TW201315750A - Composition based on compounds containing carbamoylsulphonate groups - Google Patents

Abstract

Composition containing (a) at least one compound containing carbamoylsulphonate groups, and (b) at least one carboxylic acid, which contains less than 0.001 wt% of emulsifier, based on the composition, wherein the component (a) compound containing carbamoylsulphonate groups is a reaction product of at least one organic polyisocyanate and at least one bisulphite and/or disulphite, characterized in that the organic polyisocyanate has a molecular weight of less than 400 g/mol and aliphatically or cycloaliphatically attached NCO groups.

Description

a composition based on a compound containing an aminomethyl sulfonate

The present invention relates to a composition based on a compound containing an aminomethyl sulfonate group, a method for producing the composition, and the use of the composition as a reaction component for a compound containing an amine group, for example, as Leather auxiliaries, especially as leather crepe preparations, retanning preparations or pre-tanning preparations.

Polyisocyanates having a functionality greater than 2 are useful as crosslinkers for polymeric materials and have, for example, been used successfully in, for example, metal surface coatings. Polyisocyanates can be used in unmodified form for pure organic coatings, depending on the field of use. The great demand for solvent-free systems has led to the development of coatings for solvent-free or low-solvent systems. The polymer binder in this coating is desirably crosslinked using a polyisocyanate which is dispersible in water. However, the cross-linking agent needs to be directly dispersed in water before use, since the NCO-based system is unstable in water and thus has a limited life span. Also known are water-dispersible polyisocyanates in leather (tanned, re-tanned, finished and coated), paper (wet strength enhancers, dry strength enhancers, paper coating) Cloth) and auxiliaries in the manufacture of fabrics (resin finishing for crease resistance of cotton, shrink-proof finishing of wool). Polyisocyanates can also be used to crosslink amine-containing polymers, such as monomers (eg isobutylene, butadiene, acrylonitrile, isoprene) The olefin, styrene and acrylic monomers are copolymers of the substrate, in which case the amine group can be introduced by subsequent reaction of the copolymer or during the copolymerization. Polycondensates or polyaddition products may also be considered as polymers containing amine groups.

There are certain uses in which it is advantageous or even necessary to use a crosslinking agent which forms a clear solution in water and which is sufficiently stable, i.e. before the addition of the amine-containing reaction component. It is also particularly advantageous when such crosslinkers react rapidly and fully with the amine function of the binder at low temperatures. It has long been known to crosslink amine-containing polymers with polyisocyanates. This method is, for example, a solvent-containing 2-ingredient reverse coating system based on polyamines and isocyanate-terminated prepolymers/polyester urethanes for flexible substrates such as fabrics and leathers. The situation. Due to the high reactivity of the amine groups, in this case the ingredients are directly mixed in an applicator unit. It is possible to first mix the components with each other to form a 1-component reaction system, for example by using a blocked form of polyisocyanate. In this case, a relatively high reaction temperature is usually required from the coating to also release a blocking agent. There are also formulations in which the blocking agent becomes part of the final coating and ends up being incorporated into the network.

In other words, there are also formulations in which an isocyanate-containing crosslinking agent and an amine group-containing polymer are required in a solvent-free aqueous system and also need to be at a low temperature, especially at room temperature, possibly even in the presence of water. The use of a fast reaction of a blocked polyisocyanate. This is for example when using natural amine-containing polymers like collagen, gelatin Or the case of chitosan. In this application, for example, aliphatic aldehydes such as formaldehyde or glutaraldehyde are used as crosslinking agents.

In particular, applications requiring further biomaterials (both in vivo and in vitro) must meet the conditions regarding the purity of the accompanying material or with regard to processability, and this is a disadvantage that known products still have.

No. 3,984,365 has described bisulphite adducts for leather, paper or fabric finishing, however both are based on NCO prepolymers. Such adducts based on NCO prepolymers have also been used in fabric applications in GB2003521. The same applies to GB 1 491 437 and US 3,989,458, where such products are used in applications other than leather.

DE-A 10 2006 056 479 describes bisulfite-terminated polyisocyanates obtainable in the presence of a solvent. It is also known from EP-A 0 690 135, EP-A 0 814 168 and EP-A 1 647 563 that blocked isocyanates are likewise known from US Pat. No. 4,413,997. Internal or external emulsifiers are used as auxiliaries for the synthesis of aqueous bisulfite-terminated polyisocyanates.

US4413997 utilizes IPDI-based bisulfite adducts for tanning, but they have the disadvantage that their shrinkage temperatures are not ideal.

Therefore, the problem underlying the present invention is to provide a water-soluble polyisocyanate-based crosslinking agent for aqueous systems, which is consistent with The standard, which is highly dependent on the stability of the formulation, the reactivity of the amine-containing polymer at room temperature and in an aqueous medium, and the use as a reaction component for reaction with biological materials.

Surprisingly, it has now been found that a composition comprising a) at least one amine-containing mercaptosulfonate-containing compound, and b) at least one carboxylic acid, based on the composition, containing less than 0.001% by weight An emulsifier, wherein the component a) the amine-containing mercaptosulfonate-containing compound is a reaction product of at least one organic polyisocyanate and at least one hydrogensulfite and/or disulphite, characterized in that The organic polyisocyanate has a molecular weight of less than 400 g/mole and an NCO group attached via aliphatic or cycloaliphatic, in particular 1,4-diisocyanate butane, 1,6-diisocyanate hexane ( HDI), 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanate hexane (TMHI , 1,3- and 1,4-diisocyanate hexane, 1,3- and 1,4-diisocyanatocyclohexane (CHDI) and any desired mixtures of such isomers, 1- Any of isocyanato-2-isocyanatomethylcyclopentane, 1,2-, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane and isomers Mixture, 1,2-, 1,3- and 1,4-bis(isocyanatoethyl)cyclohexane and any of these isomers Mixture, 1,2-, 1,3- and 1,4-bis(isocyanato-n-propyl)cyclohexane and any desired mixture of such isomers, 1-isocyanatopropyl 4-isocyanatomethylcyclohexane and isomer, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 1-Isocyanato-1-methyl-4-isocyanatomethylcyclohexane (IMCI), 2,4'- and 4,4'-diisocyanatodicyclohexylmethane (H12MDI) 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 desired mixtures of such diisocyanates and decyl diisocyanates of the formula

Ingredient a)

The amine-containing mercaptosulfonate-containing compound is a compound incorporated into the following structural unit: -NH-CO-SO ₃ -K ⁺

Wherein K ⁺ is a cation equivalent.

It is preferred to use the above diisocyanate. However, it is also possible to use monofunctional aliphatic isocyanates such as, for example, butyl isocyanate, hexyl isocyanate, cyclohexyl isocyanate, stearyl isocyanate. Ester or dodecyl isocyanate and/or polyisocyanate having an average NCO functionality of from 2.2 to 4.2.

The higher functional polyisocyanate is preferably a polyisocyanate mixture which consists essentially of the following components: trimeric 1,6-diisocyanate hexane, trimeric 1,2-, 1,3- or 1,4-double (isocyanatomethyl)cyclohexane, trimeric 1,2-, 1,3- or 1,4-bis(isocyanatoethyl)cyclohexane, trimer 1,2-, 1, 3- or 1,4-bis(isocyanato-n-propyl)cyclohexane, trimeric 1-isocyanatopropyl-4-isocyanatomethylcyclohexane and isomers, Or trimeric 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and optionally dimerized 1,6-diisocyanate hexane, dimerization 1, 2-, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, dimerized 1,2-, 1,3- or 1,4-bis(isocyanatoethyl) Cyclohexane, dimerized 1,2-, 1,3- or 1,4-bis(isocyanato-n-propyl)cyclohexane, dimeric 1-isocyanatopropyl-4-iso Cyanate methylcyclohexane and isomers, or dimerized 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and correspondingly higher a homologue comprising a trimeric isocyanate group and optionally a uretdione group and having an NCO content of from 19 to 24% by weight, as by conventional catalysis Polymerization and by 1,6-diisocyanate hexane, 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-iso Cyanate propyl-4-isocyanatomethylcyclohexane and isomers, or 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane It is obtained by formation of a trimeric isocyanate of an alkane, and it preferably has an (average) NCO functionality of 3.2 to 4.2.

The use of monofunctional and higher than difunctional isocyanates is preferably limited to no more than 10 mole percent in each case, based on the total polyisocyanate.

However, the above aliphatic, cycloaliphatic and araliphatic diisocyanates are very preferred. Particularly preferred are hexamethylene diisocyanate (HDI), diisocyanate cyclohexane, 1,2-, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane. And any desired mixture of isomers, 1,2-, 1,3- and 1,4-bis(isocyanatoethyl)cyclohexane and any desired mixture of such isomers, 1, 2-, 1,3- and 1,4-bis(isocyanato-n-propyl)cyclohexane and any desired mixtures of such isomers, 2,4'- and 4,4'- Diisocyanate dicyclohexylmethane, 1-isocyanatopropyl-4-isocyanatomethylcyclohexane and isomers and 1-isocyanato-3,3,5-trimethyl 5--5-isocyanatomethylcyclohexane (IPDI). This last group, specifically hexamethylene diisocyanate (HDI), 1,2-, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane, and preferably a mixture of isomers.

The bisulfite and/or pyrosulfite is preferably an alkali metal or ammonium salt thereof, especially sulfurous acid or, respectively, a sodium salt of disulphurous acid, that is, sodium hydrogen sulfite (NaHSO, respectively). ₃ ) and sodium metabisulfite (Na ₂ S ₂ O ₅ ).

It is also advantageous to use other alkali metal and ammonium salts of such acids, namely potassium hydrogen sulfite, potassium metabisulfite, lithium hydrogen sulfite, lithium metabisulfite, ammonium hydrogen sulfite, ammonium metabisulfite and the like. Simple tetraalkylammonium salts such as tetramethylammonium bisulfite, tetraethylammonium bisulfite Wait. For capping, the salts are preferably used in the form of an aqueous solution having a solids content of from 5 to 40% by weight.

