCO equivalent. Very particular preference is given to aqueous solutions prepared by reacting the polyisocyanate with the bisulfite / disulfite alkali salt are used, wherein per 1, 00 NCO equivalent, preferably 1, 00 to 1, 10 moles of bisulfite equivalents, wherein a proportion of component b) of at least 10% based on component b), already added during the reaction and the Rest after the implementation.

The aqueous solutions are particularly preferably prepared by reacting the polyisocyanate with the bisulfite / disulfite alkali salt, 1.00 mol of bisulfite being present per 1.00 NCO equivalent.

Equivalents are used. The latter case with stoichiometric equivalence 1: 1 is most preferred when acetone or methyl ethyl ketone are used as precipitating agent and it depends on a particular purity of the compound containing carbamoylsulfonate groups.

The organic solvent for precipitating the solid carbamoylsulfonate group-containing compound is preferably used in excess. The weight ratio of water to solvent is 1: 1 to 1:10, more preferably 1: 1 to 1: 5. It is possible to add the organic solvent to the aqueous solution containing the carbamoylsulfonate group-containing compound or the aqueous solution inversely to add to the submitted organic solvent. In general, the mixture is stirred during the precipitation. The precipitated product is then separated by decantation, centrifugation or filtration, preferably by suction using filter media, for example by means of a vacuum chute, a pressure filter or a chamber press, then optionally washed with fresh solvent and then dried. The separation process can also be continuous if a combination with the above-described continuous preparation of the aqueous solution is provided. The drying of the solid material is preferably carried out in vacuo at a temperature of -20 to + 40 ° C.

The aqueous solution to be used preferably has a concentration of between 10% and 60%, more preferably from 25 to 45%, based on the sum of component a) and b) and optionally c). The aqueous solution to be used preferably has a pH of 2.0 to 6.0, more preferably a pH of 2.3 to 4.0, most preferably a pH of 2.5 to 3.5.

The precipitation with organic solvent is preferably carried out below the boiling point of the organic solvent, more preferably below 50 ° C, most preferably in the temperature range of 0 ° C and 40 ° C. The temperature at the beginning of the drying is kept as low as possible and increased towards the end of the drying to the final temperature. This gentle procedure ensures that hydrolysis of the carbamoylsulfonate group-containing compound during work-up is avoided. The yield is almost quantitative when using acetone in most cases. If necessary, the filtrate can then be replenished. The combined filtrates can then be worked up in a suitable form, for example by a vacuum distillation, to recover the organic solvent. Method 2

Drying of an aqueous solution containing the carbamoylsulfonate group-containing compound by thermal drying methods.

Drying of the aqueous reaction mixtures, which does not require the use of organic solvents, is particularly preferred. The aqueous solution to be used preferably has a concentration of 10 to 60%, particularly preferably 35 to 50%.

The aqueous solution to be used preferably has a pH of 2.0 to 6.0, more preferably a pH of 2.3 to 4.0, most preferably a pH of 2.5 to 3.5.

The aqueous solution fed to the dryer is preferably adjusted to a temperature below 90 ° C., very particularly preferred is a temperature range from 10 ° C. to 80 ° C., in particular from 20 to 60 ° C. The temperature setting of the solution supplied to the spray dryer is preferably carried out shortly before the inlet nozzle of the spray dryer. It is particularly advantageous to pass the solution for heating through a separate heat exchanger in order to achieve a brief heating of the material. Suitable for drying are the technical apparatuses customary in drying technology. Particularly preferred are methods in which spray dryers are used. All known process variants are suitable. Thus, for example, spray drying towers are suitable with single-fluid nozzles, in which the aqueous solution is injected into the head of the spray dryer by means of overpressure, wherein the particle size is adjustable, inter alia, on the nozzle diameter used. Also suitable, for example, spray dryers with a disc atomizer, in which the aqueous solution is applied to an externally driven rotating plate and finely distributed by centrifugal forces. The inlet temperature in the spray dryer is for example 100 ° C to 250 ° C, but preferably 110 ° C to 200 ° C, more preferably 1 10 ° C to 180 ° C. The outlet temperature is for example 20 to 130 ° C, preferably 50 ° C to 1 10 ° C, more preferably 70 to 100 ° C. The residual moisture of the powder obtained is preferably below 20%, preferably below 10%, more preferably below 5% and most preferably below 1.5%.

The obtained carbamoylsulfonate-containing compounds are preferably obtained as colorless powders which only slightly dust. If appropriate, it may be advantageous to add a dedusting agent to the material to be dried before, during or after the spray drying. It is preferred to add the dedusting agent to the aqueous solution. Furthermore, it is possible to introduce the dedusting agent into the dryer during the spray-drying process. Furthermore, it is possible to cover the resulting powder on the surface with a dedusting agent. Method 3 = Isolation of the solid material by cryogenic techniques

It is also possible to precipitate the carbamoylsulfonate group-containing compound from the aqueous solution by cooling crystallization or to work up by freeze-drying.

The workup is carried out in a known manner by a mechanical separation of the solid or by evaporation of the water from the frozen aqueous solution.

Very particularly preferred for drying the aqueous reaction mixtures are the spray-drying processes according to Method 2.

use

The invention further relates to the use of the composition according to the invention as a reaction component for amino group-containing compounds. A l s amino-containing

Examples of suitable compounds are polymers such as gelatin, polysaccharides containing amino groups, diamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diaminocyclohexane, 1,1-diaminododecane, amino-containing polyethers, polyamines such as diethyltriamine, triethylentetramine, tetraethylenepentamine, aminoethylpiperazine, pentaethylenehexamine, Polyethyleneimine, polyvinylamine, polyamidoamine-based resins, which are used, for example, in the paper industry for increasing the wet strength and as retention aids, amino-containing (co) polymers based on monomers from the group of dienes, such as butadiene, isoprene, isobutene, olefins, such as ethylene, Propylene, styrene, acrylic acid esters, methacrylic acid esters, (meth) acrylamides, or vinyl esters such as vinyl acetate, vinyl propionate, where the amino groups can be introduced by using amino-containing comonomers or by subsequent derivatization of the (co) polymer. Suitable amino group-containing compounds can furthermore be biological material, such as, for example, tissue in association with other materials, such as skin material, connective tissue, bones, organs, muscle fibers or wall material of blood vessels, optionally in isolated or purified form. The end products used with the biological material according to the invention are advantageously suitable for the production of surgical sutures, for the production of implantological preparations, for the production of bone substitutes and for the production of body-compatible replacement materials for surgery. In the case of animal hides, the end product used according to the invention is then a tanned leather with advantageous properties.

