HK1007433A1

HK1007433A1 - Aqueous polyurethane and polyurethane carbamide dispersions, and a process for flock-coating moulded elastomeric products and for heat-sealing non-woven textile article

Info

Publication number: HK1007433A1
Application number: HK98105839A
Authority: HK
Inventors: Stockhausen Dolf; Dahman Kurt; Nagorski Herbert; Stukenbrok Karl-Heinz; Schlosser Herbert
Original assignee: Chemische Fabrik Stockhausen Gmbh
Priority date: 1988-11-26
Filing date: 1998-06-22
Publication date: 1999-04-09
Also published as: JPH04502022A; EP0445192A1; DE58909489D1; EP0445192B1; EP0445192B2; WO1990006330A1; ES2079385T3

Abstract

The invention concerns polyurethane and polyurethane carbamide dispersions and their use, together with water-soluble reactive melamine-resin or epoxy-resin pre-condensation products, for flock-coating moulded elastomeric products and for heat-sealing non-woven textile articles. The polyol component of the polyurethane or polyurethane carbamide consists of a high-molecular polycaprolactone polyol, or of a mixture of a high-molecular polyester polyol with a high-molecular polycaprolactone polyol. The polymer network has free groups which are reactive towards reactive melamine-resin and epoxy-resin pre-condensates.

Description

The invention relates to special aqueous PU dispersions, their use as flakes adhesives on rubber materials such as synthetic rubber (SBR), chloroprene rubber and ethylene-propylene-diene mixed polymerisates (EPDM) and to the hot sealing of textile surfaces.

The surface finishing of various substrates, such as textiles, leather, paper, plastics, metals, wood, etc., by blocking is now widespread. The substrate to be blocked is first coated with an adhesive, into which fiber particles are then inserted, in particular electrostatically shot.

In order to achieve a quality profile which meets the requirements, the flock adhesive must meet certain conditions: the basic requirement is that the adhesive develops a good adhesion to both the support material and the flock fibre; it must also be generally resistant to wet and dry wear, resistant to aging and UV radiation, resistant to water, detergents, oils, greases, organic solvents, etc. It must also be easy to handle and easy to process.

The choice of adhesive depends on the flocking technology, the type of flock used, the desired characteristics of the finished product and, last but not least, the type of support material to be flocked.

For the flocculation of rubber materials such as those used in particular in the automotive industry (e.g. as window or door seals), substrates such as styrene butadiene synthetic rubber, chloroprene rubber or ethylene propylene diene mix polymers (EPDM) are used, e.g. chloroprene rubber dissolved in organic solvents as an adhesive.

Polyurethane polymers dissolved in organic solvents are also used as flocculants for vulcanized and unvulcanized rubber materials (DE 3145861 and DE 3508995). The German disclosures DE 3322695 and DE 3400340 claim that polyurethane prepolymers with terminal isocyanate groups are flocculants for nonpolar elastomers. According to the information contained in these documents, these prepolymers can in principle be used in an undissolved, undiluted form. However, due to their better application, these prepolymers are preferred in the form of solutions or dispersions in organic solvents.

The health hazards, the fire and explosion hazards of solvent-containing adhesives and, above all, new environmental regulations make it desirable to use aqueous adhesive systems for the flocculation of rubber materials.

It has also been known for a long time that thermoplastic plastics such as polyethylene, PVC, polyamide or polyvinyl acetate-polyethylene copolymers are used to heat seal textile surfaces. The properties of these thermoplastics often do not meet the requirements, so that good hot-sealing adhesives are usually only achieved with customized adhesive systems and that the wide use of the known hot-glue adhesives often leads to only compromised solutions.

According to DE 17 69 482, DE 19 30 340, DE 23 42 149 and DE 34 01 129, solid polyurethanes are ground under intense cooling with e.g. liquid nitrogen, whereby polyurethane powder is obtained with a grain size distribution in the particle size range from 1 to 80 times that is favourable for the preferred paste-pressing process.

In a further process, polyurethane powder with a particle size of 1-80 but a much narrower grain size distribution is isolated from aqueous, sedimentary polyurethane dispersions, to produce special polyurethanes containing either ionic groups emulsifying according to DE 12 82 962 and DE 23 42 149 or, with the aid of external non-ionic emulsifiers according to DE 29 06 113 and DE 29 06 159, to transfer high shear forces into saturated, sedimentary polyurethane dispersions.

