WO2000059979A1

WO2000059979A1 - Dimethyl-pyrazole blocked polyurethane dispersions and polyisocyanate for dressing glass fibres

Info

Publication number: WO2000059979A1
Application number: PCT/EP2000/002483
Authority: WO
Inventors: Harald Blum; Karin Naujoks
Original assignee: Bayer Aktiengesellschaft
Priority date: 1999-04-01
Filing date: 2000-03-21
Publication date: 2000-10-12
Also published as: AU3814000A; DE19914885A1

Abstract

The invention relates to polyurethanes, polyurethane polyureas and polyureas containing dimethyl pyrazole, to a method for producing products of this type and to the use thereof in dressing glass fibres.

Description

Dimethylpyrazole blocked polyurethane dispersions and polyisocyanates for glass fiber sizing

The invention relates to polyurethanes containing dimethylpyrazole, polyurethane polyureas or polyureas, processes for producing such products and their use in sizes.

The use of polyurethane dispersions for the production of glass fiber sizes is e.g. known from US-A 4 255 317. Also e.g. from EP-A

79 29 00 is known to use hardener components based on blocked polyisocyanates in glass fiber sizes. Hard materials blocked with dimethylpyrazole or their particular suitability in sizes are not mentioned. Polyisocyanates blocked with dimethylpyrazole and lacquers or coating compositions which contain polyisocyanates blocked with dimethylpyrazole are used in the

EP-A 15 91 17 and WO 97/12924 are described. The suitability of these products for finishing is not described.

Surprisingly, it has now been found that sizes contain the polyurethanes, polyurethane-polyureas or polyureas modified with dimethylpyrazole in the form of dispersions and / or hardener components based on polyisocyanates blocked with dimethylpyrazole, show improved processability of glass fibers sized therewith and improved mechanical properties of corresponding glass fiber-reinforced plastics. Another advantage of the glass fibers sized according to the invention is their low bulk volume and the reduced tendency to electrostatic charging.

The invention relates to polyurethanes, polyurethane-polyureas or polyureas in the form of dispersions which are modified with 0.1 to 15, preferably 0.25 to 7.5% by weight of dimethylpyrazole, a process for the preparation of such

Dispersions and the use of such dispersions or of dimethylpyrazole containing hardness based on blocked polyisocyanates in or as sizes, in particular glass fiber sizes.

The invention relates to dispersions based on polyurethanes, polyurethane-polyureas or polyureas which are preferably reaction products of

a) at least one polyol component, b) at least one di-, tri- and / or polyisocyanate component, c) optionally at least one (potentially) ionic structural component, consisting of compounds having at least one group reactive toward NCO groups and at least one, optionally at least partially neutralizes the present group capable of salt formation, d) optionally at least one nonionic-hydrophilic structural component, consisting of mono- to tetrafunctional compounds having at least one hydrophilic polyether chain in the sense of the isocyanate addition reaction, e) optionally at least one different from a) to d) Build-up component of the molecular weight range 32 to 2500 with groups reactive towards isocyanate groups and f) 0.1 to 15% by weight of at least one monofunctional blocking agent which consists of at least 50% dimethylpyrazole,

where the sum of a) to f) is 100% and either c) or d) cannot be 0 and are used in such an amount that a stable dispersion is formed.

The invention relates to dispersions based on polyurethanes, polyurethane-polyureas or polyureas, which are particularly preferably reaction products of a) 30 to 90% by weight of at least one polyol component in the hydroxyl number range 5 to 350, b) 10 to 50% by weight of at least one di-, tri- and / or polyisocyanate component, c) 0 to 10% by weight. % of a (potentially) ionic structural component, consisting of at least one compound with at least one group reactive towards NCO groups and at least one, optionally at least partially neutralized, group capable of salt formation, d) 0 to 20% by weight of a nonionic hydrophilic structural component consisting of at least one compound which is mono- to tetrafunctional in the sense of the isocyanate addition reaction and has at least one hydrophilic polyether chain, e) 0 to 20% by weight of at least one structural component of the molecular weight range 32 to 2500 which is different from a) to d) groups reactive toward isocyanate groups and f) 0.1 to 15% by weight of at least one monofunctional blocking agent which consists of at least 50% dimethyl pyrazole,

The invention also relates to dispersions based on polyurethanes, polyurethane-polyureas or polyureas which are particularly preferably the reaction products of

a) 40 to 85% by weight of at least one polyol component in the hydroxyl number range 5 to 350, b) 15 to 40% by weight of at least one di-, tri- and / or polyisocyanate component, c) 0 to 7% by weight of a (potentially) anionic structural component, consisting of at least one compound having at least one group which is reactive toward NCO groups and at least one, optionally at least partially neutralized, group capable of salt formation, d) 2 to 20 % By weight of a nonionic-hydrophilic structural component consisting of at least one compound which is mono- to tetrafunctional in the sense of the isocyanate addition reaction and has at least one hydrophilic polyether chain, e) 0 to 10% by weight of at least one structural component different from a) to d) component with groups of molecular weight 32 to 2500 which are reactive towards isocyanate groups and f) 0.25 to 7.5% by weight of at least one monofunctional blocking agent which consists of at least 50% dimethylpyrazole,

where the sum of a) to f) is 100% and where c) and / or d) in such

Amount used that a stable dispersion is formed.