The invention therefore also relates to reaction products obtainable by reaction of amino-containing compounds with the compositions according to the invention.

The invention further relates to the use of the composition of the invention as a crosslinker for water-soluble protein-based polymers, preferably gelatin. An advantageous application is the stabilization of monomer suspensions in water through a sheath of stabilizing material, wherein the stabilizing material contains gelatin. The gelatin can be crosslinked with the composition according to the invention. This prevents stabilization of the capsules and coalescence of the monomer droplets. In a subsequent working step, the polymerization of the monomers can be initiated inside the capsules, for example by increasing the temperature. The use of oil-soluble initiators, which are introduced in the monomer phase before the encapsulation of the monomers with the gelatin, is advantageous. The process is particularly advantageous for the preparation of crosslinked styrene copolymers and for the preparation of ion exchangers which must have a very narrow average particle size distribution, being used for the polymerization and preparation of the monodisperse monomer droplets per se known methods and technologies.

The composition according to the invention thus represents an alternative to the previous formaldehyde crosslinking.

The reaction of the compositions according to the invention with amino-containing reaction components can be carried out in an aqueous medium or in the presence of organic

Solvents take place. Particular preference is given to solvents in which the products according to the invention are partially soluble and which are partially miscible with water, for example. Examples include: polar solvents such as pyrrolines, dimethylsulfoxide, Dimethylformamide, N-methylpyrrolidinone, N-ethylpyrrolidinone, ethanol, methanol, ethylene glycol, diethylene glycol, dipropylene glycol, methoxypropyl acetate, tetrahydrofuran.

The invention further relates to the use of the composition according to the invention as auxiliaries for papermaking, in particular for the production of wet strength agents or retention aids. In particular, the compositions according to the invention are suitable as

Reaction component for the production of chlorine-free wet strength agents by reaction with amino groups-containing polyamidoamine resins. Polyamidoamine resins are, for example, polycondensates of adipic acid with one or more polyamines, for example, a group of diethylenetriamine, ethylenediamine, caprolactam, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and their homologs or polyamines with piperazine-

Units such as aminoethylpiperazine. The reaction is advantageously carried out in aqueous solution in a stoichiometric ratio of 0.1 to 2 mol of component a) based on the amine equivalents of the polyamidoamine resin. If the desired molecular weight increase, which can be monitored, for example, by measuring the solution viscosity, is reached, the condensation can be interrupted by acidification of the reaction mixture to pH 2.5 to 4 and the resulting

Reaction product to be stabilized. The resulting reaction product may then be fed to a high dilute cellulose slurry in papermaking at a dosage of 0.1 to 8% by weight. After dewatering the cellulosic material and the sheet formation with the aid of a paper machine and subsequent drying, a paper is obtained with an increased tear strength in the dry state and with rewetting with water. The composition according to the invention can advantageously be used for the production of filter paper, photo paper, kitchen towels, handkerchiefs, tissue papers, banknotes, wallpapers, etc.

Further, the cationic polyamidoamine and polyamine resins obtained by using the compositions of the present invention, preferably high molecular weight and high cationic polyamidoamine and polyamine resins, can be used as a retention agent in papermaking. These aids accelerate dewatering in sheet formation on a paper machine and thus contribute significantly to increasing the running speed of the paper machine. For this purpose, the compositions according to the invention are added directly to the cellulose slurry in situ in papermaking as flocculant and dewatering accelerator. The invention further relates to the use of the composition according to the invention, in particular a solid, particulate composition, for example as Vorgerbstoffe, tannins or as retanning of hides and skins.

It is also preferred to carry out the reaction of the compositions according to the invention with the amino-containing compounds in an aqueous system at a pH of 6 to 10.

For the purposes of this invention, pretanning agent is understood to mean a product with which a skin or a coat can be converted into a state which permits commercial mechanical treatments such as wilting or wrinkling, but requires further treatment steps with tanning substances to complete the leather or fur.

The invention further relates to a process for the tanning of hides and skins, which is characterized in that treated after washing, liming, possibly depilation and deliming pretreated hides or skins with the composition of the invention.

The invention also relates to the wet white leather obtained by the tanning process according to the invention, including a chromium-free tanned leather intermediate for mechanical

Treatment and further (subsequent) tanning is understood.

For the tanning of furs, the depilation is of course no longer necessary.

The appropriately prepared skins (hereinafter called skins) are preferably in a commercial Gerbfass in aqueous liquor at a temperature of 10 ° C to 60 ° C and a pH of 5 to 10, preferably 7 to 9, with 0.5 to 10%, preferably 1 to 4% (based on the proportion of pure component a)) of the composition according to the invention treated in such a way that a tanned intermediate having a shrink temperature of at least 65 ° C, preferably at least 68 ° C, particularly preferably at least 70 ° C. receives. The shrinkage temperature is determined by methods known to those skilled in the art, for example by heating the tanned intermediate by immersion in a water bath whose temperature matches a certain temperature

Heating rate is increased until the contraction of the material is observed. The temperature reached on contraction is read on the display of the tester (Leather Shrinkage Tester). The shrinkage temperature can also be determined by means of the differential scanning calorimetry (DSC) method known to the person skilled in the art. After addition of the composition according to the invention, the product is preferably left to be from 0.1 to 8 h, preferably from 0.2 to 2 h, at a pH in the section of 8 to 10 and penetrate a liquor pH of 7 to 8 and then add a fixative. Suitable fixing agents in the tannery are known bases or mixtures thereof, for example sodium hydroxide, alkali metal carbonates, alkali hydrogen carbonates, magnesium oxide, dolomite, tertiary amines, etc., but especially dolomite, magnesium oxide, sodium carbonate and sodium hydroxide solution. The fixation is preferably carried out over a period of 2 to 24 h, preferably 4 to 12 h at a

Liquors pH of 7 to 10, preferably a liquor pH of 7.0 to 8.5.