For use as hot-sealing adhesives, the polyurethane powders can be transferred directly by spraying or, after the addition of emulsifiers and other auxiliaries, into aqueous, printable pastes and then applied to the textile surface by crushing these pastes.

The adhesive-coated fabric is then joined to another piece of fabric by the skilled worker by the well-known short-term hot-stick at temperatures of up to about 160 °C under mechanical pressure. In order to achieve adhesive adhesions with good adhesive strengths under these conditions, the hot-sealing adhesives used must be adjusted so that they melt or at least soften at the applied sealing temperatures. The adhesive strength achieved depends not negligibly on the viscosity of the hot-glue under the sealing conditions.

Compared with other thermoplastic plastics, the use of polyurethane powders as hot-sealing adhesives has undoubtedly led to improvements in some areas of hot-sealing adhesives, but a wide, universal application has not yet been achieved with these products either.

Err1:Expecting ',' delimiter: line 1 column 108 (char 107)

EP-A 1 2924370 describes an aqueous dispersion of a PU prepolymer whereby the prepolymer is chained with a polyamine after mixing with an epoxy resin. EP-A 219677 describes the chain extension of aqueous dispersions of NCO prepolymers whereby the amine hydrogen of the polyfunctional amine may also be present in stoichiometric excess over the terminal isocyanate groups. Such dispersions can also be mixed with epoxy resins. DE-B 1 282 962 describes a process for the production of water-sedimentating dispersible PU dispersions whereby the hot dispersions of an NCO/H repolymer with ketamine are also prepared for the solution of these dispersions, indicating the survival of these dispersions.

The purpose of the invention is to provide stable aqueous polyurethane or polyurethane resin dispersions which are not inferior in quality to the solvent adhesives used to date, particularly in terms of adhesion to the substrate and abrasion resistance of the floc (genuinity), both as an aqueous adhesive and as an adhesive for the flocculation of elastomeric materials, and which can be applied to textile surfaces, preferably after thickening, preferably by the paste-pressing process, and which are hot-sealable, i.e. durable after-sealing, temperature-stable adhesives with good adhesion and good washing and hot-resistance.

This problem is solved according to the invention by the new aqueous polyurethane or polyurethane resin dispersions described in claim 1. - at least one higher molecular weight polyol- with a molar mass of 500 to 6000 g/mol, if applicable, and, in addition, at least two lower molecular weight compounds with a molar mass of 62 to 600 g/mol each with at least two NCO-reactive groups and- at least one compound with at least two NCO-reactive groups and at least one group capable of formation of lons with at least one aromatic, aliphatic and/or cycloaliphatic polyisocyanate to a prepolymer with a finite NCO group, neutralization of the prepolymer's ionic groups, chain extension and transition with at least one NCO-reactive group and at least one reactive melamine resin precondensate, orReactive epoxy resin reactive group containing authentication enhancing modifiers, and dispersion in water, where the neutralisation of the ion-forming groups before or during, the chain extension and the implementation with the authentication enhancing modifier can be carried out before or after the dispersion of the prepolymer in water, and chain extension and modifier are used in such quantities that the number of NCO reactive groups plus the melamine resin precursors or epoxy resin reactive groups exceeds the number of the final NCO groups of the prepolymer, and containing at least two NCO reactive groups or low molecular weight and/or aromatic poly/oyleth, aliphatic or dihydro/amino/amino/amino/amino/amino/amino/amino and/or dihydrazide, and/or amine and/or amide, and/or polyhydrazide,

Surprisingly, it has been shown that aqueous polyurethane or polyurethane urine dispersions, the polyol component of which consists of a higher molecular polycaprolactone polyol alone or a mixture of a higher molecular polycaprolactone polyol and a higher molecular polyester polyol, and whose polymer surface has free, reactive groups to reven melamine resin precursors or reactive epoxy resins, and which contain a small amount of water-soluble melamine resin precursor or an aqueous reactive epoxy resin, are obtained by a very good surface treatment not previously obtained with commercial polyurethane dispersions, and also by excellent surface treatment properties such as high resistance to heat and moisture, high resistance to water and moisture, and excellent resistance to other organic solvents and moisture, as well as by excellent surface treatment with non-organic materials and other materials.