In a preferred embodiment of the invention, the amine-containing mercapto group-containing compound is based on an aliphatic polyisocyanate such as hexamethylene diisocyanate, isophorone diisocyanate, bis(isocyanato)cyclohexane Any desired mixture of alkane, 1,2-, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane and isomers, 1,2-, 1,3- and 1, 4-bis(isocyanatoethyl)cyclohexane and any desired mixture of such isomers, 1,2-, 1,3- and 1,4-bis(isocyanato-n-propyl) Any desired mixture of cyclohexane and such isomers, 1-isocyanatopropyl-4-isocyanatomethylcyclohexane and isomers, 2,4'- and 4, 4'-diisocyanatodicyclohexylmethane or mercaptotriisocyanate and mixtures thereof, but especially hexamethylene diisocyanate, 1,2-, 1,3- and 1,4-bis(isocyanate Any desired mixture of cyclohexane and isomers, 1,2-, 1,3- and 1,4-bis(isocyanatoethyl)cyclohexane and such isomers Any desired mixture, 1,2-, 1,3- and 1,4-bis(isocyanato-n-propyl)cyclohexane and any desired mixture of such isomers and/or Ketone diisocyanate, better Hexamethylene diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and 2,4'- and 4,4'-diisocyanatodicyclohexylmethane . For this last group, the amine-containing mercapto group-containing compound is particularly preferably hexamethylene diisocyanate (HDI), 1,2-, 1,3- and 1,4-bis(isocyanatomethyl). A mixture of cyclohexane and such isomers is the substrate.

In the case where the diisocyanate is used as the starting material, the component a) preferably comprises the following structural unit: K ⁺ SO ₃ ^- -[CO-NH-Q-NH] _n -CO-SO ₃ ^- K ⁺

Wherein K ⁺ is a cation equivalent, Q represents any desired divalent hydrocarbon group, which may be substituted or may be interrupted by one or more of the same or different heterologous sources, and n is 1 to 50, preferably 1 To the number of 30.

Specifically, K ⁺ represents an ammonium group NR ₄ ⁺ (R=H, C ₁ -C ₄ -alkyl), or an alkali metal cation such as sodium, potassium or lithium.

Examples of very good base Q are tetramethylene, pentamethylene, hexamethylene, trimethylhexamethylene, octamethylene, decamethylene or dodecamethylene, each of which may be Substituted or interrupted by one or more of the same or different heterologous sources, or 1,2-, 1,3- or 1,4-cyclohexylene and 1,2-, 1,3- and 1,4- Cyclohexyl dimethylene or 3,3,5-trimethyl-1,5-cyclohexyl-5-methylene.

n is particularly preferably 1 to 5 and n very preferably has a value of 1.

The above amine mercaptosulfonate group may also be present as a terminal group in the polyurethane or polyurethane-urea dispersion.

In the case of the diisocyanate as a starting material, the component a) may also comprise the following structural unit: X-[CO-NH-Q-NH] _n -CO-SO ₃ -K ⁺

Wherein X represents a group of the formula -NH-CO-SO ₃ -K ⁺ or a bivalent, as appropriate, preferably carboxyl-substituted bridge member, except Q, and each of K ⁺ , Q and n are as defined above .

This also applies to higher functional polyisocyanates which have been suitably modified.

It is particularly preferred to provide an amine-containing mercaptosulfonate-containing compound, wherein the X-based hydroxycarboxylic acid (citric acid) alkoxy group results in the removal of a hydrogen atom from the hydroxyl group of the hydroxycarboxylic acid.

Ingredient b)

Suitable compounds of component b) are especially mono- or polycarboxylic acids, preferably hydroxypolycarboxylic acids. Suitable examples include: formic acid, acetic acid, oxalic acid, glyoxylic acid, malonic acid, lactic acid, tartaric acid, maleic acid, glutaric acid, citric acid, adipic acid, malic acid, succinic acid, citric acid or Polycarboxylic acids such as (meth)acrylic acid, maleic acid, crotonic acid or itaconic acid or derivatives thereof and optionally further monomers such as ethylene, propylene, styrene, hydroxyethyl methacrylate, methyl a (co)polymer of hydroxypropyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl vinyl ether, especially having from 500 to 100 000 g/mole, especially from 500 to 30 000 g/ The average molar mass of Mohr (weight average Mw).

Preferred as component b) is at least one carboxylic acid, preferably oxalic acid, succinic acid, glutaric acid or adipic acid, especially at least one hydroxypolycarboxylic acid, preferably citric acid, tartaric acid or lactic acid or mixture.

Suitable ingredients b) also include aminocarboxylic acids such as glycine, alanine, lysine, aspartic acid, glutamic acid, leucine, isoleucine, Tyrosic acid, proline, tryptophan, etc., but also peptides, proteins or protein hydrolysates or collagen-containing materials based on plant or animal proteins, such as soy protein hydrolysates, from skin, hair or Fur waste, wet white skin waste, hydrolysis product of leather waste, hydrolysis product of keratinous material, polyaspartic acid, polyglutamic acid, and polycondensation of cis-butenamine by removing water The case is followed by the derivatization of an amine-based polybutylene diimide followed by the hydrolysis of a residual diammonium imine unit having a ring opening, which is a polyaspartamide from WO97/06279. ), which is incorporated herein by reference.

Also useful as component b) is a derivative of cellulose, oligosaccharide or monosaccharide which contains a carboxyl group, such as carboxymethylcellulose; oxidized starch, preferably having less than 100 000 g/mole, especially less than 20 Molecular weight of 000 g / mol; gluconic acid; glucuronic acid; oxidative degradation of anionic starch; alginate; pectin and the like.

Another preferred component b) is a carboxyl group-containing reaction composition of a hydroxypolycarboxylic acid and a polyisocyanate. The hydroxypolycarboxylic acid may especially be one of the above mentioned, especially citric acid. Useful polyisocyanates include, in particular, those mentioned above, especially preferred diisocyanates, primarily hexamethylene diisocyanate.

Preferred component b) contains preferably from 0 to 5% by weight and more preferably from 0 to 2% by weight, based on the composition of the reaction product of the carboxylic acid and the polyisocyanate used.

Preferably, the composition of the present invention is substantially free of emulsifiers, i.e., reduces interfacial tension between the organic phase and the aqueous phase to allow formation of an oil-in-water emulsion. The compounds, and more particularly the compositions of the invention, are emulsifiers free.

Ingredient c)

Via preferred additional materials, it may be preferred that component c) contains or does not contain fatliquoring agents, dustproofing agents, buffers and/or fillers. For the purposes of the present invention, the emulsifier is preferably a material that has not been added.

The fatliquor is preferably a substance based on biological, mineral or synthetic oil, which may be subjected to sulphatization, sulphitization, carboxylation or phosphating, for example, using a hydrophilic group. Provided to improve its use in water.

Possible fillers are preferably inert inorganic salts and organic polymers such as sulphates such as sodium or calcium sulphate, talc, cerium oxide compounds, starch or ligninsulphonates.

Useful buffering agents are those which are added in a sufficient amount to fix and stabilize the pH range, especially in the pH range of from 1 to 5, preferably from 2.0 to 3.5. Suitable buffers for this purpose are preferably mixtures of the compounds c) and their salts. Preferred salts include especially alkali metal salts, preferably sodium or potassium salts.

Examples of preferred dusting agents are alkoxides of aromatic compounds, or polyethers or certain diesters. Specific examples are ethoxylates, propoxylates or mixed polyethers based on EO/PO, and hydroquinone or phenol-styrene may be mentioned as aromatic compounds, having an average molecular mass of from 100 to 800. Polyethyl diol, poly propyl diol having an average molecular weight of 100 to 800, having an average molecular mass of 100 to 800 An EO-PO mixed polyether, a monoalkyl ether or a dialkyl ether of the above polyether, wherein the alkyl group may have 1 to 4 carbon atoms. Moreover, a suitable dustproofing agent based on mineral oil is used. The dusting agent is preferably used in an amount of from 0 to 5.0%, preferably from 0.1 to 2.0%, based on the solid material according to the present invention.

The composition of the present invention may additionally or additionally contain additional substances, and the amount of such additives including those of component c) is preferably up to 30% by weight.

Preferably, the solid composition according to the invention 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), from 0 to 15 % by weight, in particular 0 to 10% by weight, of additional substances other than a) and b), and less than 0.001% by weight of emulsifier, based on the composition.

The solid composition preferably contains 0 to 5% by weight and especially 0 to 2% by weight of water (residual moisture).

The weight of component a) to b) is preferably in the range from 1:1 to 10:1 and especially in the range from 1:1 to 1000:1.

Preferably, the aqueous composition of the invention contains from 10 to 49.9% by weight, in particular from 20 to 49.9% by weight, of component a), from 0.1 to 8% by weight, in particular from 0.1 to 5% by weight, of component b), from 0 to 7. % by weight, in particular 0 to 5% by weight, of additional substances other than a) and b), and less than 0.001% by weight of emulsifier, The composition is the benchmark.

The aqueous composition of the invention preferably contains from 35 to 90% by weight and especially from 50 to 80% by weight of water.

The composition of the invention may be present as a solid, particulate material or as a liquid, especially an aqueous composition.

The composition of the present invention is preferably present as a solid, particulate material having a melting point above 20 ° C, preferably above 60 ° C and especially above 100 ° C.

"Particle" more particularly means a material having an average particle size of from 0.1 μm to 1000 μm, preferably from 1 to 800 μm and especially from 50 to 300 μm, averaging the weight average of all particles. Other averages (volume averages) can be calculated from them via numerical methods, and vice versa. The average particle size can be determined, for example, accurately. The solid material is preferably in the form of a powder or granules.

The particulate solid material of the present invention preferably has a residual moisture content of from 0 to 10% by weight, particularly from 0 to 5% by weight and more preferably from 0 to 2% by weight, based on the material. The particulate solid material of the present invention is based on any desired particle structure, preferably one being spherical or similarly spherical or derived therefrom. It is also possible to have a particle cement of the shape described in the specific particle size range. According to the invention, the material may be in the form of a powder, granules or a so-called particulate form obtained, for example, in spray drying of a single substance nozzle.