It is also possible to interrupt the tanning by acidification to pH 4 to 6 or addition of ammonia or a primary or secondary amino compound. This is particularly advantageous if an excessive astringency of the liquor is to be avoided and a partial inactivation of the tanning agent is desired. These additional measures are appropriate to the

To influence tanning process in an advantageous manner.

Examples of suitable amino compounds are ethanolamine, diethanolamine, propylamine, butylamine, hydroxypropylamine, dihydroxypropylamine, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxy si 1, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, bis (3-triethoxysilylpropyl) amine, bis (3-trimethoxysilylpropyl) amine,

Hydroxyethylmorpholine, hydroxyethylcyclohexylamine, hydroxypropylmorpholine, hydroxypropylcyclohexylamine, hydroxyethylethylenediamine, hydroxypropylethylenediamine, bis (hydroxyethyl) ethylenediamine, bis (hydroxypropyl) ethylenediamine,

In particular, the abovementioned silanes are suitable for addition during the tanning process within the substrate by hydrolysis to silanol groups and self-condensation of the silanol groups

Polysiloxanylgruppen additionally build a three-dimensional secondary network and can therefore contribute advantageously to further stabilization of the skin material. The presence of mineral fillers can also enhance the stabilizing effect. Suitable mineral fillers are, for example, silica-containing materials such as hydrolytically produced or pyrolytically produced silicas, ground glasses, sheet silicates, aluminum silicates, zirconium dioxide, titanium dioxide. Such mineral fillers may also form an over-surface specially treated by organofunctional silanes and chemically modified. Such materials are commercially available. The stabilization of the skin is a desirable effect, especially when used as a pretanning agent, in order, for example, to positively influence the mechanical processing during the folding process. Also, this can be favorably influenced the shrinkage temperature. These silanes can also be used in the retanning in combination with the composition according to the invention can be used to influence the haptic properties (fullness, softness) and the dyeing properties (levelness, colouration).

It is particularly advantageous to choose a low initial pH of the liquor of 6 to 7 to penetrate the tanning agent and to regulate fixation in a pH range between 7.5 and 8.5 and by increasing the temperature.

The obtained, tanned intermediates are suitable for mechanical processing by z. B. Wilting, folding or splitting. In addition, these intermediates are characterized by a very white, clear and light-fast intrinsic color, which is a clear advantage over glutardialdehyde tanned leathers. The pre-tanned intermediates can be retanned by methods known to those skilled in the art and finished to give soft and airy crust leathers.

The invention further relates to a process for the production of leather and furs, characterized in that in an aqueous liquor at a temperature of 10 ° C to 60 ° C and a pH of 5 to 10, preferably 7 to 9 prepared plow material (ie for the tanning conditioned skins or delimbed and / or pickled bloom material) with 0.5 to 10%, preferably 1 to 4% (based on active ingredient of component a)) of the material according to the invention until a tanned intermediate having a shrinkage temperature of at least 65 ° C, preferably at least 68 ° C, particularly preferably at least 70 ° C receives.

If the shrinking temperature is lower, the mechanical processing of the tanned intermediates, the so-called wet white material, on e.g. Folding machines problematic because the wet white material sticks too much to the knife rollers and can be poorly processed. On the other hand, if the tanning is allowed to run for longer, if more tannin is metered or fixated at higher pH values, considerably higher shrinkage temperatures can be achieved. But these are not required for the mechanical processing of the arms. In a separate embodiment of the invention, the properties of the mechanical

Further processing and the final leather properties can be adapted to the requirements of the customer by before, during or after the addition of the composition according to the invention further in the tannery typical substances of the tannery are added.

These include the commercially known organic organic tanning agents known to those skilled in the art, such as syntans, resin tanning agents, vegetable tanning agents, filling and softening polymer (post) tanning agents, fatliquoring agents and water repellents. Preferably, these agents used in the subsequent Nachgerbschritten in the usual quantities for wet white. In the Nachgerbschritten pro rata lignosulfonates can be used.

Advantage of the tanning process according to the invention is that leather can be obtained with a wide range of properties and which can be used versatile as raw materials in the mechanical processing shavings, u.a. also for the production of valuable products that can be used in the leather manufacturing process. This provides a significant contribution to further reducing waste in leather production.

A particular advantage of compositions according to the invention is that they do not foam when used in aqueous solution and have very good stability to hydrolysis under application conditions.

Examples Example 1

(Bisulfite: NCO = 1.05: 1)

To a solution of 422.7 g of water and 609.5 g of sodium bisulfite solution (NaHSC> 3, 38-40% in water) are added 182.9 g of hexamethylene diisocyanate starting at 23 ° C in 15 minutes, the mixture by means of a dispersing with Rotor-stator principle (Ultraturrax unit from IKA) is dispersed at 15,000 to 20,000 revolutions per minute. The temperature of the reaction mixture is increased within 120 minutes after addition of the isocyanate to about 50 ° C. The pH is initially 3.04 and increases during the reaction to max. pH 5 on. The mixture still looks milky at this time, but the isocyanate has already been converted to such an extent that no organic phase is observed after stopping the dispersing machine and waiting for 120 seconds. It is then further dispersed for 1 hour at 20,000-24,000 revolutions per minute, with the temperature rising to 56 ° C. After a reaction time of a total of 3 hours, a clear solution has emerged. The pH is 3.66. The batch is then cooled to 25 ° C in 30 minutes and it will be

31.1 g of citric acid monohydrate dissolved in 25.7 g of water was added. A clear 35.0% solution with a pH of 2.00 is obtained.

At room temperature, 3000 ml of acetone are added to this solution. It is stirred for 2 hours. The precipitated white solid is filtered off, washed with acetone and dried in vacuo at 20 ° C to constant weight (yield 94.5%, residual moisture content below 1 wt .-%).

A solution of 1.75 g of powder in 5 ml of water is clear and has a pH of 2.20.