Err1:Expecting ',' delimiter: line 1 column 165 (char 164)

The generally known starting materials include essentially higher molecular di- and/or higher functional compounds with hydrogen atoms reactive to NCO, such as polyhydroxy compounds with a molar mass of 500-10000 g/mol, preferably 500-6000 g/mol. In the dispersions used according to the invention, good adhesion has been obtained by using as a polyhydroxy compound a mixture consisting of a polyester polyol with a molar mass of 500-6000 g/mol, preferably 1000-4000 g/mol, and a polycaprolactone polyhydride with a molar mass of 500-6000 g/mol, preferably 1000-3000 g/mol. Examples: Polycaprolactone di-hydroxy-di-hydroxy-di-hydride or di-hydroxy-di-hydride, such as 1,4-butyl-di-hydride, 1,4-butyl-di-hydride, 1,4-butyl-di-hydride, 1,4-butyl-di-di-hydride, 1,4-butyl-di-di-di-hydride, 1,4-butyl-di-di-di-hydride, and di-hydride, and di-hydride, and di-hydride, and di-hydride, and di-hydride, and di-hydride, and di-hydride, and di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di-di

Where mixtures of higher molecular weight polyester and higher molecular weight polycaprolactone are used, they shall preferably have a ratio of 75: 25% by weight, and in particular 10: 90% by weight polyester polyester: polycaprolactone polyol.

The Commission also notes that the Commission has not provided any information on the specifications of the product concerned, but that the Commission has not provided any information on the specifications of the product concerned.

In addition to the higher molecular compounds, low molecular compounds with at least two, preferably three, NCO-reactive H atoms with molar masses of 62 to about 600 g/mol (e.g. as a connector) may be used for polyurethane construction, e.g. di- and/or polyols, aliphatic or aromatic di- and/or polyamine compounds, amino alcohols or thiol compounds. For example, ethylene glycol, diethylene glycol, 1,4-butandiol, 1,6-hexanediol, neopentylglycol, 1,4-dihydroxycyclohexane, trimethylpropan, glycerin, hexantriol, ethylene, thiamine and ethylene glycol. The low molecular weight of ethylene glycol is between 0,5% and 10,5% of the molecular weight of two compounds with higher molecular weight than NCO.

The inclusion of ionic groups in the polyurethane polymer is possible with compounds having at least two NCO reactive groups and at least one group capable of anion or cation formation. Suitable groups that react with NCO are in particular hydroxyl and primary and secondary amino groups. Carboxylic and sulphonic acid groups are generally used as anion-forming groups. Tertiary amino groups are particularly suitable for cation formation. Compounds that have at least two NCO reactive groups and at least one anion-forming group are dihydroxycarboxylic acids, e.g. dihydroxybutanolamines, bisphenol dihydroxypropionic acid, dihydroxybutanolamines or dihydroxypropanolamines.

Inorganic or organic bases such as tertiary amines and/or alkaline and alkaline hydroxides are generally used to neutralize the anion-forming groups, for example triethylamine, tributylamine, N-ethylmorpholine, ammonia, sodium hydroxide and potassium hydroxide.

The cation-forming groups are either neutralized with inorganic or organic acids such as hydrochloric acid, phosphoric acid, acetic acid, fumaric acid, maleic acid, lactic acid, tartaric acid and oxalic acid or converted into solubility mediating groups by transformation with a quaternizer such as methyl chloride, methyl iodide, dimethyl sulphate, chloracetamide, chlorosyl ethyl ester and benzyl chloride.

In addition to the ionic groups, the solutions and dispersions of the invention may also contain ethylene oxide and/or propylene oxide units as hydrophilic solubility mediating structural units, both within end and/or laterally arranged and internally embedded polyether chains.

The quantity of ionic components is generally chosen so that the dispersions of the invention have 2 to 100, preferably 5 to 50 milli-equivalents of ionized groups per 100 g of solid.

Polyocyanates may be used as aliphatic, cycloaliphatic, araliphic, aromatic or heterocyclic di- and/or technical polyisocyanates, preferably with molar masses up to 300 g/mol. The diisocyanates preferred are the isomeric toluene isocyanate, isophorondiisocyanate, 2,2,4 and/or 2,4,4-trimethyl-1,6-hexamethylenediisocyanate, 4,4'- and/or 2,4'-diphenylmethandiisocyanate or hexan-1,6-diisocyanate.