Dispersions are very particularly preferably characterized in that the solid of the dispersion is the reaction product of

a) 40 to 85% by weight of at least one polyol component with a molecular weight of 600 to 3500 based on carbonate diols, polytetrahydrofuran diols and / or polyethers based on propylene oxide or propylene oxide / ethylene oxide, b) 15 to 40% by weight of at least one Di-, tri- and / or polyisocyanate component, c) 0 to 7% by weight of a (potentially) anionic build-up component, consisting of at least one compound with at least one group reactive towards NCO groups and at least one, optionally at least partially neutralized present group capable of salt formation, d) 2 to 20% by weight of at least one nonionic-hydrophilic structural component with a molecular weight of 1000 to 2500, consisting of at least one polyfunctional polyether in the sense of the isocyanate reaction with a built-in propylene oxide content of 15 to 57% and a built-in ethylene oxide content of 85 up to 43%, e) 0.2 to 6% by weight of at least one structural component of the molecular weight range 32 to 400 different from a) to d) with primary or secondary amino and / or hydroxyl groups reactive towards isocyanate groups and f 0.5 to 4.5% by weight of at least one monofunctional blocking agent or blocking agent mixture which consists of at least 70% dimethylpyrazole,

the sum of a) to f) being 100%, either c) and / or d) being used in such an amount that a stable dispersion is formed.

The invention also relates to a process for the preparation of the dispersions according to the invention, characterized in that from the components a), b), if appropriate c) and / or d) mentioned, if appropriate with the use of a hydroxy-functional component e), firstly an NCO-functional prepolymer is then optionally added solvent, some of the remaining NCO groups are reacted with component f) and the other NCO groups are reacted with component c) and / or a further amino-functional component e) either before, during or after dispersion and the solvent is then optionally removed by distillation.

The invention also relates to the use of the dispersions according to the invention in lacquers and coatings, in particular in sizes and particularly preferably in glass fiber sizes. The invention also relates to the use of polyisocyanate-based hardnesses which may have been hydrophilized and blocked with dimethylpyrazole in sizes, in particular in glass fiber sizes.

Polyol components a) suitable for producing the dispersions according to the invention are e.g. Polyester polyols (e.g. Ulimann's Encyclopedia of Industrial Chemistry, 4th edition, volume 19, pp. 62-65). Suitable raw materials for the production of these polyester polyols are difunctional alcohols such as ethylene glycol, 1,2- and 1,3-propylene glycol, 1,3-, 1,4-, 2,3-butanediol, 1,6-hexanediol, neopentylglycol, trimethylhexane - Diol, triethylene glycol, hydrogenated bisphenols, trimethylpentanediol, diethylene diglycol, dipropylenediglycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and difunctional carboxylic acids or their anhydrides such as adipic acid, phthalic acid (anhydride), isophthalic acid, maleic acid (anhydride) , Terephthalic acid, tetrahydrophthalic acid (anhydride), hexahydrophthalic acid (anhydride), succinic acid (anhydride), fumaric acid, azelaic acid, dimer fatty acid. Other suitable polyester polymers are monocarboxylic acids such as benzoic acid, 2-ethylhexanoic acid, oleic acid, soybean oil fatty acid, stearic, peanut oil fatty acid, linseed oil fatty acid, nonanoic acid, cyclohexane-monocarboxylic acid, isononanoic acid, sorbic acid, conjuene fatty acid, höherfünktionelle carboxylic acids or alcohols such as trimellitic acid (anhydride), butanetetracarboxylic acid, trimer fatty acid, trimethylolpropane, Glycerin, pentaerythritol, castor oil, dipentaerythritol and other polyester raw materials not mentioned by name.

Also suitable polyol components a) are polycarbonate diols which can be obtained, for example, by reacting diphenyl or dimethyl carbonate with low molecular weight diols or triols or ε-caprolactone-modified diols or triols.

Lactone-based polyester diols are also suitable, which are homo- or copolymers of lactones, preferably terminal hydroxyl-containing addition products of lactones, such as ε-caprolactone or γ-butyrolactone, on difunctional starter molecules. Suitable starter molecules can include the diols mentioned above, but also low molecular weight polyester or poly be ether diols. Instead of the polymers of lactones, the corresponding hydroxycarboxylic acids can also be used.