Example 2

(Bisulfite: NCO = 1.05: 1)

To a solution of 384.3 g of water and 554.1 g of sodium bisulfite solution (NaHSC> 3, 38-40% in water) are added 166.3 g of hexamethylene diisocyanate at 23 ° C in one portion, the mixture by means of a dispersing machine with rotor - Stator principle (Ultraturrax aggregate of

Company IKA) is dispersed at 10,000 revolutions per minute. The temperature of the reaction mixture is raised to 63 ° C within 45 minutes after addition of the isocyanate. The pH is 3.06 at the beginning and increases to 5.91 during the reaction. After a reaction time of 60 minutes a clear solution was created. The batch is then cooled to 30 ° C in 120 minutes, the pH is 4.18. There are added 28.3 g of citric acid monohydrate dissolved in 23.4 g of water. A clear 35.0% solution with a pH of 2.10 is obtained.

To the solution filtered through a pleated filter, 3000 ml of acetone are added at room temperature. After 1 hour, the precipitated white solid is filtered off, washed with acetone and dried in vacuo at 20 ° C to constant weight (yield 92.5%>, residual moisture 0.6 wt .-%).

 A solution of 1.75 g of powder in 5 ml of water is clear and has a pH of 2.10. Example 3

 (Bisulfite: NCO = 1.05: 1)

To a solution of 422.7 g of water and 609.5 g of sodium bisulfite solution (NaHSO ₃ , 38-40% in water) are added 182.9 g of hexamethylene diisocyanate at 23 ° C in one portion, the mixture by means of a dispersing machine with rotor Stator principle (Ultraturrax aggregate of

Company IKA) is dispersed at 12,000 revolutions per minute. The temperature of the reaction mixture is raised to 56 ° C. within 45 minutes after addition of the isocyanate. The pH is initially 3.51 and increases to 4.84 during the reaction. After a reaction time of 60 minutes, the solution is clear. The speed is reduced to 8000 revolutions per minute and cooled to 33 ° C within 2 hours. The solution has a pH of 3.50. To this solution is added 2600 ml of acetone. It is stirred for 2 hours. The precipitated white solid is filtered off, washed with acetone and dried in vacuo at 20 ° C to constant weight (yield 86.5%, residual moisture 0.69 wt .-%).

The solid is then homogeneously mixed with 31.1 g of citric acid monohydrate by means of a grinder. A solution of 1.75 g of powder in 5 ml of water is clear and has a pH of 2.00.

Example 4

 (Bisulfite: NCO = 1.00: 1)

To a solution of 391.4 g of water and 527.6 g of sodium bisulfite solution (NaHSC> 3, 38-40% in water) are added 166.3 g of hexamethylene diisocyanate at 23 ° C in one portion, the mixture by means of a dispersing machine with rotor - Stator principle (Ultraturrax unit from IKA) is dispersed at 15,000 revolutions per minute. The temperature of the reaction mixture is raised to 60 ° C. within 60 minutes after addition of the isocyanate. The pH is 3.02 at the beginning and increases to 5.84 during the reaction. After a reaction time of 180 minutes, a turbid solution has formed. The speed will be 12000

Reduced revolutions per minute and cooled to 34 ° C within 2 hours. The batch is filtered. The clear solution has a pH of 4.34. There are added 28.3 g of citric acid monohydrate dissolved in 23.4 g of water. A solution having a solids content of 35.25% by weight and a pH of 2.12 is obtained.

To this solution is added 3000 ml of acetone. It is stirred for 2 hours. The precipitated white solid is filtered off, washed with acetone and dried in vacuo at 20 ° C to constant weight (yield 90.3%, residual moisture 0.5 wt .-%).

A solution of 1.75 g of powder in 5 ml of water is clear and has a pH of 2.20.

Example 5

(Bisulfite: NCO = 1.05: 1)

To a solution of 431.8 g of water and 554.1 g of sodium bisulfite solution (NaHSC> 3, 38-40% in water) are added 191.8 g of bis (isocyanatomethyl) cyclohexane (mixture of isomers, 1.4 and 1.3 - Isomer) at 20 ° C in one portion, wherein the mixture is dispersed by means of a dispersing machine with rotor-stator principle (Ultraturrax unit from IKA) at 15,000 revolutions per minute. After 2 hours, the setting of the dispersing unit is increased to 18,000 revolutions per minute. After another 30 minutes, the speed is increased to 20,000 revolutions per minute. The temperature of the reaction mixture is 3 hours after addition of the isocyanate 60 ° C. After a reaction time of 3.5 hours, the organic phase has disappeared. It is then cooled in 1, 5 hours at 40 ° C, while further dispersed at 15000 revolutions per minute. After a total reaction time of 5 hours, the mixture is filtered and mixed with a solution of 28.3 g of citric acid monohydrate in 23.4 g of water, resulting in a pH of 2.58. A 35.0% solution with a pH of 2.58 is obtained.

At room temperature, 3000 ml of acetone are added to this solution. It is stirred for 2 hours. The precipitated white solid is filtered off, washed with acetone and dried in vacuo at 20 ° C to constant weight (yield 80.5%, residual moisture content 0.9 wt .-%).

A solution of 1.75 g of powder in 5 ml of water is clear and has a pH of 2.60.

Example 6

(Bisulfite: NCO = 1.05: 1.0). A solution of 326.5 g of water, 461.7 g of sodium bisulfite solution (NaHSO ₃ , 38-40% in

Water) and 9.8 g of an adduct of 2 moles of citric acid and 1 mole of hexamethylene diisocyanate (obtained by drying the aqueous solution, dispersing at 12,000 revolutions per minute). To this template are added at 20 ° C 138.6 g of hexamethylene diisocyanate in one portion. The temperature of the reaction mixture is increased to 50 ° C. with dispersion within 60 minutes. After reaching 50 ° C., 7.8 g of citric acid monohydrate dissolved in 6.5 g of water are added, resulting in a pH of 3.05. The mixture is kept for 1 hour at 50 ° C and then cooled to 25 ° C within 2 hours. The pH of the clear solution is 2.92 at room temperature. There are 23.6 g of citric acid monohydrate dissolved in 19.5 g of water. After adjusting the solids content with 26.4 g of water to obtain a clear 35.0% solution with a pH of 2.30.

At room temperature, 3000 ml of acetone are added to this solution. It is stirred for 2 hours. The precipitated white solid is filtered off, washed with acetone and dried in vacuo at 20 ° C to constant weight (yield 93.5%, residual moisture 0.7 wt .-%).