As chain-extenders, low molecular weight compounds with at least two H atoms reactive to NCO and with molar masses of 62 to approximately 400 g/mol are suitable, such as di- and/or polyoles, aliphatic or aromatic di- and/or polyamines, di- and/or polyhydrazides, aminohydrazides and amidines, in particular low molecular weight amines such as ethylene diamine.

Examples are hydrazine (hydrate), ethylene glycol, diethylene glycol, 1,4-butandiol, 1,6-hexandiol, glycerol, trimethylolpropane, propylene, isophorondiamine and other chain-extenders.

To improve the authenticity of the products, reactive groups are incorporated into the polymer molecule which react when the flock adhesive is dried with the addition of reactive melamine resin pre-condensates or reactive epoxy resins under interlacing.

The good adhesive accuracies obtained by the use of the polyurethane or polyurethane urethane dispersions of the invention for use as a flock adhesive and for hot sealing are achieved by a cross-linking process during the hot sealing process, which results in a maximum loss of the adhesive's thermoplasticity.

The interlacing component is a reactive melamine resin pre-condensate or a reactive epoxy resin. The interlacing of polyurethane dispersions with melamine resins is known in itself and is described, for example, in DE 35 16 806, US 3,835,081 and NL 7302704.

According to O. Lorenz, 12th Colloquium on the Chemistry and Technology of Macromolecular Substances at the Aachen University of Technology, 8 May 1987 (53rd publication of the Aachen University of Applied Sciences, pp. 115-121), the linkage is achieved by linking soluble carboxyl groups contained in the polymer backbone with hexamethoxymethylmelamine in a reaction under methanol decomposition and ester formation.

Surprisingly, the good authenticity of the adhesions according to the invention was found to be achieved only if, in addition to the carboxyl groups, there are other groups free from reactivity to melamine resin precursors or epoxy resins, in particular hydroxyl groups in the polymer cast.

The common auxiliaries used in polyurethane chemistry can also be used to produce polyurethanes, such as catalysts such as tertiary amines (e.g. triethylamine, tributylamine, N-methylmorpholine) or metal compounds (e.g. iron acetyl acetate, zinc dioctoate, dibutyl zinc dilavate), oxidation and light stabilizers, pigments and fillers.

The dispersions used in accordance with the invention were preferably produced by first extracting from the starting components, e.g.

- a polyester and a polycaprolactone polyol- or a low molecular weight di- or polyol- containing an ion-forming group and at least functionally reactive to NCO in which a prepolymer containing a finite isocyanate group is produced by the melting of the specified starting materials in a NCO/OH equivalent ratio of 1,2:1 to 2,5:1, preferably 1,2:1 to 1,8:1, the reaction temperature of which is generally 30 to 150 °C, preferably 50 to 1100 °C.

The method is preferably solvent-free and in cases of high prepolymer viscosity, organic NCO-inert solvents such as acetone, methyl-ethyl ketone, N-methylpyrrolidone and the like may be used.

The necessary amount of base, e.g. in the form of a tertiary amine, is added to the prepolymer and the prepolymer is then added to the dispersion water to neutralize anion-forming groups. Neutralization may also be carried out by introducing the base required for neutralization in the form of a tertiary amine and/or an alkali or alkaline hydroxy compound into the dispersion water and the prepolymer is cooled into this basic solution. The temperature of the dispersion water is generally 10-60 °C, preferably 15-40 °C. Neutralization of cation-forming groups may be achieved by incorporating into the prepolymer a third type of neutral base.The final NCO groups of the prepolymer are added to the chain extender and the authenticity enhancer to be transformed into either pure form or into a dilute, preferably aqueous solution. The chain extender and authenticity enhancer can be added as a mixture or separately. The addition can be done before or preferably after dispersion. In this transformation, the reaction temperature is 10-80°C, preferably 15-500°C. Since the pre-resin resins or epoxy resins react with the ketone groups in the same NCO group, the pre-extension and authenticity enhancer are usually added in such quantities that the number of NCO groups is higher than the number of NCO groups, and the number of NCO resins is higher than the number of NCO groups.where, for example, a diamine is used as a chain extender and an amino alcohol as an authentication modifier, the amounts of these components to be used are preferably chosen so that the amino groups react with the terminal NCO groups of the prepolymer under reactive extension and chain termination and the hydroxyl groups from the amino alcohol are available as the terminal groups for the reaction with the reactive melamine or epoxide.