Also suitable polyol components a) are polyether polyols. They are especially by polymerization of ethylene oxide, propylene oxide, tetrahydrofuran,

Styrene oxide and / or epichlorohydrin can be obtained with itself, for example in the presence of BF ₃ or basic catalysts or else by addition of these compounds, if appropriate also in a mixture or in succession, on starter components with reactive hydrogen atoms, such as alcohols, amines, amino alcohols or water.

The polyol components a) mentioned can also be used as mixtures, if appropriate also together with other polyols a) such as Polyesteramides, polyether esters, polyacrylates are used.

The hydroxyl number of the polyols a) is 5 to 350, preferably 8 to 200 mg KOH / g substance. The molecular weights of the polyols a) are between 350 and 25,000, preferably between 600 and 15,000, polyols a) with a molecular weight of> 9000 g / mol being at least partially used in a particularly preferred embodiment. Particularly preferred as component a) are hydrolysis-stable polyols of molecular weight 600 to 3500 based on carbonate diols, tetrahydrofuran diols and / or polyethers based on propylene oxide or propylene oxide / ethylene oxide.

Component b) consists of at least one organic di-, tri- or poly-isocyanate with a molecular weight of 140 to 1500, preferably 168 to 262. For example, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4'-diisocyanatodicyclohexylmethane are suitable (H12MDI), 1,4-butane diisocyanate, hexahydrodiisocyanatotoluene, 1, 3-bishydroxymethylcyclohexane, hexahydrodiisocyanatoxylol, nonanetriisocyanate. Aromatic isocyanates such as 2,4- or 2,6-diisocyanatotoluene (TDI), xylylene diisocyanate and 4,4'-diisocyanatodiphenyl methane are also suitable, but less preferred. Known polyisocyanates based on the above and also other isocyanates with uretdione, biuret, allophanate, isocyanurate, iminoxadiazinedione or urethane structural units can also be used. The use of isophorone diisocyanate, hexamethylene diisocyanate and / or 4,4'-diisocyanatodicyclohexylmethane is particularly preferred.

Component c) consists of at least one (potentially) ionic compound with at least one group which is reactive towards isocyanate groups. These compounds are preferably at least one, preferably one or two hydroxyl and / or primary or secondary amino groups having carboxylic acid, sulfonic acid and phosphoric acid or salts thereof. Suitable acids are e.g. Hydroxypivalic acid, dimethylolacetic acid, 2,2'-dimethylolpropionic acid, 2,2'-dimethylolbutyric acid, 2,2'-dimethylolpentanoic acid, aminobenzoic acid, addition products of acrylic acid and diamines such as e.g. Ethylenediamine or isophoronediamine. The use of sulfonate diols of the type described in US Pat. No. 4,108,814, optionally containing ether groups, is also suitable. Amino-functional sulfonates are also suitable. Also suitable, but less preferred are compounds with at least one hydroxyl and / or primary or secondary amino group and at least one free tertiary amino group, or their salts with carboxylic, sulphonic or phosphoric acid.

The free acid or amino groups, in particular carboxyl and sulfonic acid groups, represent the “potentially ionic or anionic” groups mentioned above.

Groups, while the salt-like groups obtained by neutralization with bases or acids, in particular carboxylate groups and sulfonate groups, are the “ionic or anionic” groups mentioned above. In a preferred embodiment, at least 50% of the addition product of acrylic acid and isophoronediamine is used as component c). The cycloaliphatic group of this hydrophilizing agent results in particularly favorable compatibility, a reduced tendency to crystallize the polymer, improved physical drying after application and overall improved

Get application properties.

Component d) consists of at least one nonipnic hydrophilic compound which has one or two groups which are reactive toward isocyanate groups per molecule, in particular hydroxyl and / or primary or secondary amino groups. The polyether chains of these compounds consist of at least 30% built-in ethylene oxide units, in a preferred embodiment 40 to 95% built-in ethylene oxide units in addition to 5 to 60% built-in propylene oxide units. Suitable such components d) have molecular weights of 300 to 6000 and are e.g. monofunctional polyethylene

/ propylene glycol monoalkyl ethers such as Breox® 350, 550, 750 from BP Chemicals, polyether LB 25, LB 30, LB 34, LB 40 from Bayer AG, polyethylene propylene glycols such as Carbowax® 300, 400, 1000, 2000, 6000 from Union Carbide, di - or monofunctional polyetheramines such as Jeffamine® ED600, ED900, ED4000, M715, Ml 000, M2070 from Texaco. Monofunctional components d) with a molecular weight of 1000 to 2500 with a built-in propylene oxide content of 15 to 57% and a built-in ethylene oxide content of 85 to 43% are particularly preferably used.