A solution of 1.75 g of powder in 5 ml of water is clear and has a pH of 2.4.

Comparative example

According to US4413997 (column 2, lines 54-60), an isophorone diisocyanate (IPDI) bisulfite

Adduct prepared and applied in a 30% aqueous solution according to the specifications of US4413997.

Nips (3, 3-3, 5mm) are pretreated with 300% water (20 ° C) and 2% calcium hydroxide overnight (reliming) and the liquor is drained off. Subsequently, the arms are washed with 200% water (based on weight of the body) and the liquor is drained off. The pod material is then destined for deliming in 100% fresh water with 0.1% sodium bisulfite and 1.2% of an N-free decalcifying agent for 30 minutes. Annually (pH 8.4) 0.2% of a fatty alcohol ethoxylate-based degreaser, 150% water and 0.15% of a beeignem (Novobate® 1547, product of Novozyme) are added and agitated for 1 hour. The liquor is then drained and the buff washed again. In fresh liquor with 70% water, 7% sodium chloride, 0.5% formic acid (1: 5) and 1.5% sulfuric acid (1:10) is pickled for 3 hours (pH 2.7). The material was then divided for the experiments and returned to the barrel.

The keg is moved overnight (pH 2.1). The next morning, the fleet is drained and the

Pure with 100% water, 0.5% sodium formate and 1.75% sodium bicarbonate (1:20) de-prepared (pH 4.5).

In 100% fresh liquor, the buff is treated for 30 minutes with 10% of the isophorone diisocyanate bisulphite adduct (addition of 33% of a 30% aqueous solution) according to the specifications of US4413997 (pH 4.1). Then, by adding sodium bicarbonate solution (1:10) over 5 hours, the pH was adjusted to 9.0. The barrel is then moved overnight. The next morning, the shrinking temperature is measured. The resulting leathers were finally adjusted to pH 5 with 5% acetic acid in 3 hours, stored overnight on the box. For the according to US4413997 with the isophorone diisocyanate bisulfite adduct without the

Leather obtained using a carboxylic acid, the shrinkage temperature was 66 ° C. In comparison, the retanning by addition of 24.9 g of anhydrous citric acid to 950 g of the above 30% aqueous solution by the same procedure, a shrinkage temperature of 68 ° C were measured. In each case, 33% of the isophorone diisocyanate-bisulphite adduct solution was used in relation to pum weight. In addition, the leather treated without citric acid was not so good foldable and shows an undesirable scar pull.

B) Examples of use (Gerbungeni

The quantities of the respective products used (for example commercial products as supplied) are based on the weight of the raw materials or intermediates used.

B 1: medical sheepskin, chromium free

In a commercially available reel, air-dried sheep skins are backwashed with 20 l of water per coat and 2.0 g / l of a nonionic emulsifier based on a fatty alcohol ethoxylate at 25 ° C. overnight and then defiled. The thus prepared skins are at 35 ° C twice in an aqueous liquor with 2.0 g / 1 of a nonionic emulsifier based on a fatty alcohol ethoxylate for 60 min. degreased and thoroughly rinsed with warm water after draining the liquor.

To prepare the tanning new liquor is submitted and mixed without pimple at 25 ° C with 5.3 g / 1 inventive product of Example 1. By adding magnesium oxide in three doses, the pH is gradually increased to 8.8 and then the temperature is raised to 40 ° C. After 12 h run time, 7 g / 1 sulfated synthetic fatliquor and 2.0 g / l lecithin-based dispersing aid are added to the same bath. After 2 h, the pH is reduced to 5.5 with formic acid. After draining the liquor, thoroughly rinse with cold water and finish the skins in a commercial manner and have a shrinkage temperature of 77 ° C.

Compared to commercially tanned with glutaraldehyde furs skins of the invention have a much lighter color of both the leather and the wool and a better light fastness.

In the aldehyde test DIN 53315 A, the measured values are significantly reduced compared to the prior art and are below the detection limit of the method of 20 ppm.

Good results were also obtained with the powders of Examples 2 to 6.

B 2: Production of wet white for full grain upholstery leather Salted cowhides are washed commercially, limed, depilated, fleshed, and split. The pod material (2.7 mm) is washed with 200% water and drained the liquor. For deliming, the bars are stirred in 30% fresh water with 0.4% sodium bisulfite and 1.4% of an N-free decalcifier (Decaltal® AN, product of BASF) for 10 minutes. Then, 0.15% of a fatty alcohol ethoxylate-based degreaser is added and agitated for 1 h at 25 ° C (pH 8.4). Then 50% water and 1% of a Beeignym (Novobate 1547, product of Novozyme) are added and agitated for 1 hour. The liquor is then drained and the buff washed again.

In 50% fresh liquor, the buff is conditioned for 1 hour with 0.25% magnesium oxide to pH 9.5 and mixed with 6% of the product according to the invention from Example 1 (as powder or diluted with water 1: 1) (pH 8.3 ). After 3 hours, the pH of the liquor is raised to 9.0 to 9.5 by adding 0.3% of magnesium oxide, and the shrinkage temperature is measured. After a period of 1 hour, 0.2% of magnesium oxide and 0.1% of an aqueous ammonia solution (diluted with water 1: 5) are added (after 1 hour, the pH is 9.1) and the barrel at 35 ° C over Night moves (pH 9.2).

To prepare the retanning, the pH is reduced to 5.3 in 3 portions with 0.6% of formic acid (diluted with water 1: 5) in 3 portions. After 90 minutes, the fleet is drained. The wet white leather (chrome-free tanned leather intermediate for mechanical treatment and further (subsequent) tanning) are washed and wilted. The shrinking temperature is measured again (77 ° C) and the leathers folded to 1, 0 mm.

With regard to the properties, a leather having a shrinking temperature of 77 ° C., a smooth grain texture, a dry, firm feel, and a very good wiping and folding properties were obtained.

Good results were also obtained with the powders of Examples 2 to 6. The shrinking temperature was always above 70 ° C, the grain pattern was smooth, the leather have a dry, firm grip and a good to very good Abwelkbarkeit and folding.