The resulting polyurethane or polyurethane urea dispersions shall be treated with a water-soluble melamine resin pre-condensate or a reactive water-soluble epoxy resin in a quantity of 0,5 to 10% by weight, preferably 1 to 5% by weight, as a thermally activated net, either immediately after manufacture or immediately before use.

Reactive melamine resin pre-condensates and epoxy resins are known, e.g. the commercial products Cassurit HML liquid (50% aqueous solution) = Hexamethyl melamine and Eurepox 756 D (67%), by F. Schering AG.

For the coating of elastomeric moulds, the aqueous polyurethane or polyurethane urine dispersions described above are applied to the substrate after the addition of the reactive melamine resin pre-condensate or, where appropriate, the reactive epoxy resin after prior thickening, loaded with textile short fibre coatings and dried, condensed and, where appropriate, removed from excess flock at elevated temperature.

The mixture of polyurethane or polyurethane urea dispersion and water-soluble reactive melamine resin pre-condensate or water-soluble reactive epoxy resin used for flocculation shall be applied to the substrate to be flocculated by appropriate methods, preferably a brush, brush or spray gun.

Drying and condensation are preferably carried out at temperatures in the range of 70 to 180 °C.

It has been shown to be advantageous to apply the dispersions used as flocculants according to the invention with a dry matter content of 30 to 160 g/m2, preferably 50 to 100 g/m2.

For the hot sealing of textile surfaces such as fabrics, knitted or crocheted, the aqueous polyurethane or polyurethane resin dispersions described above are applied to a position on the textile surface, preferably by the paste-point method, after the addition of 0,5 to 10% by weight of reactive epoxy resin, if necessary after prior thickening, and the coated textile material is then dried at elevated temperatures and, if necessary, subsequently a second textile surface is formed under pressure and at elevated temperature with the first surface.

The manufacture of the dispersions used in accordance with the invention is described in more detail in the following examples.

The following is the list of the categories of products:

The approach: After 60 minutes of stirring, mix 1 is drained in a vacuum at 120 °C. After cooling to 80 °C and aeration with nitrogen, the diisocyanate is added. It is stirred in an N2 atmosphere at 90-95 °C until a constant NCO value is reached. It is then cooled to 80 °C, the N-ethylmorpholine is added and stirred for another 15 minutes at 80 °C. The hot melt is then introduced into the cold, well-stirred dispersion water within 5 minutes.

The following is the list of the

The approach: After 60 minutes of stirring, dilute the mixture 1 in a vacuum at 120 °C. After cooling to 80 °C and aeration with nitrogen, add the diisocyanate. Stir the mixture in an N2 atmosphere for 2 hours at 90-95 °C. Then add dimethylolpropionic acid and stir the mixture at 90-95 °C until a constant NCO value is reached. Then cool to 80 °C, add the N-ethyl morpholine ketone and stir for another 15 minutes at 80 °C. Then stir the hot shot in the cold, well-stirred dispersant for 5 minutes.

The following is the list of the

The approach: After cooling to 80 °C and aeration with nitrogen, the diisocyanate is added. It is stirred in an N2 atmosphere at 90-95 °C until a constant NCO value is reached. It is then cooled to 80 °C, the N-ethylmorpholine is added and stirred for another 15 minutes at 80 °C. The hot melt is then stirred into the cold, well-stirred dispersing water within 5 minutes. After dispersing for 30 minutes, the ethanolamine solution is first stirred and then the ethylenelamine solution. Finally, the solution is stirred at room temperature for another one hour.

The following is the list of the

The approach: Implementation: analogue Example 1 A fine dispersion is produced with a solid content of 40% and a Brookfield viscosity of 40 mPa.s.

The following is the list of the

The approach: Implementation: analogue Example 1 A fine dispersion is produced with a solid content of 40% and a Brookfield viscosity of 1370 mPa.s.

The following is the list of the

The approach: Implementation: analogue Example 1 A fine dispersion is produced with a solid content of 30% and a Brookfield viscosity of 22 mPa.s.

The following is the list of the

The approach: Implementation: analogue Example 1 A fine dispersion is produced with a solid content of 60% and a Brookfield viscosity of 3240 mPa.s.