Component e) is at least one, preferably at least two other mono-, di- or polyfunctional compounds of molecular weight 32 to 2500 with primary or secondary amino and / or hydroxyl groups. Suitable are e.g. Ethylene diamine, diethylene triamine, isophorone diamine, hexamethylene diamine, 4,4-diaminodicyclohexyl methane, hydrazine (hydrate), propylene diamine, dimethylethylene diamine, ethylene glycol, 1,2-, 1,3-propylene glycol, 1,4-

Butanediol, neopentylglycol, 1,6-hexanediol, trimethylpentanediol, trimethylolprop- pan, glycerin, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltributoxysilane, aminoethylaminopropyltrimethoxysilyl ester, maliethyl ester product from maleinethylester with Meth) acrylic acid and the glycidic ester of versatic acid (Cardura® E10, Shell), reaction product of 2 moles of propylene carbonate and 1 mole of hydrazine, adipic acid dihydrazide and / or mixtures of the components e) mentioned, optionally also with other components e). Components e) are very preferably used in amounts of 0.2 to 6% by weight, the molecular weights of

Components e) are preferably 62 to 400.

By suitable selection of component e), the molecular weight build-up can be influenced by chain extension, chain branching and / or chain termination and / or functional groups can be introduced. If components e) are used to produce the prepolymer, preference is given to using hydroxy-functional components e) of the type mentioned. If components e) are used for chain extension of the prepolymer in organic solution or in aqueous dispersion, di- and / or trifunctional amine components e) are preferably used. For chain termination reactions, monoamino-functional alkoxysilanes such as e.g. 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane or their reaction products with maleic dialkyl esters of the type mentioned above, e.g. in amounts of 0.2 to 5, particularly preferably in amounts of 0.5 to 2.5,% by weight.

Suitable components f) in addition to dimethylpyrazole are e.g. Diisopropylamine, triazole, dimethyl malonate, diethyl malonate, dibutyl malonate, methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate, butanone oxime, cyclohexanone oxime, acetone oxime, epsilon-caprolactam, phenol, e.g. Diisopropylamine, diethylamine,

Cyclohexylamine, butylamine, monofunctional alcohols such as butanol, cyclo- hexanol, isoprpanol, tert. Butanol, ethanol, and other known blocking agents. Component f) consists of at least 50%, preferably at least 70%, very particularly preferably 100%, of dimethylpyrazole. Component f) is used in amounts of 0.1 to 15, preferably in amounts of 0.25 to 7.5 and very particularly preferably in amounts of 0.5 to 4.5% by weight. Preferred further components f) which can be used in addition to dimethylpyrazole are butanone oxime, ε-caprolactam and triazole.

Components a) and b) can be reacted in one or more stages, optionally with the use of c) and / or d) and / or a hydroxy-functional component e). The reaction can be carried out in bulk or in organic solvents, then preferably in acetone. The equivalent ratio of the OH-functional components a) and optionally c) and or d) and / or e) to the NCO-functional component b) is chosen so that an NCO excess of 20 to 200, preferably 30 to 150% results. The NCO-functional prepolymer initially produced in this way is optionally mixed with solvent and then some of the remaining NCO groups are reacted with component f). This reaction is preferably carried out at temperatures from 30 to 110, very particularly preferably at 30 to 80 ° C. The remaining NCO groups are reacted with an amino-functional component c) and / or another amino-functional component e) either before dispersing, then in acetone solution, or during or after dispersing, and then, if appropriate, the solvent is removed by distillation. The hydrophilic components c) and b) are used in such quantities that stable dispersions are formed. If the hydrophilic components are incorporated into the prepolymer, preference is given to using hydroxyl-functional hydrophilizing agents. The use of amino-functional hydrophilizing agents is preferably carried out in the presence of a solvent and subsequent to the prepolymer preparation, for example in the chain extension step. In a preferred embodiment, mixed hydrophilization is carried out from ionic and nonionic components, 3 to 18% by weight of nonionic monofunctional components being very particularly preferred. nenten d) are used together with 0.1 to 5 wt .-% ionic components b).

The reaction of the components can be carried out with the addition of catalysts such as e.g. Dibutyltin dilaurate, tin 2-octoate, dibutyltin oxide or diazabicyclononane can be carried out.

For converting the acid groups into salt groups, e.g. Amines such as triethylamine, N-methylmorpholine, diisopropylamine and potassium or sodium hydroxide can be used. The degrees of neutralization are between 40 and 120%.

After dispersing in / by water, stirring is continued until all NCO groups have reacted with component b) and / or e) by means of an NCO water reaction and / or chain extension reaction. A complete conversion of all NCO groups with the OH or NH-functional groups mentioned above is also possible

Components before dispersing in / with water.

The solvents which may be used to prepare the dispersion can be partially or preferably completely removed from the dispersion by distillation. The dispersions preferably contain no volatile organic compounds

Substances. The preferred solvent is acetone.