The composition of the present invention is also preferably an aqueous composition, especially an aqueous solution, preferably having a solid content of 10 to 49.9% by weight and preferably 20 to 49.9% by weight.

In a preferred embodiment, the composition of the invention contains less than 1% by weight of an organic or inorganic hydrazine formulation, preferably less than 0.1% by weight and more particularly, the composition is substantially free of organic or inorganic hydrazine formulations and Its very special is no organic or inorganic bismuth preparation.

Also preferably, for the solid composition of the invention, 0 to 15% by weight, especially 0 to 10% by weight and most preferably 0.01 to 5% by weight of component c) are based on the solid composition.

Also preferred for the aqueous compositions of the present invention are those which additionally comprise from 0 to 7.5% by weight, especially from 0 to 5% by weight and most preferably from 0.005 to 2.5%, based on the aqueous composition. In the case of aqueous compositions, the formulation contains ingredients a) to c) which are reduced by a percentage corresponding to the water content.

In a particularly specific embodiment, the material of the invention also contains the reaction product of a polyisocyanate/polyisocyanate-bisulfite adduct with citric acid. Such a reaction product (which contains an urethane group and an amine mercapto sulfonate group) can be reacted, for example, by an excess of polyisocyanate with component b) and with bisulfite and/or pyrosulfite. Salt is obtained by successive reactions. Compounds of this type are, for example, formed from 1 mol hexamethylene diisocyanate and 2 mol citric acid bis urethane or, for example, formed from 1 mol hexamethylene diisocyanate and 1 mol citric acid. The monocarbamate, while remaining the NCO group, reacts in situ with bisulfite and/or pyrosulfite to form an amine mesylate group.

Particularly preferred compositions are those having an amine-containing mercaptosulfonate group and at least one organic isocyanate and at least one bisulfite and/or Or a compound obtained by the reaction of pyrosulfite and at least a monohydroxypolycarboxylic acid (ingredient b), especially citric acid, preferably in an amount of 0.05 to 3, preferably 0.1 to 2% by weight, based on the composition Benchmark.

Preferred materials of the invention contain less than 5% and especially less than 1% of a dimeric, trimeric or polymeric amine methyl sulfonate containing urea groups and It is produced by-product by the hydrolysis of polyisocyanate during the synthesis.

Preferably, the composition of the present invention contains 0.1 to 49.9% by weight, in particular 10 to 49.9% by weight, of component a) an amine-containing mercaptosulfonate-containing compound, and 0.1 to 10% by weight, in particular 0.1 to 5% by weight, most preferably 0.1 to 3 by weight The component b), 40.1 to 99.8% by weight, especially 50 to 89.9% by weight, based on the composition, contains less than 0.001% by weight of an emulsifier based on the composition.

Manufacturing

The invention further provides a process for the manufacture of a composition according to the invention, characterized in that component a) is admixed with component b), with or without additional substances.

The invention further provides a process for the manufacture of a composition of the invention, characterized in that at least one organic polyisocyanate having a molecular weight of less than 400 g/mol and an aliphatic or cycloaliphatic NCO group attached With at least one hydrogen sulfite and/or pyrosulfite The reaction is carried out in the presence of water under simultaneous application of shear forces, wherein the carboxylic acid of component b) is additionally added before, during or after the reaction of the bisulfite and/or metabisulfite And optionally the reaction mixture obtained is subsequently dried.

The present invention further provides a process for producing the solid particulate composition of the present invention, characterized in that at least one organic polyisocyanate is simultaneously applied with at least one hydrogensulfite and/or pyrosulfite in the presence of water. The lower reaction, and then drying the obtained aqueous solution, wherein the carboxylic acid of component b) is added before, during or after the hydrogen sulfite reaction or only after the drying step.

It is further advantageous to filter the reaction solution according to the process of the invention before the drying step. Useful forces for this are known as separation techniques, such as filtration through porous filter media known per se, such as paper, ceramic materials or porous plastics. Simple methods can be used for this, such as vacuum filtration through nutsches, pressure filtration via pressure nutsches, chamber filter presses, filter bags, or use of filter cartridges, such as for example for HPLC analysis or More complex separation techniques for sterile filtration. It is also possible to use sedimentation by centrifugation to separate suspended fractions of low fractions.

Both continuous and batch process variants are suitable for the synthesis of aqueous compositions and solid compositions.

High enough shear stress is suitable for use with the following equipment: commercially available blenders, high speed mixers and dispersers, such as dissolvers And a rotor-stator type mixer, such as an Ultraturrax instrument with a slotted disk, and an ultrasonic generating device, in which a sonotrode is immersed in the reaction medium, or else it can be designed, for example, for high pressure (for example 10 to 1000) A high pressure homogenizer of bar) or a jet disperser using, for example, a nozzle operating in the medium range of the pressure range (for example 10 to 1000 bar).

It is further possible to prepare the amine-containing mercaptosulfonate-containing compound in a continuous manner, wherein the reaction components are fed into the plant element in a continuous manner, which makes the ingredients possibly become intimately mixed, and the reaction blend is improved The temperature is preferably in the range of 20 to 100 ° C and in the process of adapting to the short residence time of the temperature, in the microreactor, for example to form the final product, the resulting reaction mixture is optionally adjusted in temperature, pH, concentration and Additional ingredients are added and fed to the drying unit, and the resulting reaction mixture is fed after evaporation of the water. The solid particulate material is discharged from the factory and filled into a suitable container. Suitable microreaction systems include, for example, those from Ehrfeld BTS GmbH or GEA/Niro.

Component b) and optionally additional substances can likewise be added to the reaction in a continuous manner during the reaction.

Continuous operation makes it possible to set the reaction temperature at 20 to 100 °C. The residence time in the re-reaction system can be shortened to a few minutes by increasing the reaction temperature.

In a preferred embodiment, the solution is prepared from an alkali metal bisulfite/pyrosulfite in water. This aqueous solution and polyisocyanate Stoichiometric ratios in the range of 1.0:1.0 to 1.2:1.0 and preferably 1.0:1.0 to 1.05:1.0, respectively, in a continuous manner and in the corresponding bisulfite group (HSO3-) versus NCO group. Add to the mixer integrated into the microreaction plant at a rate. For example, a microreactor factory from the modular structure of Ehrfeld BTS GmbH can be used for continuous manufacturing. The two liquid streams are preferably metered into the microreaction plant via an inlet module using a pulsation free high pressure pump. The liquid stream fed to the mixer is intimately mixed by the microstructure of the mixer, arranged through the heat exchanger and then in the microreactor at a temperature of 20 to 120 ° C, preferably for a residence time of a few seconds to 15 minutes. So that a complete conversion of the NCO group is obtained. After exiting the reactor, the product aqueous solution is cooled by a heat exchanger and pumped from the microreaction system to the separation vessel via an outlet module. Thereafter, the solution can optionally be mixed with the additional substances of component b) and optionally component c) in this container in a continuous manner and can be arranged directly into the spray dryer. The rate at which the feedstock is metered into the microreactor is advantageously in accordance with the rate at which the spray dried material is discharged from the spray dryer. The spray dryer inlet temperature setting is preferably in the range of 120 to 200 ° C and preferably in the range of 130 ° C to 180 ° C. When the solid material has a residual water content of more than 2%, a similar continuous drying step downstream in a fluidized bed dryer or paddle dryer, such as reducing the residual water content to a value below 2%, can advantageously be performed. The material obtained is then filled into a suitable container in a continuous manner. It may be advantageous to add a dusting agent before, during or after the spray drying operation, for example to obtain a Free flowing and easy to meter in the dust free product. The solid materials obtained are very soluble in water (at 20-25 ° C) and the solid materials are noteworthy for superior storage stability even at high temperatures (60 ° C).

The aqueous reaction mixture, regardless of whether or not the intervening isolation of the aqueous reaction mixture is carried out, can be suitably dried by conventional equipment such as spray dryers, thin film evaporators, evaporative screws, for cooling. A crystallization device or a vacuum dryer, such as a device for freeze drying or a vacuum dryer with forced conveyance. Spray dryers are particularly suitable, including where it may be a spray dryer with integrated fluidized bed drying. Re-drying the pre-dried product may be necessary to minimize the maximum residual water content. The residual water content is typically in the range of 0 to 5%, preferably in the range of 0 to 2% and more preferably in the range of 0 to 1%, based on the solid material.

Spray drying is particularly a suitable drying method, preferably a single product spray drying using a high pressure or a spinning-chamber nozzle or a spray drying using a spray tray, freeze drying with upper or downstream granulation or drying processing, Optionally, partially pre-dried products such as accretional granulation, fluidized bed drying and granulation, mixed agglomeration, and the like by pan or drum granulation methods Drying in combination with fluidized or moving bed drying, as appropriate. In addition, it is possible to use a mixture of downstream fluidization or moving bed drying, as appropriate, to cohesion in the suspension. Medium, by mash formation and downstream re-drying and granulation of pulverization or granulation and steam jet agglomeration. Combinations of the mentioned methods are equally possible. It is also possible to dry the aqueous solution, which evaporates water by expanding the solution subjected to the high-pressure treatment of the carbonized carbon to obtain a fine powder as well.

Particularly preferred are spray drying methods using high pressure or spinning channel nozzles, spray drying methods with integrated and/or downstream fluidized bed agglomeration and/or fluidized bed drying, by pan process An accelerating granulation method and a fluidized bed granulation and drying method.

Solid compounds containing an aminomethylsulfonate group can be obtained using different methods. Three methods will now be outlined.

A process for producing a solid composition of the present invention in the form of the present invention, which is preferably characterized in that a liquid reaction mixture obtained by following one of the above-described methods of the present invention is a precipitating agent such as acetone, ethanol or isopropyl. The alcohol or methyl ethyl ketone is mixed and the resulting precipitate is dried.

Three exemplary methods of making solid compositions will now be described.

Method 1 = Precipitation of an amine-containing mercaptosulfonate group-containing compound from an aqueous solution.