The following is a list of the

Approach: 92,82 g of a polycaprolactone with an OH number of 56 4,80 g dimethylpropionic acid25,02 g of a technical mixture of 2,2,4 and 2,4,4 trimethyl-1,6-hexamethylpropionic acid4,12 g N-ethylmorpholine1,47 g ethyleneethylamine1,54 g ethanolamine188,00 g waterConduct: The mixture of polycaprolactone and dimethylpropionic acid is drained by stirring for 60 minutes at 120°C in a vacuum. After cooling at about 90°C and aeration with nitrogen, the diisocyanate is added to the ketone. It is stirred in an N2 atmosphere at 90-95°C until a constant NCO value is reached.

The following is the list of the categories of products: Manufacture from materials of any heading

The approach: Execution: Component A is drained for 1 hour at 90-95 °C under vacuum stirring.After a clear polyester mixture has been formed,the apparatus is aerated with nitrogen and the diisocyanate is added within a few minutes at 90 °C.After a reaction time of 2 hours at 90-95 °C,component B is added and stirred for 1 hour at 90-95 °C.The prepolymer is then neutralized by adding the NEM and a post-stirring time of 20 minutes.The prepolymers thus produced are introduced into the dispersion water within 5-10 minutes and stirred for 1 hour.The chain extension or chain closure is done by adding the two subsequent components to the dispersion chain and the dispersion is effected at a pH of 604.4 mPa.The dispersion is then removed from the liquid at a temperature of 60 °C for 1 hour.The dispersion chain is then removed at a pH of 405.4 mPa.

The Commission has

The approach: Execution: Component A is drained under vacuum stirring for 1 hour at 90-95 °C.After obtaining a clear polyester mixture, the apparatus is aerated with nitrogen and the diisocyanate is added within a few minutes at 90 °C.After a reaction time of 2 hours at 90-95 °C,component B is added and stirred for 1 hour at 90-95 °C.Neutralization of the prepolymer is achieved by adding the NEM after a stirring time of 20 minutes.The prepolymer thus produced is introduced into the dispersion water within 5-10 minutes and stirred for 1 hour.The subsequent extension or termination of the chain is done by successive addition of the two components at 90-95 °C and stirred for 1 hour.The dispersion is effected by a solid solution with a pH of 7.60.

The test chemical is used to determine the concentration of the active substance in the test chemical.

The approach: The method of analysis is based on the following equation:

The test chemical is a desmodur W (= aliphatic diisocyanate)

The approach: The method of analysis is based on the following equation:

The following is a list of the

The approach: The mixture of polycaprolactone, polyester and dimethylolpropionic acid is drained in a vacuum for 60 minutes at 120 °C by stirring. After cooling to about 90 °C and aeration with nitrogen, the diisocyanate is added. It is stirred in an N2 atmosphere at 90-95 °C until a constant NCO value is reached. The N-ethylmorpholine is then added and the hot melt is introduced into the cold, well-stirred dispersion water. 30 minutes after dispersion, the extended chain (chain termination) is made by adding the ethylene-ethylamine solution by dripping. Finally, the food is stirred for one hour at a room temperature.

The following is a list of the

The approach: Implementation: Analogue Example 13 A fine dispersion is produced with a solid content of 40% and a Brookfield viscosity of 960 mPa.s.

The following is a list of the

The approach: Implementation: Analogue Example 13A fine dispersion is produced with a solid content of 40% and a Brookfield viscosity of 1550 mPa.s.

The following is a list of the

The approach: Implementation: Analogue Example 13 A fine dispersion is produced with a solid content of 40% and a Brookfield viscosity of 400 mPa.s.

Comparison example

Approach: 88,17 g of a polycaprolactone with an OH number of 56 200,72 g of an adipic acid hexandiol polyester with an OH number of 4114.25 g dimethylolpropionic acid68,12 g of a technical mixture of 2,2,4 and 2,4,4 trimethyl-1,6-hexamethylenediisocyanate12,23 g N-ethylmorpholine4,23 g ethylene diamine in 29,4 g water552,18 g waterConduct: analogue Example 13A fine dispersion with a solid content of 40% and a Brookfield viscosity of 630 mPa.s. is formed.

The method of application of the dispersions as a flaky adhesive is as follows: A mixture of: 100 T of dispersion and 2-5 T of reactive melamine resin precondensate or 2-5 T of reactive epoxy resin is applied to the substrate to be flooded by means of a brush, brush or spray gun to produce a moisture content of 200 to 250 g/m2.