If necessary, auxiliaries and additives, such as anti-settling agents, defoamers, thickeners, emulsifiers, catalysts, leveling agents, adhesion promoters, biocides, antistatic agents, light stabilizers, lubricants, thermal stabilizers, etc., but also special oligomers, can optionally be added to the polymers before, during or after dispersing or polymeric compounds without hydrophilic groups are added.

The dispersions according to the invention have average particle diameters (determined, for example, by laser correlation spectroscopy) from 20 to 900, preferably from 50 to 400 nm. The solids content of the dispersions is at least 30, preferably at least 35%, with viscosities of 10 to 150 seconds run-out time (DIN-4 cup, 23 ° C.). The pH values are preferably between 6.0 and 10.0.

The dispersions according to the invention are particularly suitable for use in or as sizes, preferably glass fiber sizes. The dispersions can be used as the sole binder or together with other polymers such as e.g. Polyurethane dispersions, polyacrylate dispersions, polyester dispersions, polyether dispersions, polyepoxide dispersions, polyvinyl ester or polyvinyl ether dispersions, polystyrene or polyacrylonitrile dispersions, blocked polyisocyanates, amino crosslinking resins such as e.g. Melamine resins are used.

The dispersions according to the invention or the sizes produced therewith can contain the usual auxiliaries and additives, such as e.g. Defoaming agents, thickening agents, flow control agents, dispersing aids, catalysts, skin preventing agents, anti-settling agents, emulsifiers, biocides, adhesion promoters, e.g. based on the known low or high molecular weight silanes, lubricants, wetting agents, antistatic agents.

Hardeners based on polyisocyanates blocked with dimethylpyrazole are also suitable for use in sizes. These hardeners contain polyisocyanates with at least one aliphatic, aromatic, heterocyclic and / or aromatic group and optionally one or more hydrophilizing groups such as mono- or dihydroxy-functional polyethers based on ethylene oxide and / or

Ethylene propylene oxide or polyhydroxycarboxylic acids. Corresponding products are described, for example, in WO 97/12924 or in EP-A 159 117.

Not mentioned there, but also very suitable for hydrophilization, are monohydroxycarboxylic acids, aminocarboxylic acids, hydroxysulphonic acids, aminosulfonic acids, hydroxyphosphonic acids and aminophosphonic acids. Preferred hardeners contain polyisocyanates with uretdione, biuret, isocyanurate, iminooxadiazinedione, allophanate and / or urethane structural units based on 1,6-hexamethylene diisocyanate, isophorone diisocyanate and / or H ^ -MDI. The corresponding polyisocyanates are available, for example, as Desmodur N 3400®, N 3300® or N 100® from Bayer AG.

Non-hydrophilized hardeners can e.g. are used in such a way that they are admixed with hydrophilic polymers for sizes before dispersing, and the polymer acts as an emulsifying substance for the hardener.

Hydrophilized hardeners can also be retrofitted with film-forming size dispersions of any composition

Proportions are mixed. The sizes preferably contain 10 to 50% by weight of hardener, based on the film-forming polymer.

The sizes can be applied by any method, for example with the help of suitable devices such as Spray or roller applicators. You can pull the glass filaments out of spinnerets at high speed immediately after they have solidified, i.e. be applied before winding up. It is also possible to size the fibers in an immersion bath after the spinning process. The sized glass fibers can be processed either wet or dry, for example into chopped glass. The final or intermediate product is dried at temperatures of 100 to 200 ° C. Drying is not only to be understood as the removal of other volatile components, but e.g. also the setting of the size components. The proportion of the size is 0.1 to 4%, preferably 0.2 to 2% by weight, based on the sized glass fibers.

Both thermoplastic and thermoset polymers can be used as matrix polymers. The dispersions according to the invention obtained are furthermore suitable for all fields of use in which solvent-based, solvent-free or other types of aqueous coating and coating systems with an increased property profile are used, for example coating mineral substrates, painting and sealing wood and wood-based materials, painting and coating metallic

Surfaces, painting and coating of plastics as well as the coating of textiles and leather. The dispersions according to the invention can be used as a primer, adhesive coat, adhesive primer, filler, topcoat, single-coat paint, topcoat or finish in the form of clearcoats or clear coatings or else in pigmented form.