The precipitation is carried out by an aqueous solution with an excess of a non-solvent which is at least partially water-miscible with respect to component a), preferably ethanol, methanol, n-propanol, isopropanol, methoxypropanol, acetone, methyl ethyl ketone or Ethyl acetate was mixed and carried out. Acetone is very good.

The aqueous solution to be used preferably has a concentration of from 10 to 50% and more preferably from 25 to 45%. Particularly preferred is an aqueous solution obtained by reacting a polyisocyanate with an alkali metal salt of bisulfite/pyrosulfite using a reaction of preferably 1.00 to 1.10 mol of hydrogensulfite equivalent per 1.00 NCO equivalent. Particularly preferred is an aqueous solution obtained by reacting a polyisocyanate with an alkali metal salt of bisulfite/pyrosulfite using a 1.00 to 1.05 molar hydrogen hydrogen sulfate equivalent equivalent per 1.00 NCO equivalent. Very particularly preferred is the use of a polyisocyanate with an alkali metal salt of bisulfite/pyrosulfite using a reaction of preferably from 1.00 to 1.10 mol of bisulfite equivalent per 1.00 NCO equivalent, and during the reaction and during the reaction. The remainder is added to an aqueous solution obtained by at least 10% fraction of component b) (based on component b).

It is particularly preferred to prepare an aqueous solution by reacting a polyisocyanate with an alkali metal salt of bisulfite/pyrosulfite using a 1.00 molar hydrogen sulphate equivalent per 1.00 NCO equivalent. When acetone or methyl ethyl ketone is used as a precipitant and the amine-containing mercapto sulfonate-based compound is particularly pure, the latest situation with a stoichiometric balance of 1:1 is very particular.

The solid compound for precipitating the amine-containing mercaptosulfonate group is preferably used in an excess amount. The weight of water to solvent is preferably in the range of 1:1 to 1:10 and more preferably in the range of 1:1 to 1:5. The organic solvent may be added to the aqueous solution containing the amine-containing mercaptosulfonate-containing compound, or the aqueous solution may be added to the initially loaded organic solvent. In general, the mixture is stirred during the precipitation step.

The precipitated product is then separated by suction, centrifugation or filtration, preferably using a filter medium, for example by vacuum, using a vacuum nutche, a pressure nutche or a chamber filter press. It is then optionally washed with fresh solvent and then dried. Separation can also be carried out in a continuous manner in combination with the continuous process described above for the manufacture of aqueous solutions. The solid material is preferably dried at a temperature of -20 to +40 ° C under reduced pressure.

The aqueous solution to be used preferably has a concentration between 10% and 60% and more preferably in the range of 25 to 45%, based on the total components a) and b) and, as the case may be, 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, and an optimum pH of 2.5 to 3.5.

The precipitation using an organic solvent is preferably carried out below the boiling point of the organic solvent, more preferably lower than 50 ° C and most preferably in the range of 0 ° C to 40 ° C. The temperature is desirably kept very low at the beginning of drying and increases for the end temperature of the end of drying. This gentle procedure ensures that hydrolysis of the amine-containing mercaptosulfonate-containing compound during operation is avoided.

When acetone is used, the yield is almost quantitative in most cases. However, if necessary, the filtrate can be reprecipitated. The combined filtrate can then be treated in a suitable form, for example, via vacuum distillation to recover the organic solvent.

Method 2

The aqueous solution containing the amine-containing mercaptosulfonate-containing compound is dried via a dry thermal procedure.

It is particularly preferred to dry the aqueous reaction mixture in such a manner that it does not require the use of an organic solvent.

The aqueous solution to be used preferably has a solubility of from 10 to 60% and more preferably from 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, and an optimum pH of 2.5 to 3.5.

The aqueous solution fed to the dryer is preferably set to a temperature below 90 ° C and preferably in a temperature range of from 10 ° C to 80 ° C and especially in the range of from 20 to 60 ° C. The temperature of the solution to adjust the feed to the spray dryer is preferably completed immediately prior to the inlet nozzle of the spray dryer. Here, in order to achieve a brief heating of the material, it is particularly advantageous to heat the solution by passing it through individual heat exchangers.

The technical devices known in the drying art are suitable for drying duty. Particularly preferred is a method of using a spray dryer. Any known method is suitable for the system. Suitable systems are, for example, spray drying towers with single substance nozzles, wherein the aqueous solution is injected at the top of the spray dryer using excess pressure, while the particle size can be adjusted, inter alia, via the nozzle diameter used. Also suitable is, for example, a spray dryer having a disc atomizer in which an aqueous solution is applied to an externally driven rotating cam and finely dispersed by centrifugal force. The inlet temperature in the spray dryer is, for example, 100 ° C to 250 ° C but preferably 110 ° C to 200 ° C, and more preferably 110 ° C to 180 ° C. The outlet temperature is, for example, in the range of 20 to 130 ° C, preferably in the range of 50 ° C to 110 ° C, and more preferably in the range of 70 to 100 ° C.

The residual moisture content of the obtained powder is preferably less than 20%, more preferably less than 10%, even more preferably less than 5% and most preferably less than 1.5%.

The resulting amine-containing mercaptosulfonate-based compound is preferably a colorless powder which is only low-dusting. It may also be advantageous for the material to be dried to have a dusting agent added thereto before, during or after the spray drying. In this case, it is preferred to add a dusting agent to the aqueous solution. It is also possible to introduce a dusting agent into the dryer during the spray drying operation. It is also possible to use a dust-proof agent for surface coating of the obtained powder.

Method 3 = Single solid material via cryotechniques

It is also possible to separate the amine-containing mercaptosulfonate-containing compound from the aqueous solution by precipitation by cooling crystallization or by processing by lyophilization.

The processing is carried out by mechanical removal of the solids in a known manner or separately by evaporating water from the frozen aqueous solution.

The spray drying process according to method 2 is very particularly good for drying aqueous reaction mixtures.

use

The invention also provides the use of a composition of the invention as a reactive component for an amine-containing compound. Examples of possible amine-containing compounds are polymers such as gelatin, amine-containing polysaccharides; diamines such as ethylidene diamine, propylene diamine, butyl diamine, hexamethylene diamine , diaminocyclohexane, 1,12-diaminododecane; amine-containing polyether; polyamines such as di-ethyltriamine, tri-ethyltetramine, tetra-ethylpentamine Aminoethylpiperine , pentaethylhexamine, polyethylenimine, polyvinylamine; for example, polyamine amine-based resin used as wet strength enhancers and retention aids in the paper industry Amino-based (co)polymers based on monomers from the group: dienes, such as butadiene, isoprene, isobutylene, olefins, such as ethylene, propylene, styrene, acrylic acid Ester, methacrylate, (meth) acrylamide or vinyl ester, such as vinyl acetate, vinyl propionate, wherein the amine group is used by using an amine group-containing comon or by Introduced by derivatizing (co)polymer.

Suitable amine-containing compounds may additionally be biological materials, such as tissues associated with other materials in the body, such as skin materials, connective tissue, bone, organs, muscle fibers or vasospasm materials, optionally in isolated or purified form.

In the use according to the invention, the final product obtained using biological materials is very useful for the manufacture of surgical suture materials, the manufacture of implantological products, the manufacture of bone graft materials and the manufacture of implants compatible with the body for surgery. material. In the case of animal hides, the end products obtained in the use according to the invention are tanned leathers having advantageous properties.

Accordingly, the present invention also provides a reaction product obtainable by the reaction of an amine group-containing compound with the composition of the present invention.

The invention further provides for the use of a composition according to the invention as a crosslinker for a protein-based water-soluble polymer, in particular gelatin. An advantageous use is by stabilizing gelatin The outer shell of the material stabilizes the monomer suspension in water. Gelatin can be crosslinked by the compositions of the present invention. This stabilizes the capsule and prevents the monomer droplets from coalescing. In the next operation, polymerization of the monomers within the capsule can be initiated, for example, by increasing the temperature. It is advantageous to use an oil-soluble starter which is introduced into the monomer phase prior to coating the monomer with gelatin. The process is particularly useful for the manufacture of crosslinked copolymers of styrene and for the manufacture of ion exchangers which require a very narrow average particle size distribution, although techniques and processes known per se are used for the monodispersion of the manufacture and polymerization of monomers. Droplet.

The compositions of the present invention are therefore the choice of prior formaldehyde crosslinks.

The reaction of the composition of the invention with the amine-containing reaction component can occur in an aqueous medium or in the presence of an organic solvent. Particularly preferred are, for example, solvents in which the product of the invention is partially soluble and miscible with the water portion. Examples are polar solvents such as pyrrolidone, dimethyl hydrazine, dimethylformamide, N-methylpyrrolidone, N-ethylpyrrolidone, ethanol, methanol, ethylene glycol, and Ethyl glycol, dipropylene glycol, methoxypropyl acetate, tetrahydrofuran.

The invention further provides for the use of the composition according to the invention as an auxiliary for the production of paper, in particular for the manufacture of wet strength or retention aids. The composition of the present invention is more particularly useful as a reaction component for preparing a chlorine-free wet strength agent by reaction with a so-called polyamidoamine resin containing an amine group. The polyamidamine resin is, for example, a polycondensate of adipic acid and one or more polyamines, such as from the group diethyltriamine, ethyldiamine, caprolactam, and triplet. Tetraamine, tetraethylamamine, pentaethylhexamine, and the like or have a piperidine a polyamine such as an aminoethylpipe . The reaction is advantageously carried out in an aqueous solution at a stoichiometric ratio of component a) of 0.1 to 2 moles, based on the amine equivalent of the polyamidoamine resin. When the desired molecular weight increase (which can be traced, for example, by measuring solution viscosity) has occurred, it can be interrupted by acidifying the reaction mixture to pH 2.5-4 to stabilize the reaction product obtained. The reaction product obtained can then be added to the very diluted cellulose slurry in the paper at a rate of from 0.1 to 8% by weight. Dewatering the cellulosic material and forming a sheet using a paper machine and subsequent drying results in a paper sheet having an increased tensile strength in a dry state and with rewet with water. The composition of the present invention can be advantageously used in the manufacture of filter paper, photographic paper, kitchen paper towels, facial tissues, toilet paper, banknotes, wallpaper, and the like.