The bonding layer is made of a fibre strand, preferably of polyamide or polyester fibres, which is electrostatically injected into the bonding layer and the excess is removed by suctioning. Immediately afterwards, the stranded substrate is dried to initiate the formation of the adhesive film. After evaporation of the water or any solvent (N-methylpyrrolidone) present, it is meshed at temperatures above 140 °C and, if appropriate, sintered at 180 °C. The resulting compensation ensured optimal integration of the stranded fibres and a high concentration of the latter on the substrate.

After the interlinking and compensation, unbound flax fibres are removed by brushing and suctioning.

Application example A: A rubber mixture of EPDM is processed into a profile by extruder and nozzle, on which, after roughing, an adhesive mixture of: 100 T of dispersion from sample 1 and 2 T of reactive melamine resin pre-condensate is applied, with a wet flow of 215 g/m2. In this adhesive bed, a polyamide flax fibre of 0.75 mm 1.5 dtex with a voltage of 70 KV and a current of 0.02 A is injected and the whole is dried in stages at 100, 130 and 180 °C, but continuously. Finally, the profiles thus produced are brushed and wrapped. A abrasion test is carried out, as is usual in the flax industry, e.g. according to the Opel test method - GME 60248.

Application example B: Analogue Application example A: A profile of EPDM is made with a mixture of glues 100 T of dispersion from examples 3 and 3 T of reactive epoxy resin, with a moisture content of 227 g/m2 is obtained.

Err1:Expecting ',' delimiter: line 1 column 263 (char 262)

Err1:Expecting ',' delimiter: line 1 column 349 (char 348)

The printing process, as mentioned, uses rotary printing molds with different mesh sizes, which are adjusted to the viscosity of the printing paste.

After drying, between 5 and 55 g/m2, preferably 15 to 25 g/m2, of the hot-sealable polyurethane or polyurethane resin is found on the substrate.

A textile product line (inlay or braid) is then glued to a second textile surface (back of a garment) on so-called fixing presses, with temperatures in the adhesive between 140 and 175 °C, a pressure of 0.2 to 4.0 bar and a residence time of 12 to 30 seconds.

After cooling, the compound already shows its full adhesion and usability.

The test shall be carried out on the test vessel. The following information shall be provided to the Commission by the Member States: The product is mixed with each other to give a storage-stable usable paste with a Brookfield viscosity of 11400 mPa.s. It was printed on a cotton netting of 80 g/m2 (inlay) with an 11 mesh rotary press and dried at 100 °C. This resulted in a drying pressure of 15,7 g/m2.

The pre-filled material was sealed against a polyester/cotton 66:33 top of 180 g/m2 under the following conditions. Other

The laminate thus produced had a separating power of The test chemical is then applied to the test chemical.

Comparative use case

An adhesive produced under the same conditions with the non-inventional dispersion of the comparator example (without amino alcohol) yielded the following separating forces at a dry pressure of 23,3 g/m2: Other

The adhesive strengths obtained with dispersions 10-12 are listed in the following table.

Claims

1. Aqueous dispersions of polyurethane or polyurethane urea obtainable by reaction of a mixture of

- at least one high-molecular polyol,

- with a molar mass of 500 - 6,000 g/mol optionally additional low-molecular compounds with a molar mass of 62 - 600 g/mol and at least two NCO-reactive groups each, and

- at least one compound having at least two NCO-reactive groups and at least one group capable of forming ions with at least one aromatic, aliphatic and/or cycloaliphatic polyisocyanate to form a prepolymer having terminal NCO-groups, neutralization of the ion-forming groups of the prepolymer, chain extension and reaction with a fastness-improving modifying agent comprising at least one NCO-reactive group and at least one group which is reactive towards reactive melamine-resin precondensates or towards reactive epoxide resins, and dispersion in water, wherein the neutralization of the ion-forming groups may be effected either prior to or during the dispersion of the prepolymer in water, and the chain extension and reaction with the fastness-improving modifier may be effected either prior to or after dispersion of the prepolymer in water, the chain prolongation agent and the modifying agent being used in such an amount that the number of NCO-reactive groups plus the groups which are reactive towards melamine-resin precondensates or epoxide resins exceeds the number of terminal NCO-groups of the prepolymer, wherein low-molecular diols and/or polyols comprising at least two NCO-reactive groups, aliphatic or aromatic diamines and/or polyamines, dihydrazides and/or polyhydrazides, amino hydrazides and/or amidines, in particular low-molecular diamines, such as ethylene diamine are used as chain extenders, and amino alcohols are used as fastness-improving modifying agent.