Examples

In the following examples, all percentages, unless otherwise stated, relate to percentages by weight. All information regarding the hydroxyl and acid numbers refer to mg KOH / g substance.

example 1

432 g of a difunctional polypropylene glycol with a molecular weight of 1000 and 67 g of polyether are placed in a 3-1 stirred vessel with a stirring, cooling and heating device

LB25 (Bayer AG, monofunctional polyether based on ethylene oxide propylene oxide, molecular weight 2250) and 24 g trimethylolpropane, weighed, melted at 70 ° C. and then reacted with 293 g isophorone diisocyanate until the theoretical NCO value has been reached. The NCO-functional polyurethane prepolymer is then diluted with 550 g of acetone and reacted with 39.9 g of dimethylpyrazole until the theoretical NCO value is reached. Then a 30% aqueous solution of 4.9 g of ethylenediamine and 49.3 g of the adduct of one mole of isophoronediamine and one mole of acrylic acid (molecular weight 242) is added and stirred until no more NCO groups can be detected in the IR spectrum are. Then 12 g of neutralizing agent dimethylethanolamine and 9 g of a thermal stabilizer / light stabilizer (Tinuvin® 765, Ciba-Geigy) are added and the acetone polyurethane-polyurea solution is dispersed with so much water that after distilling off the acetone a 40% solution according to the invention Dispersion results.

Using the dispersion 1 according to the invention, the customary auxiliaries, including a lubricant and 3-aminopropyltriethoxysilane as an adhesion promoter (10% based on the amount of dispersion used), glass fibers were produced, sized, cut and dried in a customary and known manner. The glass fibers were compounded in polyamide 6 for reinforcement. With the dispersion according to the invention, compared to a dispersion produced without the use of dimethylpyrazole, improved processability was achieved, which can be seen in showed a significantly reduced amount of "specks" or specks and precipitates during the sizing process and in a reduced bulk volume (1 / Kg) of the coated and crushed glass fibers. The tensile and flexural strength of the test specimens produced therefrom was also 10 to 20% improved.

Example 2

1000 g of a difunctional polypropylene glycol with a molecular weight of 1000, 162 g of polyether LB 25, 107.2 g of trimethylolpropane and 69.4 g of a dihydroxy-functional hydrophilizing agent with sodium sulphonate groups are (6) in a 6-1 stirred vessel with stirring, cooling and heating device. Molecular weight 432) weighed, homogenized at 80 ° C, cooled to 60 ° C and reacted with 932.4 g of isophorone diisocyanate until the theoretical NCO value is reached. After cooling to 45 ° C., 65.3 g of dimethylpyrazole are added so that the reaction temperature does not exceed 65 ° C. After the theoretical NCO value has been reached, 2750 g of water at 40 ° C. are added in 15 minutes and immediately afterwards a mixture of 25 g of hydrazine hydrate, 32.6 g of ethylenediamine and 270 g of water is added in 5 minutes. The reaction mixture is stirred until no more NCO groups can be detected in the IR spectrum. A 44% dispersion according to the invention is obtained.

Using the dispersion 2 according to the invention, the usual auxiliaries, including a lubricant and 3-aminopropyltriethoxysilane as an adhesion promoter (10% based on the amount of dispersion used), glass fibers were produced, sized, cut and dried in a customary and known manner. The glass fibers were compounded into an unsaturated polyester resin for reinforcement. With the dispersion according to the invention, in comparison to a Charpy Impact dispersion produced without using dimethylpyrazole, values were found which were approximately 25% higher and tensile strength values which were approximately 20% higher. Example 3

500 g of a difunctional polypropylene glycol with a molecular weight of 1000 and 500 g of a difunctional polytetrahydrofuran with a molecular weight of 1000.183 g of polyether LB 25 are placed in a 6-1 stirred vessel with a stirring, cooling and heating device.

Homogenize 124.3 g of propoxylated trimethylolpropane (molecular weight 306) at 80 ° C, cool to 60 ° C and react with 677 g of isophorone diisocyanate until the theoretical NCO value is reached. After adding 320 g of acetone, 64 g of dimethylpyrazole and 30 g of ε-caprolactam are added. After the theoretical NCO value has been reached, the mixture is diluted with 1000 g of acetone and a mixture of

115 g of the isophoronediamine / acrylic acid adduct described in Example 1, 11.3 g of ethylenediamine and 240 g of water were added in 5 minutes. The reaction mixture is stirred until no more NCO groups can be detected in the IR spectrum. Then 23 g of Tinuvin® 765 (Ciba-Geigy) are added and dispersed by adding 3130 g of water. After distilling off the acetone, a 40% dispersion according to the invention is obtained.

Example 4

In a 6-1 stirred vessel with a stirring, cooling and heating device, 1777 g of a difunctional polycarbonate (Desmophen 2020, Bayer AG) with a molecular weight of 2000 and 101 g of polyether LB 25 are homogenized at 80 ° C, cooled to 60 ° C and with 253.5 g of isophorone diisocyanate and 192 g of hexamethylene diisocyanate are reacted until the theoretical NCO value is reached. After adding 3200 g of acetone, 38.9 g of dimethylpyrazole are added. After reaching the theoretical NCO

116 g of isophoronediamine, dissolved in 184 g of acetone in 5 minutes and then a mixture of 36 g of a diaminofunctional hydrophilizing agent of molecular weight 190 with a sodium sulphonate group, 4.5 g of hydrazine hydrate and 300 g of water are added in 2 minutes. The reaction mixture is stirred for 15 minutes at 50 ° C. and then by adding 3400 g Water dispersed. After the acetone has been distilled off, a 40% dispersion according to the invention is obtained.