The cationic polyamidoamines and polyamine resins obtained by using the compositions of the present invention, preferably high molecular weight and high cationic polyamine amines and polyamine resins, are additionally useful as retention aids in papermaking. The retention aid rapidly drains under the formation of the sheet on the paper machine and thus significantly contributes to the speed of operation of the paper machine. .

To this end, the compositions of the present invention are added directly to the cellulose slurry in situ during the papermaking process for use as a coagulant and drainage accelerants.

The invention further provides for the use of the composition according to the invention, in particular the use of solid particulate compositions, for example as pre-carrying preparations, sputum preparations or retanning preparations for hides and skins.

It is also preferred that the composition of the present invention is reacted with an amine-containing compound in an aqueous system at a pH of from 6 to 10.

The pre-tanning preparation for the purpose of the present invention is a product whereby the raw hide or skin can be converted into a commercial mechanical treatment (such as samming or shaving) but used to complete leather or fur (fur) The state of the additional processing steps of the tanning substance.

The invention further provides a method for tanning raw hides and skins, characterized in that the raw hides or sheaths which have been cleaned, limed, optionally depilated and delimated with lime are treated with the composition according to the invention.

The present invention also provides wet white leather obtained by the tanning process of the present invention, which is used for mechanical treatment and further (re)tanned chrome-free tanned leather intermediates.

It will be understood that the tanning of the skin is omitted.

The appropriately pretreated skin (hereinafter referred to as pelts) is preferably in a commercially available crucible cylinder at a temperature of from 10 ° C to 60 ° C in an aqueous float and at a pH of from 5 to 10 (preferably 7). Treating the composition according to the invention with 0.5 to 10% (preferably 1 to 4%) (based on the pure component a) as far as 9), so as to obtain at least 65 ° C, preferably at least 68 ° C and preferably Tanning intermediates at a shrinkage temperature of at least 70 °C. The shrinkage temperature is measured by methods known to those of ordinary skill in the art, such as by dipping into a water bath to heat the tantalum intermediate, wherein the bath temperature is increased at a certain heating rate until material shrinkage is observed. Temperature system to reach the shrinkage point Read on the display of the leather shrinkage tester. The shrinkage temperature can also be determined using a differential scanning calorimetry (DSC) method known to those skilled in the art to which the present invention pertains.

Preferably, after the addition of the composition according to the present invention, the product is allowed to permeate in the fur portion at a pH of 8 to 10 and the floating liquid at a pH of 7 to 8 preferably for 0.1 to 8 hours, more preferably 0.2 to 2 hours, and A fixative is then added. Useful fixing agents include any of the bases known per se, or mixtures thereof, examples of which are aqueous sodium hydroxide, alkali metal carbonates, alkali metal hydrogencarbonates, magnesium oxide, dolomite, tertiary amines, etc. It is preferably dolomite, magnesia, sodium carbonate and aqueous sodium hydroxide. Immobilization is preferably carried out for 2 to 24 hours, preferably 4 to 12 hours, at a floating liquid pH of 7 to 10, preferably a floating liquid having a pH of 7.0 to 8.5.

It is also possible to interrupt the tanning by acidification to pH 4 to 6 or the addition of ammonia or a primary or secondary amine compound. This is especially advantageous when it is desirable to avoid excessive astringency of the floating liquid and partial deactivation of the sputum preparation. These additional methods are suitable for affecting the tanning operation in an advantageous manner.

Useful amine-based compounds include, for example, ethanolamine, diethanolamine, propylamine, butylamine, hydroxypropylamine, dihydroxypropylamine, 3-aminopropyltriethoxydecane, 3-aminopropylpropane Trimethoxy decane, N-(2-aminoethyl)-3-aminopropyltriethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane , bis(3-triethoxymercaptopropyl)amine, bis(3-trimethoxydecylpropyl)amine, hydroxyethylformin, hydroxyethylcyclohexylamine, hydroxypropyl-familin , hydroxypropylcyclohexylamine, hydroxyethylethylidene diamine, hydroxypropyl Diamine, bis(hydroxyethyl)ethylidene diamine, bis(hydroxypropyl)ethylidene diamine.

In particular, the above decanes are useful for additionally constructing a three-dimensional secondary in the range of a substrate by hydrolysis to a sterol group and a sterol-based self-condensing synthesis of a polyoxyalkylene group during a tanning operation. The network, and thus the advantageous contribution of the additional stabilizing skin material. The presence of mineral fillers also increases the stabilizing effect. Suitable mineral fillers include, for example, vermiculite-containing materials such as vermiculite, ground glass, sheet-silicates, aluminosilicates, zirconia, titania produced by hydrolysis or pyrolysis. . Such mineral fillers may also have surfaces that have been specially treated and chemically modified by the use of organofunctional decane. Such materials are commercially available. Stabilization of the skin is a desirable effect, particularly for use as a pre-tanning agent, for example in order to positively influence the machining during the sharpening operation. It is also possible to advantageously influence the shrinkage temperature. Such steranes can also be used in the reconstitution in combination with the compositions of the present invention in order to influence tactile properties (fullness, softness) and color traits (levelness). Penetration).

It is particularly advantageous to select a low initial float liquid pH 6 to 7 to permeate the bismuth formulation and to control the fixed pH range between 7.5 and 8.5 by increasing the temperature.

The tanning intermediate obtained is used for further processing by means of, for example, twisting, sharpening or splitting the machine. In addition, these intermediates are characterized by distinct white, clear and light-resistant monochromatic colors, as well as the superiority of this system compared to leather made from glutaraldehyde. point. The pre-tanned intermediates can be tanning using conventional methods to provide a soft and airy embryo skin.

The invention further provides a method for the manufacture of leather and furs, characterized in that the prepared fur material (i.e., the conditioned skin or the lime-dried and/or pickled fur material for tanning) ) in the aqueous floating liquid at a temperature of 10 ° C to 60 ° C and pH 5 to 10, preferably 7 to 9, using 0.5 to 10%, preferably 1 to 4% (based on the active ingredient of component a) The material according to the invention is treated until a tanning intermediate having a shrinkage temperature of at least 65 ° C, preferably at least 68 ° C and more preferably at least 70 ° C is obtained.

When the shrinkage temperature is lower, the mechanical operation of the tanning intermediate product (i.e., wet white skin material) is problematic on, for example, a sharpener because the wet white skin material is excessively adhered to the blade rolls and the processing is difficult. . In contrast, a significantly higher shrinkage temperature can be achieved by allowing more tanning to be carried out for a longer period of time, adding more tanning agents or performing fixation at higher pH values. However, there is no need for mechanical manipulation of the fur.

In a particular embodiment of the invention, the properties of the further processing of the machine and the properties of the final leather can be applied to the customer by the addition of the composition according to the invention, the addition of the composition according to the invention being typical of the addition of tanning. The bubbling liquid of the other substance is before, after or after.

It contains common commercially available organic bismuth preparations, such as synthetic sputums (syntans), resin sputum preparations, vegetable sputum preparations, filling and soft (Re) hydrazine formulations, fatliquors, and hydrophobic agents. These agents are preferably added in the subsequent re-tanning step in an amount conventionally used for wet white skin. Lignosulphonates can be used as a component in the re-tanning step.

An advantage of the tanning operation according to the present invention is that a leather having a wide range of properties and the resulting shavings during mechanical operation can be widely used as a raw material, including for the manufacture of useful products for use in leather manufacturing operations. This produces a significant contribution to further reducing waste in leather manufacturing.

A particular advantage of the composition according to the invention is that it does not foam when used in an aqueous solution and is very stable to the hydrolysis system in the state of use.

Instance Example 1 (bisulfite: NCO=1.05:1)

182.9 grams of hexamethylene diisocyanate was added to a solution of 422.7 grams of water and 609.5 grams of sodium bisulfite solution (NaHSO3, 38-40% in water) at 23 ° C for more than 15 minutes while operating on a rotor-stator basis The disperser (Ultraturrax assembly from IKA) disperses the mixture at 15,000 to 20,000 revolutions per minute. The temperature of the reaction mixture was increased to about 50 ° C for more than 120 minutes from the addition of isocyanate. The pH was 3.04 at the start and increased to a maximum pH of 5 during the course of the reaction. The mixture at this stage still has The milky appearance, but the isocyanate has been converted to such an extent that no organic phase is observed anymore, after switching to the dispersing machine and waiting for 120 seconds. During the temperature climb to 56 ° C, it was then dispersed for 1 hour at 20 000-24 000 rpm. After a total reaction time of 3 hours, a clear solution was formed. The pH system is 3.66. This batch was then cooled to 25 ° C for more than 30 minutes and mixed with 31.1 grams of citric acid monohydrate dissolved in 25.7 grams of water to obtain a clear 35.0% strength solution having a pH of 2.00.

This solution was mixed with 3000 ml of acetone at room temperature. The mixture was then stirred for 2 hours. The precipitated white solid was filtered with suction, washed with acetone and dried under vacuum at 20 ° C to constant weight (yield 94.5%, residual moisture content less than 1% by weight).

A solution of 1.75 grams of powder in 5 ml of water was clear and had a pH of 2.20.

Example 2 (bisulfite: NCO=1.05:1)

166.3 g of hexamethylene diisocyanate was added at one time to a solution of 384.3 g of water and 554.1 g of sodium hydrogen sulfite solution (NaHSO 3 , 38-40% in water) at 23 ° C while operating on a rotor-stator basis. The disperser (Ultraturrax assembly from IKA) disperses the mixture at 10,000 rpm. The temperature of the reaction mixture was increased to about 63 ° C for more than 45 minutes from the addition of isocyanate. The pH was 3.06 at the start and increased to pH 5.91 during the course of the reaction. After a total reaction time of 60 minutes, a clear solution was formed. This batch was then cooled to 30 ° C for more than 120 minutes and the pH was 4.18. This batch was mixed with 28.3 grams of citric acid monohydrate dissolved in 23.4 grams of water to obtain a clear 35.0% strength solution having a pH of 2.10.