B 3: Preparation of wet white for a full-grain upholstery leather

Salted cowhides are washed commercially, limed, depilated, fleshed, and split. The pod material (2.7 mm) is washed with 200% water and drained the liquor. For deliming, the bins are agitated in 30% fresh water with 0.4% sodium bisulfite and 1.4% of an N-free decalcifying agent (Decaltal AN, product of BASF) for 10 minutes. Then 0.15% of a fatty alcohol ethoxylate-based degreaser is added and for 1 h at 25 ° C (pH 8.4). Then 50% water and 1% of a Beeignym (Novobate® 1547, product of Novozyme) are added and agitated for 1 hour. The liquor is then drained and the buff washed again.

In 50% fresh liquor, the buff is conditioned for 1 hour with 0.25% magnesium oxide to pH 9.5 and mixed with 6% of the product of Example 1 according to the invention (as powder or diluted with water 1: 1) (pH 8.7 ). After 1 h of penetration time, 2.0% of a 4,4'-dihydroxydiphenylsulfone / naphthalenesulfonic acid / formaldehyde condensate (eg TANIGAN® BN, product of LANXE SS) and 1% of the formaldehyde condensate of aromatic sulfonic acids (eg TANIGAN® PR, Product of Lanxess). After a further 2 hours (pH 7.8), 0.2% of magnesium oxide and 0.1% of an aqueous ammonia solution (diluted with water 1: 5) are added (pH after 1 hour 9.0) and the shrinkage temperature is measured. The cask is agitated overnight at 35 ° C (pH 8.9).

To prepare the retanning, the pH is reduced to 5.3 with 0.6% formic acid (diluted with water 1: 5) in 3 portions. After 90 minutes, the fleet is drained. The wet white leathers are washed and wiped off. The shrink temperature is measured again (76 ° C) and the leather folded to 1.0 mm.

Good results were also obtained with the powders of Examples 2 to 6. B 4: Production of wet white for a padding leather:

Salted cowhides are washed commercially, limed, depilated, fleshed, and split. The pod material (2.7 mm) is washed with 200% water and drained the liquor. For deliming, the bins are agitated in 30% fresh water with 0.4% sodium bisulfite and 1.5% of an N-free decalcifying agent (Decaltal® A-N, product of BASF) for 10 minutes. Then, 0.15% of a fatty alcohol ethoxylate-based degreaser is added and agitated for 90 minutes at 25 ° C (pH 8.5). Then 50% water and 1% of a Beeignym (Novobate® 1547, product of Novozyme) are added and agitated for 45 minutes. The liquor is then drained and the buff washed again.

The prepared fin is conditioned in 50% liquor with 1% sodium acetate and 1% sodium carbonate to pH 9.9 and then admixed with 6% of the product according to the invention from Example 1 (as powder or diluted with water 1: 1) (pH 8, 6). After a 30 minute penetration time, 4% of a 4,4'-dihydroxydiphenylsulfone / naphthalenesulfonic acid / formaldehyde condensate (e.g.

TANIGAN® BN, product of LANXESS) and 2% of a formaldehyde condensate of aromatic sulfonic acids (eg TANIGAN® PR, product of LANXESS) (added as 50% solutions, pH 7) was added. After 1 hour (pH 8.2), the pH of the liquor is raised to 8.7 and the shrinkage temperature is measured by addition of a total of 1% sodium carbonate (diluted 1:10 with water) in the course of 2 hours. The leather is then agitated overnight at 30 ° C (pH 8.1). To prepare the retanning, add 0.6% formic acid (diluted 1:10 with water) in 3

Portions of pH reduced to 7.2, the liquor drained and the wet white leather wilted off. The shrink temperature is measured (70 ° C) and the leather folded to 1.0 mm thickness.

Good results were also obtained with the powders of Examples 2 to 6.

B 5: Preparation of wet white for shoe upper Salted cowhides are washed, limed, depilated, fleshed, and split in commercial manner. The pumice material (2.6 mm) is washed with 200% liquor and drained the liquor. For deliming the bins are in the barrel in 100% liquor and 0.3% sodium bisulfite, 1.0% of an N-free decalcifying agent (eg Decaltal® ES-N, product of BASF) and 0.3% of a mixture of dicarboxylic acids (eg Bascal® S, product of BASF) for 1 hour at 25 ° C moves. At pH 7.7, 1% of a beeignem (Novobate 1547, product of Novozyme) and 0.1

% of a fatty alcohol ethoxylate-based degreaser was added, agitated for an additional 45 minutes, and then the liquor was drained and the buff washed twice.

The prepared boshes are conditioned for 1 hour with 1% sodium acetate to pH 8.0 and mixed with 1.7% of the product according to the invention from Example 1 (as a powder or diluted with water 1: 1). After 20 minutes of penetration time, 0.2% sodium carbonate (diluted 1:10 with water) is added and agitated for 30 minutes. Then another 3.4% of the product according to the invention from example 1 (diluted as powder or with water 1: 1) is added. After 1.5 hours, the pH is raised to 8.2 and the shrinkage temperature is measured by adding in portions a total of 0.4% sodium carbonate (diluted 1:10 with water) within 2 hours. Then the barrel is moved at 35 ° C overnight. The pH is then reduced to 7.0 with formic acid (diluted 1:10 with water). You move the barrel for 2 hours. Then the fleet is drained. The wet white leathers are washed and wiped off. The shrink temperature is measured again (72 ° C). The leathers can be processed without problems and are folded to a thickness of 1, 2 mm. Good results were also obtained with the powders of Examples 2 to 6.