2. Aqueous polyurethane or polyurethane urea dispersions according to claim 1 characterized in that a high-molecular polycaprolacton polyol or a mixture of a high-molecular polyester polyol and a high-molecular polycaprolacton polyol is used as high-molecular polyol.

3. Aqueous polyurethane or polyurethane urea dispersions according to claim 1 or 2 characterized in that a polyester polyol having a molar mass of 1,000 - 4,000 g/mol is used as high-molecular polyester polyol.

4. Aqueous polyurethane or polyurethane urea dispersions according to claim 1 or 2 characterized in that a polycaprolacton polyol having a molar mass of 1,000 - 3,000 g/mol is used as high-molecular polycaprolacton polyol.

5. Aqueous polyurethane or polyurethane urea dispersions according to claim 1 or 2 characterized in that a mixture of a high-molecular polyester polyol and a high-molecular polycaprolacton polyol at a ratio of 75:25%-wt. to 10:90%-wt. is used.

6. Aqueous polyurethane or polyurethane urea dispersions according to claim 1 or 2 characterized in that diols and/or polyols, aliphatic or aromatic diamines and/or polyamines, amino alcohols, or thiol compounds, preferably trimethylolpropane or glycerol, are used as low-molecular compounds having at least two NCO-reactive groups.

7. Aqueous polyurethane or polyurethane urea dispersions according to claim 1 or 2 characterized in that a tertiary dihydroxyamine capable of forming cations or a dihydroxycarboxylic acid capable of forming anions, preferably dimethylolpropionic acid, is used as compound comprising at least two groups reacting with NCO and at least one group capable of forming ions.

8. Aqueous polyurethane or polyurethane urea dispersions according to claim 1 or 2 characterized in that an aromatic, aliphatic and/or cycloaliphatic diisocyanate, preferably a technical mixture of 2,2,4- and 2,4,4,-trimethyl-1,6-hexamethylene diisocyanate, is used.

9. Aqueous polyurethane or polyurethane urea dispersions according to claim 1 or 2 characterized by a content of 0.5 - 10, preferably 1 to 5%-wt. of a water-soluble, reactive melamine-resin precondensate or of a reactive, water-soluble epoxide resin precondensate.

10. A process for flock-coating moulded elastomeric articles characterized in that either an aqueous dispersion as defined in any one of claims 1 - 8, after addition of 0.5 - 10%-wt. of a reactive melamine-resin precondensate or of a reactive epoxide resin, or an aqueous dispersion as defined in claim 9, optionally after previous thickening, is applied to the substrate, charged with textile ground fibers by flock-coating, dried at an elevated temperature, condensed, and, if necessary, released from excess flock.

11. The process according to claim 10 characterized in that the mixture employed for flocking that consists of polyurethane or polyurethane urea dispersion and water-soluble, reactive melamine-resin precondensate or water-soluble, reactive epoxide resin and which optionally comprises a thickener, is applied to the substrate to be flock-coated by means of a paint-brush, brush or spray gun.

12. The process according to claim 10 characterized in that temperatures ranging from 70 - 180 _°C are employed for drying and condensation.

13. The process according to claim 10 characterized in that a dispersion used as an adhesive is applied at a dry layer thickness of 30 - 160 g/m², preferably 50 - 100 g/m².

14. The process according to claim 10 characterized in that dispersions are used comprising 30 - 60%-wt., preferably 35 - 45%-wt. of solid substance.

15. A process for heat-sealing textile articles, such as woven fabrics, knitwear, or non-wovens, characterized in that an aqueous dispersion as defined in any one of claims 1 to 8, after addition of 0.5 to 10%- wt. of a reactive melamine-resin precondensate or of a reactive epoxide resin, optionally after previous thickening, is applied to a layer of the textile article, preferably by means of the paste-point-process, the textile article thus coated is dried at elevated temperatures, and that optionally a second textile article is glued to the first textile article under pressure and at an elevated temperature.

16. The process according to claim 15 characterized in that the coated textile article is dried at temperatures ranging from 80 to 100°C.

17. The process according to claims 15 or 16 characterized in that the dispersion used as heat-sealing adhesive is applied at a dry layer thickness of 5 to 25 g/m², preferably 15 to 25 g/m².