The solution filtered through a fluted filter was mixed with 3000 ml of acetone at room temperature. After 1 hour, the precipitated white solid was filtered with suction, washed with acetone and dried under vacuum at 20 ° C to constant weight (yield 92.5%, residual moisture content: 0.6% by weight).

A solution of 1.75 grams of powder in 5 ml of water was clear and had a pH of 2.10.

Example 3 (bisulfite: NCO=1.05:1)

182.9 g of hexamethylene diisocyanate was added in one portion to a solution of 422.7 g of water and 609.5 g of sodium hydrogen sulfite solution (NaHSO 3 , 38-40% in water) at 23 ° C while operating on a rotor-stator basis. The disperser (Ultraturrax assembly from IKA) disperses the mixture at 12,000 rpm. The temperature of the reaction mixture was increased to 56 ° C for more than 45 minutes from the addition of isocyanate. The pH was 3.51 at the start and increased to pH 4.84 during the course of the reaction. After a reaction time of 60 minutes, the solution was clear. The speed was reduced to 8000 rpm and the solution was cooled to 33 ° C for more than 2 hours. This solution has a pH of 3.50.

This solution was mixed with 2,600 ml of acetone. The mixture was then stirred for 2 hours. The precipitated white solid was filtered with suction, washed with acetone and dried under vacuum at 20 ° C to constant weight (yield 86.5%, residual moisture content: 0.69% by weight).

The solid was then homogenously mixed with 31.1 grams of citric acid monohydrate using a milling system. A solution of 1.75 grams of powder in 5 ml of water was clear and had a pH of 2.00.

Example 4 (bisulfite: NCO = 1.00:1)

166.3 g of hexamethylene diisocyanate was added in one portion to a solution of 391.4 g of water and 527.6 g of sodium hydrogen sulfite solution (NaHSO 3 , 38-40% in water) at 23 ° C while operating on a rotor-stator basis. The disperser (Ultraturrax assembly from IKA) disperses the mixture at 15,000 rpm. The temperature of the reaction mixture was increased to about 60 ° C for more than 60 minutes from the addition of isocyanate. The pH was 3.02 at the start and increased to pH 5.84 during the course of the reaction. After a reaction time of 180 minutes, a cloudy solution formed. The speed was reduced to 12,000 rpm and the solution was cooled to 34 °C for more than 2 hours. This solution has a pH of 3.50. This batch was then cooled to 30 ° C for more than 120 minutes and the pH was 4.18. Filter this batch. The clear solution had a pH of 4.34 and was mixed with 28.3 grams of citric acid monohydrate dissolved in 23.4 grams of water to obtain a solution having a solids content of 35.25% by weight and a pH of 2.12.

This solution was mixed with 3000 ml of acetone. The precipitated white solid was suction filtered, washed with acetone and dried under vacuum at 20 ° C to constant weight (yield 90.3%, residual moisture content: 0.5% by weight).

A solution of 1.75 grams of powder in 5 ml of water was clear and had a pH of 2.20.

Example 5 (bisulfite: NCO=1.05:1)

191.8 g of bis(isocyanatomethyl)cyclohexane (mixture of isomers or more precisely 1,4- and 1,3-isomers) was added at once to 201.8 g of water and 554.1 g at 20 °C A solution of sodium bisulfite solution (NaHSO3, 38-40% in water) was used while dispersing the mixture at 15,000 rpm using a rotor-stator based disperser (Ultraturrax apparatus from IKA). After 2 hours, the setting of the disperser was increased to 18,000 rpm. After another 30 minutes, the speed increased to 20,000 rpm. The temperature of the reaction mixture was 60 ° C 3 hours after the addition of the isocyanate. After a reaction time of 3.5 hours, the organic phase disappeared. It was then cooled at 40 ° C for more than 1.5 hours while continuing to disperse at 15,000 rpm. After a total reaction time of 5 hours, the batch was filtered and mixed with a solution of 28.3 g of citric acid monohydrate dissolved in 23.4 g of water to obtain a solution having a pH of 2.58 and a concentration of 35.0%, which had a pH of 2. 58.

This solution was mixed with 3000 ml of acetone at room temperature. The mixture was then stirred for 2 hours. The precipitated white solid was filtered with suction, washed with acetone and dried under vacuum at 20 ° C to constant weight (yield 80.5%, residual moisture content: 0.9% by weight).

A solution of 1.75 grams of powder in 5 ml of water was clear and had a pH of 2.60.

Example 6 (bisulfite: NCO=1.05:1.0)

One solution was prepared from 326.5 grams of water, 461.7 grams of sodium bisulfite solution (NaHSO3, 38-40% in water) and 9.8 grams of 2 molar lemons. An adduct of citric acid with 1 mol of hexamethylene diisocyanate obtained by drying an aqueous solution at a dispersion of 12,000 rpm. This initial loading was once mixed with 138.6 grams of hexamethylene diisocyanate at 20 °C. The temperature of the reaction mixture was increased to 50 ° C for more than 60 minutes by dispersion. When it reached 50 ° C, 7.8 g of citric acid monohydrate dissolved in 6.5 g of water was added, which resulted in a pH of 3.05. The batch was then maintained at 50 °C for 1 hour and then cooled to 25 °C for more than 2 hours. The pH of the clear solution was 2.92 at room temperature. Dissolved in 23.6 grams of a portion of citric acid monohydrate in 19.5 grams of water. The solids content was adjusted with 26.4 grams of water to obtain a clear 35.0% strength solution having a pH of 2.30.

This solution was mixed with 3000 ml of acetone at room temperature. The mixture was then stirred for 2 hours. The precipitated white solid was filtered with suction, washed with acetone and dried under vacuum at 20 ° C to constant weight (yield 93.5%, residual moisture content: 0.7% by weight).

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

Comparative example

The isophorone diisocyanate (IPDI)-bisulfite adduct is prepared as described in US Pat. No. 4,413,997 (column 2, lines 54-60) and as indicated in US 4,413,997, in an aqueous solution at 30% strength.

Pelt splits (3.3-3.5 mm) were pretreated (rehydrated) with 300% water (20 ° C) and 2% calcium hydroxide overnight and dehydrated. Then wash the fur with 200% water (based on the weight of the fur) Dehydration. The fur material was then degreased for 30 minutes by stirring it in 100% fresh water containing 0.1% sodium hydrogen sulfite and 1.2% N free deliming agent. At this point, (pH 8.4) 0.2% of a fatty alcohol ethoxylate-based degreasing agent, 150% water and 0.15% bating enzyme (product from Novozyme, Novobate®) was added. 1547) before stirring for 1 hour. The floating liquid is then dehydrated and the fur is washed again. It was then pickled (pH 2.7) for 3 hours in fresh float with 70% water, 7% sodium chloride, 0.5% formic acid (1:5), and 1.5% sulfuric acid (1:10). Subsequently, the fur material is separated and placed back into the drum for testing.

The cylinder was stirred overnight (pH 2.1). The next morning, the floats were dehydrated and the fur was depickled (pH 4.5) using 100% water, 0.5% sodium formate and 1.75% sodium bicarbonate (1:20).

The fur was treated with 10% of the isophorone diisocyanate-bisulfite adduct as indicated in US4413997 (addition of 33% of a 30% strength aqueous solution) in 100% fresh float for 30 minutes. Sodium bicarbonate solution (1:10) was then added during 5 hours to adjust the pH to 9.0. The cylinder was then stirred overnight. The contraction temperature was measured the next morning. The leather obtained was finally adjusted to pH 5 with 5% acetic acid for more than 3 hours and horsed overnight. For example, US Pat. No. 4,413,997 describes the use of isophorone diisocyanate-bisulfite adduct and the absence of a carboxylic acid to obtain a fur shrinkage temperature of 66 °C.

For comparison, after the same procedure, by adding 24.9 g of anhydrous citric acid to 950 g of the above 30% aqueous solution, for the retanning agent (retannage), the shrinkage temperature of 68 ° C was measured. In each case, a 33% isophorone diisocyanate-bisulfite adduct solution was used, based on the weight of the fur. In addition, citric acid-free leathers are not easily scratchable and exhibit undesired drawn grain.

B) Use examples (manufacturing)

The amount of particular product used, such as commercially available products, is based on the weight of the starting materials or intermediates used.

B 1: Medical sheepskin, chrome free

In industrially used paddles, air-dried sheepskins are moisturized at 20 ° C overnight and then cut with 20 liters of water per skin and 2.0 grams per liter of non-ionic emulsifier based on fatty alcohol ethoxylates. (fleshed). The prepared skin was thus degreased twice at a temperature of 35 ° C in an aqueous floating liquid having a nonionic emulsifier based on a fatty alcohol ethoxylate of 2.0 g/liter for 60 minutes each time, and dropped in a floated manner. After the object, wash thoroughly with warm water.

For the preparation of tanning, the new float liquid was initially loaded and not pickled, which was mixed at 5.3 g/liter of the inventive product from Example 1 at 25 °C. Magnesium oxide was added in three doses to increase the pH to 8.8 in stages. And then the temperature is increased to 40 °C.

After 12 hours of operation, 7 g/l of sulfated synthetic fatliquor and 2.0 g/l of lecithin-based dispersing aid were introduced into the same bath. At 2 hours, the formic acid was used to lower the pH to 5.5. After discarding the floating liquid, the skin is thoroughly washed with cold water and uploaded commercially. The system is completed and has a shrinkage temperature of 77 °C.

The skin of the present invention has a clear, lighter color than leather made from glutaraldehyde in a commercially conventional manner, not only for leather but also for wool, and better lightfastness. In the DIN 53315 A aldehyde test, the measured values were clearly reduced compared to the prior art and were below the detection limit of the method by 20 ppm.

The same good results were obtained using the powders from Examples 2 to 6.