Example 5

In a 2-1 stirred vessel with a stirring, cooling and heating device, 264 g of a difunctional polyester of phthalic anhydride and hexanediol with a molecular weight of 2000, 67 g of polyether LB 25 and 6.9 g of 1,4-butanediol are homogenized at 80 ° C. and with a mixture of 85 g of isophorone diisocyanate and 24.8 g of Desmodur W (Bayer AG) until the theoretical NCO value is reached. To

The addition of 1.7 g of dimethylpyrazole is diluted with 470 g of acetone, stirred for 30 minutes and then a mixture of 13.4 g of the diamino-functional hydrophilizing agent described in Example 4), 1.8 g of diethylenetriamine, 9.4 g of 3 -Aminopropyltriethoxysilane and 60 g of water added in 10 minutes. The reaction mixture is stirred for 15 minutes at 50 ° C. and then by adding 750 g

Water dispersed. After the acetone has been distilled off, a 37% dispersion according to the invention is obtained.

Example 6

a) 160 g of a difunctional polyester of adipic acid, hexanediol and neopentyl glycol with a molecular weight of 1700 and 5.8 g of polyether LB 25 are homogenized at 80 ° C. in a 1 l stirred vessel with a stirring, cooling and heating device and mixed with a mixture of 24 g of isophorone diisocyanate and 18 g of hexamethylene diisocyanate until the theoretical NCO value is reached. The mixture is then diluted with 270 g of acetone and a mixture of 2.5 g of the diaminofunctional hydrophilizing agent described in Example 4), 15 g of isophoronediamine and 25 g of water are added in 5 minutes. The reaction mixture is stirred at 50 ° C. for 15 minutes and then dispersed by adding 300 g of water. After the

Acetone gives a 41.5% dispersion. b) 177 g of a polyisocyanate based on hexamethylene diisocyanate (Desmodur® N3300, Bayer AG) and 4 g of polyether LB 25, 5.2 g of 1, 4-butanediol, are placed in a 1-l stirred vessel with a stirring, cooling and heating device. 30.5 g of the hydrophilizing agent described in Example 2), 55.1 g of dimethylpyrazole and 11.7 g of butanone oxime are reacted in the presence of 50 g of acetone until no more NCO groups can be detected. The reaction mixture was dispersed by adding water. After the acetone has been distilled off, a 30% dispersion of a hydrophilic polyisocyanate blocked with dimethylpyrazole is obtained.

c) 500 g of dispersion a) are mixed with 136 g of dispersion b) to give a dispersion according to the invention with a solids content of 39%.

Using dispersion 5 or 6 according to the invention, the usual auxiliaries, i.a. a lubricant and 3-aminopropyltriethoxysilane as an adhesion promoter (8% based on the amount of dispersion used), glass fibers were prepared, sized, cut and dried in a customary and known manner. The glass fibers were compounded into an unsaturated polyester resin for reinforcement. With the dispersions according to the invention, in comparison to a dispersion which contained a hardener based on a polyisocyanate blocked with ε-caprolactam, a significantly reduced and thus improved styrene solubility and an average of 10 to 15% better mechanical values were found.

Claims

claims

1. Polyurethanes, polyurethane-polyureas or polyureas in the form of dispersions which are modified with 0.1 to 15% by weight of dimethylpyrazole.

2. Dispersions based on polyurethanes, polyurethane polyureas or polyureas according to claim 1, which are reaction products of

a) at least one polyol component, b) at least one di-, tri- and / or polyisocyanate component, c) optionally at least one (potentially) ionic structural component, consisting of compounds having at least one group which is reactive toward NCO groups and at least one, optionally at least partially neutralizes the present group capable of salt formation, d) optionally at least one nonionic-hydrophilic structural component, consisting of compounds which are mono- to tetrafunctional in the sense of the isocyanate addition reaction and have at least one hydrophilic polyether chain, e) optionally at least one different from a) to d) Build-up component of the molecular weight range 32 to 2500 with groups reactive towards isocyanate groups and f) 0.1 to 15% by weight of at least one monofunctional blocking agent which consists of at least 50% dimethylpyrazole,

3. Dispersion according to claim 1 and 2, characterized in that the solid of the dispersion is the reaction product of a) 30 to 90% by weight of at least one polyol component in the hydroxyl number range 5 to 350, b) 10 to 50% by weight of at least one di-, tri- and / or polyisocyanate component, c) 0 to 10% by weight. % of a (potentially) ionic structural component, consisting of at least one compound with at least one G ppe reactive towards NCO groups and at least one, optionally at least partially neutralized, G ppe capable of salt formation, d) 0 to 20% by weight of one nonionic-hydrophilic structural component consisting of at least one compound which is mono- to tetrafunctional in the sense of the isocyanate addition reaction and has at least one hydrophilic polyether chain, e) 0 to 20% by weight of at least one structural component of the molecular weight range 32 to which is different from a) to d) 2500 with groups reactive towards isocyanate groups and f) 0.1 to 15% by weight of at least one monofunctional blocking agent which consists of at least 50% dimethylpyrazole consists,