B 6: Chrome-tanned car upholstery leather: The crimped wet white leathers of Example B 4 are agitated with 300% water (35 ° C) and 0.2% of a fatty alcohol ethoxylate at pH 7.6 for 20 minutes. After draining the liquor, 50% water, 3% of a naphthalenesulfonic acid / formaldehyde condensate (TANIGAN® RFS, product of LANXESS), 1.5% sodium formate and 3% of a lecithin-based fatliquoring agent (BAYKANOL® Licker SL, product of Lanxess) (diluted with water 1: 8) was added. After a running time of 30 minutes, 2% of a polyacrylate dispersion (LEUKOTAN® 1084, product of Dow / Lanxess) (diluted with water 1: 3) and after a further 10 minutes 3% of a modified polyamide carboxylic acid (LEVOTAN® L, product of Lanxess ) (diluted with water 1: 3) were added as filling and softening retanning agents. After another 10 minutes run time, 8% tare and 5% of a synthetic tanning agent based on a 4,4'-dihydroxydiphenylsulfone / naphthalenesulfonic acid / formaldehyde condensate (TANIGAN® BN, product of LANXESS) and after 30 minutes (pH 5.5) are still 8% Mimosa and another 5% of a synthetic tanning agent based on a 4,4'-dihydroxydiphenylsulfone / naphthalenesulfonic acid / formaldehyde condensate (TANIGAN® BN, product of LANXESS). Then 2 hours with 3% dye dyed (pH 5.5 - 5.8). After Auffleet with 50

% Of water, another 4% of a lecithin-based fatliquor (BAYKANOL® Licker SL, product of Lanxess) (diluted with water 1: 8) is added and drummed at 50 ° C for 1 hour. Then, by adding 2% formic acid (diluted with water 1: 5) in 2 portions fixed for 45 minutes (pH 4) and drained the liquor. It is washed with 200% water (50 ° C). In fresh liquor (100% water, 50 ° C) is mixed with 4% of a lecithin-based fatliquor

(BAYKANOL® Licker SL, product of Lanxess) (diluted with water 1: 8) for a period of 1 hour the top-greasing performed. Then it is acidified with 1% formic acid (diluted with water 1: 5) in two steps to pH 3.4 and fixed for 45 minutes. Then the liquor is drained, washed twice with 200% water and the leather commercially available by stretching, vacuum drying (50 ° C), hanging drying, galleries, Millen, studs completed.

You get very soft, yet solid-grained, no matter colored crust leather with a very uniform millet, which can be prepared excellent.

B 7: Chrome-free tanned upper leather:

The folded wet-white leather from example B 5 are washed at 35 ° C. in 150% liquor with 0.3% formic acid (diluted 1:10 with water) for 20 min. (PH 4.3) and the liquor is drained off.

In fresh liquor (100% water 30 ° C) is used for pre-greasing with a mixture of 2% of a synthetic fatliquor and 1% of a lecithin-based fatliquor (diluted with water 1: 8) and 5% of a 4,4'-dihydroxydiphenylsulfone-based tanning agent (TANIGAN® 3LN, product of Lanxess). After 20 minutes, 10% of a dihydroxydiphenylsulfone / naphthalenesulfonic acid / formaldehyde condensate (TANIGAN® CF liquid, product of LANXESS) (diluted with water 1: 1) are added in 2 portions and infiltrated for 45 minutes (pH 4.5). Then, 70% water and 2% of a dispersant based on aromatic

Sulfonic acids (TANIGAN® PAK, product of Lanxess) added. After a running time of 15 minutes, initially 4% of a modified polyamide carboxylic acid (LEVOTAN LB, product of Lanxess) (diluted with water 1: 3) and 3% of a polyacrylate dispersion (LEUKOTAN® 8090, product of Dow / Lanxess) are added. After a further 20 minutes, a mixture of 3% of a synthetic and 2% of a lecithin-based fatliquor (BAYKANOL® Licker

FSU and SL, products of Lanxess) (diluted with water 1: 5) was added and after a further 15 minutes a mixture of 5% Mimosa and 12% of synthetic tanning agents based on 4,4'-dihydroxydiphenylsulfone / formaldehyde condensates (TANIGAN® V , TANIGAN® 3LN, products of LANXESS). After a running time of 30 minutes is sweetened with 12% of a mixture of chestnut and synthetic tannins based on a

Dihydroxydiphenylsulfone / naphthalenesulfonic acid / formaldehyde condensate (TANIGAN VR, product of LANXESS) and a resin tanning agent (RETINGAN® ZF Plus, product of Lanxess) in the presence of 1% dye and 2% of a dyeing aid (BAYKANOL® TF-2N, product of Lanxess) tanned and dyed. The next morning, after adding 100% water (50 ° C) with a mixture of 3% of a lecithin-based fatliquor, 3% of a lanolin-based fatliquor (BAYKANOL® Licker LA, product of Lanxess), 2% of a synthetic fatliquor (BAYKANOL® Licker SL, FSU, Lanxess products) as well as 1% claw oil (eg Atlas Neatsfoot® Oil 30 CT) (diluted with water 1: 5) performed a top greasing. After a running time of 60 minutes is fixed with 3% formic acid (diluted with water 1:10) in 3 portions within 80 minutes (pH 3.6) and drained the liquor. The leathers are washed and finished commercially.

You get very soft, yet solid-grained, no matter colored crust leather with a very uniform millet, which can be prepared excellent.

Cl) Preparation of a cationic polycondensate based on the product of Example 2

216.8 g (2.105 mol) of diethylenetriamine and 302 g (2.07 mol) of adipic acid are combined and heated to 140 ° C and stirred for 1 hour at this temperature. Subsequently, the temperature slowly increased to 180 ° C within 2 hours. It is held at this temperature for a further hour until 75 g of water have distilled off. The resulting polycondensate is taken up in 450 g of water. This gives a 50% solution with a viscosity of 415 mPas (23 ° C) and a base equivalent weight of 398 g / mol of base N. 398 g of the above prepared 50% polyamidarnine solution (1 mol) and 398 g of water are presented.

At 20 ° C 0.7 mol of a 25% solution of the product of Example 2 are added dropwise in water within 30 minutes. The mixture is stirred for 8 hours at 20 ° C after. Then, 4.45 g (0.11 mol) of the above-described polyarnidamine solution is added keeping the pH above 7. The mixture is heated to 50 to 55 ° C and held for about 4 hours at this temperature until the viscosity of a 15% solution to 60-70 mPas at 23 ° C has risen. Dilute with water to a solids content of 15% and stop the reaction by adding 15 g of 48% sulfuric acid and add a 50% citric acid solution until a pH of 2.7 is reached. After adjusting the solids content with water to obtain a 15% yellowish solution with a viscosity of 70 mPas at 23 ° C.