B 2: Making wet white for full-grained decorative leather

Salted cowhide is commercially traditionally cleaned, limed, depilated, fleded, and split. Wash the fur material (2.7 mm) with 200% water and discard the float. To remove lime, the fur was stirred in 30% fresh water using 0.4% sodium bisulfite and 1.4% N-free deliming agent (product from BASF, Decaltal® A-N) for 10 minutes. Subsequently, 0.15% of a degreaser based on a fatty alcohol ethoxylate was added (pH 8.4) by stirring at 25 ° C for 1 hour. Then, 50% water and 1% glycolysis (product from Novozyme, Novobate® 1547) was added by stirring for 1 hour. After that, the floating liquid is discarded and the fur is washed again.

In 50% fresh floating liquid, the fur was conditioned with 0.25% magnesium oxide at pH 9.5 for 1 hour and mixed with 6% of the inventive product from Example 1 (eg powder or 1:1 dilution with water). , resulting in pH 8.3. After 3 hours, 0.3% magnesium oxide was added to increase the float pH to 9.0-9.5 and the shrinkage temperature was measured. After 1 hour of operation, add 0.2% magnesium oxide and 0.1% ammonia solution (diluted with water 1:5) () After 1 hour, pH 9.1) and stirring the drum at 35 ° C overnight (pH 9.2).

For the preparation of the tanning, 0.6% formic acid (diluted 1:5 with water) was used to reduce the pH to 5.3 in three portions. After 90 minutes, the floating liquid was discarded. Wet white leather (chromic tanned leather intermediate for mechanical processing and additional (re)tanned) is washed and sammed. The shrinkage temperature (77 ° C) was measured again and the leather was scraped to 1.0 mm.

Regarding the properties, a leather having a shrinkage temperature of 77 ° C, a smooth grain appearance, a dry and thick hand, and also very good sammability and shavability was obtained.

The same good results were obtained using the powders from Examples 2 to 6. In each case, the shrinkage temperature is higher than 70 ° C. In each case, the grain-outside relationship is smooth, and the leather has the advantages of a dry and thick hand and a very good water-wrinkling property and sharpness.

B 3: Manufacture of wet white leather for full grain decorative leather

Salted cowhide is commercially traditionally cleaned, limed, depilated, cut and split. Wash the fur material (2.7 mm) with 200% water and discard the float. To remove lime, the fur was stirred in 30% fresh water using 0.4% sodium bisulfite and 1.4% N-free deliming agent (product from BASF, Decaltal A-N) for 10 minutes. Subsequently, 0.15% of a degreaser based on a fatty alcohol ethoxylate was added (pH 8.4) by stirring at 25 ° C for 1 hour. Then, 50% water and 1% glycolysis (product from Novozyme, Novobate® 1547) It was then added by stirring for 1 hour. After that, the floating liquid is discarded and the fur is washed again.

In 50% fresh floating liquid, the fur was conditioned with 0.25% magnesium oxide at pH 9.5 for 1 hour and mixed with 6% of the inventive product from Example 1 (eg powder or 1:1 dilution with water). , resulting in a pH of 8.7. After 1 hour of infiltration time, 2.0% of 4,4'-dihydroxydiphenylphosphonium/naphthalenesulfonic acid/formaldehyde condensate (eg, product from LANXESS, TANIGAN® BN) and 1% aromatic sulfonic acid were added. Formaldehyde condensate (eg product from Lanxess, TANIGAN® PR). After 1 hour of operation, 0.2% magnesium oxide and 0.1% aqueous ammonia solution (diluted 1:5 with water) (1 hour later, pH 9.1) and a drum at 35 ° C overnight (pH 9.2) were added. .

After another 2 hours (pH 7.8), 0.2% magnesium oxide and 0.1% aqueous ammonia solution (diluted 1:5 with water) (pH system 9.0 after 1 hour) were added and the shrinkage temperature was measured. The drum was stirred overnight (pH 8.9) at 35 °C.

For the preparation of the tanning, 0.6% formic acid (diluted 1:5 with water) was used to reduce the pH to 5.3 in three portions. After 90 minutes, the floating liquid was discarded. The wet white leather is washed and twisted. The shrinkage temperature (76 ° C) was measured again and the leather was scraped to 1.0 mm.

The same good results were obtained using the powders from Examples 2 to 6.

B 4: Manufacture of wet white leather for decorative leather:

Salted cowhide is commercially traditionally cleaned, limed, depilated, cut and split. Wash the fur material (2.7 mm) with 200% water and throw it away Discard the floating liquid. To remove the lime, the fur was stirred in 30% fresh water using 0.4% sodium bisulfite and 1.5% N-free deliming agent (product from BASF, Decaltal® A-N) for 10 minutes. Subsequently, 0.15% of the degreaser based on the fatty alcohol ethoxylate was added (pH 8.5) by stirring at 25 ° C for 90 minutes. Then, 50% water and 1% fermented enzyme (product from Novozyme, Novobate® 1547) was added by stirring for 45 minutes. After that, the floating liquid is discarded and the fur is washed again.

In a 50% float liquid, the prepared fur was conditioned with 1% sodium acetate and 1% sodium carbonate at pH 9.9 and with 6% of the inventive product from Example 1 (such as powder or water 1). : 1 dilution) mixed, resulting in a pH of 8.6. After a 30 minute permeation time, 4.0% of 4,4'-dihydroxydiphenylphosphonium/naphthalenesulfonic acid/formaldehyde condensate (eg, product from LANXESS, TANIGAN® BN) and 2% aromatic sulfonic acid were added. Formaldehyde condensate (eg, product from LANXESS, TANIGAN® PR) (added as 50% solution, pH 7). After 1 hour (pH 8.2), a total of 1% sodium carbonate (diluted 1:10 with water) was added in portions to increase the pH of the floating liquid to 8.7 over 2 hours, and the shrinkage temperature was measured. The leather was then stirred at 30 ° C overnight (pH 8.1).

For the preparation of the tanning process, 0.6% formic acid (diluted 1:10 with water) was used to lower the pH to 7.2 in three portions, the floating liquid was discarded, and the wet white leather was twisted. The shrinkage temperature (70 ° C) was measured and the leather was scraped to 1.0 mm.

The same good results were obtained using the powders from Examples 2 to 6.

B 5: Manufacture of wet white leather for upper leather

Salted cowhide is commercially traditionally cleaned, limed, depilated, cut and split. Wash the fur material (2.6 mm) with 200% float and discard the float. For lime removal, the fur is in a cylinder at 25 ° C in 100% float and 0.3% sodium bisulfite, 1.0% N-free lime remover (eg from BASF products, Decaltal® ES-N) and 0.3% dicarboxyl The acid mixture (for example, product from BASF, Bascal® S) was stirred for 1 hour. Then, at pH 7.7, 1% fermented enzyme (from Novozyme's product, Novobate® 1547) and 0.1% fat alcohol ethoxylate-based degreaser were added by stirring for another 45 minutes. And then discard the floating liquid and wash the fur twice.

The prepared fur was conditioned with 1% acetic acid sodium at pH 8.0 for 1 hour and mixed with 1.7% of the inventive product of Example 1 (such as powder or 1:1 dilution with water). After a 20 minute penetration time, 0.2% sodium carbonate (diluted 1:10 with water) was added by stirring for 30 minutes. Subsequently, an additional 3.4% of the inventive product from Example 1 (such as a powder or 1:1 dilution with water) was added. After 1.5 hours, a total of 0.4% sodium carbonate (diluted 1:10 with water) was added in portions to increase the pH to 8.2 over 2 hours and the shrinkage temperature was measured. Thereafter, the drum was stirred at 30 ° C overnight. Next, the pH was lowered to 7.0 using formic acid (diluted with water 1:10). The cylinder was then stirred for 2 hours. Subsequently, the floating liquid is discarded. Wash the wet white leather and wring the water. The shrinkage temperature (72 ° C) was measured again. The leather can be handled without problems and scraped to 1.2 mm.

The same good results were obtained using the powders from Examples 2 to 6.

B 6: Leather for car decoration without chrome:

The shaved wet white leather from Example B4 was stirred with 300% water (35 ° C) and 0.2% fatty alcohol ethoxylate at pH 7.6 for 20 minutes. After discarding the floating liquid, add 50% water, 3% naphthalenesulfonic acid/formaldehyde condensate (product from LANXESS, TANIGAN® RFS), 1.5% sodium formate and preliminary fatliquoring, 3% to lecithin A base fatliquor (from Lanxess's product, BAYKANOL® Licker SL) (diluted 1:8 with water). After a 30 minute run time, 2% polyacrylate dispersion (from Dow/Lanxess, LEUKOTAN® 1084) (diluted 1:3 with water) and 3% after another 10 minutes were added. Polyammonium carboxylic acid (from Lanxess's product, LEVOTAN® L) (diluted 1:3 with water) was used as a filling and softening retanning preparation. After an additional 10 minutes of operation, add 8% tara and 5% of a synthetic bismuth preparation based on 4,4'-dihydroxydiphenyl hydrazine/naphthalenesulfonic acid/formaldehyde condensate (from LANXESS) The product, TANIGAN® BN) and after 30 minutes (pH 5.5), an additional 8% of mimosa and an additional 5% of 4,4'-dihydroxydiphenylphosphonium/naphthalenesulfonic acid/ The formaldehyde condensate is a synthetic bismuth preparation (product from LANXESS, TANIGAN® BN). Next, it was dyed with 3% dye (pH 5.5-5.8) for 2 hours. After floating in 50% water, another 4% lecithin-based fatliquor (from Lanxess's product, BAYKANOL® Licker SL) (diluted with water 1:8) followed by tumbling at 50 °C Join for 1 hour. After that, add 2% formic acid in 2 parts (diluted with water 1:5) Release) 45 minutes for fixing (pH 4) and discarding the floating liquid. The leather was washed with 200% water (50 ° C).

Fresh float (100% water, 50 ° C) with 4% lecithin-based fatliquor (from Lanxess's product, BAYKANOL® Licker SL) (diluted with water 1:8) Used for top fatliquoring during 1 hour of operation. The leather was then acidified to pH 3.4 in 2 steps using 1% formic acid (diluted 1:5 with water) and then fixed for 45 minutes. Then discard the floating liquid; wash the leather twice with 200% water and set out, vacuum dry (50 ° C), suspension drying, staking, milling, shovel soft It is done in a commercially customary way.