Dispersion according to Anspmch 1 and 2, characterized in that the solid of the dispersion is the reaction product of

a) 40 to 85% by weight of at least one polyol component in the hydroxyl number range 5 to 350, b) 15 to 40% by weight of at least one di-, tri- and / or polyisocyanate component, c) 0 to 7% by weight of a (potentially) anionic structural component, consisting of at least one compound having at least one group which is reactive towards NCO groups and at least one, possibly at least partially neutralized, group capable of salt formation, d) 2 up to 20% by weight of a nonionic-hydrophilic structural component consisting of at least one compound which is mono- to tetrafunctional in the sense of the isocyanate addition reaction and has at least one hydrophilic polyether chain, e) 0 to 10% by weight of at least one of a) to d ) various structural components of the molecular weight range 32 to 2500 with groups reactive towards isocyanate groups and f) 0.25 to 7.5% by weight of at least one monofunctional blocking agent which consists of at least 50% dimethylpyrazole,

the sum of a) to f) being 100%, either c) or d) cannot be 0 and being used in such an amount that a stable dispersion is formed.

5. Dispersion according to Anspmch 1 and 2, characterized in that the solid of the dispersion is the reaction product of

a) 40 to 85% by weight of at least one polyol component with a molecular weight of 600 to 3500 based on carbonate diols, polytetrahydrofuran diols and / or polyethers based on propylene oxide or propylene oxide / ethylene oxide, b) at least 15 to 40% by weight a di-, tri- and / or polyisocyanate component, c) 0 to 7% by weight of a (potentially) anionic structural component consisting of at least one compound with at least one towards NCO groups reactive and at least one, possibly at least partially neutralized, group capable of salt formation, d) 2 to 20% by weight of at least one nonionic-hydrophilic structural component of molecular weight 1000 to 2500, consisting of at least one in the sense the isocyanate reaction monofunctional polyether with a built-in propylene oxide content of 15 to 57% and a built-in ethylene oxide content of 85 to 43%, e) 0.2 to 6% by weight of at least one structural component different from a) to d) of the molecular weight range 32 to 400 with primary or secondary amino and / or hydroxyl groups reactive towards isocyanate groups and f) 0.5 to 4.5% by weight of at least one monofunctional blocking agent or blocking agent mixture which consists of at least 70% dimethylpyrazole consists,

6. Dispersion according to claims 1 to 5, characterized in that the

(Potentially) anionic component c) at least 50% of which the addition product consists of 1 mole of acrylic acid and 1 mole of isophoronediamine.

7. Dispersion according to claims 1 to 5, characterized in that the polyol component a) at least partially consists of a polyol of the molecular weight range> 9000 g / mol.

8. Dispersions according to claims 1 to 5, characterized in that the chain-terminating component e) 0.2 to 5 wt .-% monoaminofunctional alkoxysilanes are included.

9. Dispersions according to claims 1 to 5, characterized in that 0.5 to 2.5% by weight of monoamino-functional alkoxysilanes are contained as chain-terminating component e).

10. A process for the preparation of the dispersions according to the invention, characterized in that an NCO-functional prepolymer is first prepared from components a), b), optionally c) and / or optionally d), optionally with the use of a hydroxy-functional component e), then a Part of the remaining NCO groups with component f) implemented, the other NCO groups either before, during or after

Dispersing brought to reaction with component and / or a further amino-functional component e), optionally, if not previously done, neutralizing agent added, dispersed and then, if appropriate, the solvent added before, during or after the prepolymer preparation is removed by distillation.

11. Use of the dispersions according to claims 1 to 9 for aqueous painting and coating systems with an increased profile of properties such as the coating of mineral substrates, the painting and sealing of wood and wood-based materials, the painting and coating of metallic surfaces, the painting and coating of Plastics.

12. Use of the dispersions according to claims 1 to 9 for the coating of textiles and leather.

13. Use of the dispersions according to claims 1 to 9, optionally together with other polymers and customary auxiliaries and additives in sizes for glass fibers.

14. Use of polyisocyanate-based hardness blocked with dimethylpyrazole in sizes.

15. Use of hydrophilized polyisocyanate-based hardness blocked with dimethylpyrazole in sizes.

16. glass fiber sizing containing dispersions according to claims 1 to 9.

17. Glass fiber sizes optionally containing hydrophilized polyisocyanate-based hardeners blocked with dimethylpyrazole.