C2): Preparation of a cationic polycondensate based on the product from Example 6 Analogously to Example C1, 1 mol of the basic polyamine damin solution was initially charged and dissolved in a solution

Concentration of 25% with 0.7 mol of a 25% aqueous solution of the product of Example 6 implemented. After reaching a viscosity of 60 mPas is diluted with water to a solids content of 15% and the reaction stopped by adding a 48%> sulfuric acid. Formic acid is added until a pH of 2.9 is reached. After adjusting the solids content with water to obtain a 15%> yellowish solution with a viscosity of 58 mPas at 23 ° C.

C3): Application of the products according to Example Cl) and C2) as a wet strength agent for paper

The resulting cationic polymer solutions according to Examples Cl) and C2) are suitable for increasing the wet strength of paper.

Bleached pine / birch sulphate pulp (weight ratio 80:20) is ground to a freeness of 38 ° Schopper-Riegler at a stock consistency of 2.5% in Dutch. From the preserved

Pulp suspension is placed 100 g in a beaker and diluted to 1000 ml with water. The amounts of the polycondensate solutions (% by weight of the application form, based on pulp) prepared according to Example C1) and Example C2) given in the following table are then added to the pulp and stirred for 3 minutes. Thereafter, the contents of the beakers are placed on a sheet former (Rapid-Köthen apparatus), diluted with 8000 ml of water and forms paper sheets with a basis weight of about 80 g / m ² (according to DIN 54358, part 1). The paper sheets are dried for 8 minutes at 85 ° C and 60 mbar and heated in a drying oven for 10 minutes at 110 ° C.

After conditioning, 5 test strips each 1.5 cm wide are cut out of each paper sheet and immersed in deionized water for 5 minutes. Then the wet strips of a tensile testing machine (DIN 53112, Part 2) are tested for their wet fracture load.

The results obtained are summarized in the following table.

 Product from Example wet fracture load [N] at an input quantity (based on pulp) of

 2% 4% 6%

 Cl 10,8 15,8 18,5

 C2 10.2 14.8 17.9

Claims

claims

A composition comprising a) at least one carbamoylsulfonate group-containing compound and b) at least one carboxylic acid containing less than 0.001% by weight, based on the composition of emulsifier, wherein the carbamoylsulfonate-containing compounds of component a) comprises a reaction product at least one organic polyisocyanate and at least one bisulfite and / or disulfite, characterized in that the organic polyisocyanate has a molecular weight of less than 400 g / mol and attached to aliphatic or cycloaliphatic NC O groups, in particular 1, 4-diisocyanatobutane, 1 , 6- diisocyanatohexane (HDI), 1, 5-diisocyanato-2,2-dimethylpentane, 2,2,4-b zw. 2, 4, 4- trimethyl-l, 6-diisocyanatohexane (TMHI), 1, 3- and 1, 4-diisocyanatohexane, 1, 3- and 1, 4-di-isocyanato-cyclohexane (CHDI) and any mixtures of these isomers , 1-isocyanato-2-isocyanatomethyl-cyclopentane, 1, 2-, 1, 3- and 1, 4-bis (isocyanatomethyl) cyclohexane and any mixtures of isomers, 1, 2, 1, 3 and 1, 4 - Bis (isocyanatoethyl) cyclohexane and any mixtures of these isomers, 1, 2, 1, 3- and 1, 4-bis (isocyanato-n-propyl) cyclohexane and any mixtures of these isomers, l isocyanatopropyl-4-isocyanatomethyl - cyclohexane and isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 1-isocyanato-1-methyl-4-isocyanatomethylcyclohexane (IMCI), 2,4'- and 4 , 4'-diisocyanatodicyclohexylmethane (Hi ₂ MDI) and I somere, dimery 1-diisocyanate (DDI), bis (isocyanatomethyl) bicyclo [2.2.1] heptane (NBDI), bis (isocyanatomethyl) tricyclo [5.2 .1.0 ² ' ⁶ ] decane (TCDDI) and isomers and any mixtures of such diisocyanates and xylylene diisoc yanate of the formulas

2. Composition according to at least one of the preceding claims, characterized in that as further additives fatliquoring agents, fillers and / or buffer substances are contained or are not contained.

3. A composition according to at least one of the preceding claims, characterized in that it contains as component b) at least one carboxylic acid, preferably oxalic acid, succinic acid, glutaric acid or adipic acid, in particular at least one hydroxy-polycarboxylic acid, preferably citric acid, tartaric acid or lactic acid or mixtures thereof, or at least one reaction product of a polycarboxylic acid and a polyisocyanate containing carboxylic acid groups contains.

4. Composition according to at least one of the preceding claims, characterized in that the composition is an aqueous solution.

5. Composition according to at least one of the preceding claims, characterized in that the composition is solid and particulate.

6. A process for the preparation of the composition according to at least one of claims 1 to 8, which comprises at least one organic polyisocyanate having a molecular weight of less than 400 g / mol with aliphatic or cycloaliphatic NCO groups with at least one bisulfite and / or disulfite in the presence of water and with simultaneous action of shear forces, preferably with a rotor-stator mixer, the carboxylic acid of component b) and optionally further additives added before, during or after the bisulfite and / or disulfite reaction and the resulting reaction mixture is then optionally dried.

7. A process for the preparation of the composition according to claim 6, characterized in that the resulting liquid reaction mixture is added to a precipitant and the precipitate is dried.

8. Use of the composition according to at least one of claims 1 to 5 as Vorgerbstoffe, retanning or tanning agents for tanning, pretanning or retanning of hides and skins.

9. Use of the composition according to at least one of claims 1 to 5 as a reaction component for amino-containing compounds.

10. Use according to claim 9, characterized in that the amino group-containing compounds are biological material, in particular tissue in association with other materials present in vivo such as skin material, connective tissue, bones, organs, muscle fibers or, wall material of blood vessels optionally in isolated or purified Shape.

11. Use of the composition according to at least one of claims 1 to 5 as auxiliaries for papermaking, in particular for the production of wet strength agents or retention aids.

12. Use of the composition according to at least one of claims 1 to 5 as a crosslinker for water-soluble protein-based polymers, in particular gelatin.

13. Reaction products obtainable by reacting amino-containing compounds with the compositions according to claim 1.