This provides a very soft and firm grained, level-dyed embryo skin with very consistent milled grain that is finishable and has excellent results.

B 7: Upper chrome-free tanned leather:

The shaved wet white leather from Example B5 was washed in a 150% float liquid at 35 ° C using 0.3% formic acid (diluted with water 1:10) for 20 minutes (pH 4.3), and the float liquid was discarded.

Fresh floating liquid (100% water 30 ° C) is used for 2% synthetic fatliquor, 1% lecithin-based fatliquor (diluted with water 1:8) and 5% with 4,4'-two A mixture of hydroxydiphenyl hydrazine as a base preparation (from Lanxess's product, TANIGAN® 3LN) allows the leather to undergo initial fatliquoring. After 20 minutes, add 10% dihydroxy two in 2 parts. Phenylhydrazine/naphthalenesulfonic acid/formaldehyde condensate (product from LANXESS, TANIGAN® CF liquid) (1:1 dilution with water) and drummed in for 45 minutes (pH 4.5). Thereafter, 70% water and 2% dispersant based on aromatic sulfonic acid (from Lanxess, TANIGAN® PAK) were added. After 15 minutes of operation, start adding 4% modified polyamine carboxylic acid (from Lanxess, LEVOTAN LB) (diluted 1:3 with water) and 3% polyacrylate dispersion (from Dow/) Lanxess's product, LEUKOTAN® 8090). After another 20 minutes, add 3% synthetic fatliquor and 2% lecithin-based fatliquor (from Lanxess's product, BAYKANOL® Licker FSU and SL) (diluted with water 1:5), then After another 15 minutes, 5% mimosa and 12% synthetic bismuth preparation based on 4,4'-dihydroxydiphenyl hydrazine/formaldehyde condensate (product from LANXESS, TANIGAN® VR, TANIGAN® 3LN) mixture. After 30 minutes of operation, the leather was sweetened with a 12% chestnut mixture and a synthetic bismuth preparation based on dihydroxydiphenyl hydrazine/naphthalene sulfonic acid/formaldehyde condensate (product from LANXESS, TANIGAN VR) The resin enamel preparation (from Lanxess's product, RETINGAN® ZF Plus) was fully tanning and dyed in the presence of 1% dye and 2% dyeing auxiliaries (from Lanxess's product, BAYKANOL® TF-2N).

The next morning, after adding 100% water (50 ° C), use 3% lecithin-based fatliquor, 3% lanolin-based fatliquor (from Lanxess, BAYKANOL® Licker LA) ,2% A top fatliquor is prepared from a mixture of a synthetic fatliquor (from Lanxess's product, BAYKANOL® Licker SL, FSU) and 1% beef foot oil (eg Atlas Neatsfoot® Oil 30 CT) (mixed with water 1:5). After 60 minutes of operation, 3% formic acid (diluted 1:10 with water) was used to fix the leather (pH 3.6) in 3 portions and discard the floating liquid over the course of 80 minutes. The leather is cleaned and finished in a commercially customary manner.

This provides a very soft and firm grained, level-dyed embryo skin with very consistent milled grain that is finishable and has excellent results.

C1) Preparation of a cationic polycondensate based on the product from Example 2

216.8 g (2.105 mol) of diethyltriamine and 302 g (2.07 mol) of adipic acid were added together and heated to 140 ° C and stirred at 140 ° C for 1 hour. The temperature was ramped up to 180 °C for more than 2 hours. This temperature was maintained for an additional hour until 75 grams of water had been distilled off. The obtained polycondensate was taken up to 450 g of water to obtain a 50% strength solution having a viscosity of 415 mPas (23 ° C) and a base-N base equivalent of 398 g/mole.

Initially, 398 g of the 50% strength polyamine amine solution (1 mol) prepared above and 398 g of water were loaded. 0.7 mol of a 25% solution of the product from Example 2 in water was added dropwise at 20 ° C for more than 30 minutes. It was then stirred at 20 ° C for 8 hours. Thereafter, 4.45 g (0.11 mol) of the above polyamine amine solution was added while maintaining the pH at 7 or higher. The temperature is raised to 50 to 55 ° C and maintained at this level for about several hours until the viscosity of the 15% strength solution has increased to 60-70 mPas at 23 °C. Add water to dilute to 15% solids and add 15 grams of 48% sulfur by adding The reaction was stopped with acid, followed by the addition of a 50% strength citric acid solution until pH 2.7 had been reached. The solid content was adjusted using water to obtain a 15% concentration pale yellow solution having a viscosity of 70 mPas at 23 °C.

C2): Preparation of a cationic polycondensate based on the product from Example 6

In a manner similar to Example C1, a 1 molar aqueous solution of the basic polyamine amine was initially loaded and reacted at a concentration of 25% with 0.7 mole of a 25% strength aqueous solution of the product from Example 6. After reaching a viscosity of 60 mPas, water was added to dilute to 15% solids and the reaction was stopped by adding 48% strength sulfuric acid. Formic acid was added until a pH of 2.9 was reached. The solid content was adjusted using water to obtain a 15% concentration pale yellow solution having a viscosity of 58 mPas at 23 °C.

C3): According to examples C1) and C2) as product use for wet strength of paper

The cationic polymer solutions obtained according to Examples C1) and C2) are used to improve the wet strength of paper.

Bleached pine/birch sulphate pulp (weight ratio 80:20) was hammered to a freeness of 38° Schopper-Riegler at 2.5% consistency. 100 g of the obtained pulp suspension was introduced into a glass beaker and diluted to 1000 ml with water. Thereafter, the polycondensate solution (% by weight of the pulp-based use form) prepared according to the examples C1) and C2) shown below was added to a fibrous stuff, followed by stirring for 3 minutes.

Next, the contents of the glass beaker are added to a sheet former (Rapid-Köthen), diluted with 8000 ml of water, and formed into a paper sheet having a basis weight of about 80 g/m 2 (eg according to DIN 54358 part 1) . The paper sheets were dried in a dry box at 85 ° C and 60 mbar for 8 minutes and at 110 ° C for an additional 10 minutes.

After conditioning, each sheet was cut into 5 test strips each 1.5 cm wide and immersed in deionized water for 5 minutes. Thereafter, the wet strip was tested in a tensile tester for its wet breaking load (DIN 53112 part 2).

The results obtained are summarized in the table below:

Claims (13)

a composition comprising a) at least one amine-containing mercaptosulfonate-containing compound, and b) at least one carboxylic acid, based on the composition, containing less than 0.001% by weight of an emulsifier, wherein Component a) The amine-containing mercaptosulfonate-containing compound is a reaction product of at least one organic polyisocyanate and at least one hydrogensulfite and/or pyrosulfite, characterized in that the organic polyisocyanate has less than 400 g. /Mole molecular weight and NCO groups attached via aliphatic or cycloaliphatic, especially 1,4-diisocyanate butane, 1,6-diisocyanate hexane (HDI), 1,5-diiso Cyanate-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanate hexane (TMHI), 1,3- and 1, 4-diisocyanate hexane, 1,3- and 1,4-diisocyanatocyclohexane (CHDI) and any desired mixture of such isomers, 1-isocyanato-2-isocyano Any desired mixture of acid methylcyclopentane, 1,2-, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane and isomers, 1,2-,1 , 3- and 1,4-bis(isocyanatoethyl)cyclohexane and any desired mixtures of such isomers, 1,2-, 1,3- and 1,4- (isocyanato-n-propyl)cyclohexane and any desired mixtures of such isomers, 1-isocyanatopropyl-4-isocyanatomethylcyclohexane and isomers , 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 1-isocyanato-1-methyl-4-isocyanate Methylcyclohexane (IMCI), 2,4'- and 4,4'-diisocyanatodicyclohexylmethane (H ₁₂ 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 isomerism And any desired mixture of such diisocyanates and a mercapto diisocyanate of the formula A composition according to the above patent application, characterized in that it contains or does not contain fatliquoring agents, fillers and/or buffer substances as additional substances. A composition according to one or both of the above claims, characterized in that it contains at least one carboxylic acid, preferably oxalic acid, succinic acid, glutaric acid or adipic acid, in particular at least one hydroxyl group, as component b) a polycarboxylic acid, preferably citric acid, tartaric acid or lactic acid or a mixture thereof, or a reaction product of at least one polycarboxylic acid and a carboxylic acid group-containing polyisocyanate. A composition according to at least one of the above claims, characterized in that the composition is an aqueous solution. A composition according to at least one of the preceding claims, characterized in that the composition is a solid and a particulate. A method for producing a composition according to at least one of claims 1 to 5, characterized in that in the presence of water and Simultaneously applying a shearing force to at least one organic polyisocyanate having a molecular weight of less than 400 g/mol and an NCO group attached via an aliphatic or cycloaliphatic group, with at least one bisulfite and/or coke For the sulfite reaction, a rotor-stator mixer is preferably used, wherein the carboxylic acid of the component b) is optionally reacted with the bisulfite and/or pyrosulfite. The reaction mixture obtained before, during or after the addition and optionally is subsequently dried. A method for producing a composition according to claim 6 of the invention, characterized in that the obtained liquid reaction mixture is mixed with a precipitating agent, and the resulting precipitate is dried. Use of a composition according to at least one of claims 1 to 5 as a pre-tanning preparation, re-preparation preparation for tanning, pre-tanning or re-sampling of hides and skins or鞣 preparation. Use of a composition according to at least one of claims 1 to 5 as a reaction component for an amine group-containing compound. The use of the ninth aspect of the patent application is characterized in that the amino group-containing compound is a biological material, especially a tissue related to other materials in the body and in vitro, such as skin material, connective tissue, bone, organ, muscle fiber or vasospasm material. , as appropriate, in isolated or purified form. Use of a composition according to at least one of claims 1 to 5 as an auxiliary for papermaking, in particular for the manufacture of wet strength or retention aids. Use of a composition according to at least one of claims 1 to 5 as a crosslinking agent for a protein-based water-soluble polymer, especially gelatin. A reaction product obtainable by reacting an amine-containing compound with a composition as in the first aspect of the patent application.