Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/80—Masked polyisocyanates
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
  • C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
  • C08G18/3834—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing hydrazide or semi-carbazide groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
  • C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
  • C08G18/3844—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing one nitrogen atom in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
  • C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
  • C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/7806—Nitrogen containing -N-C=0 groups
  • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
  • C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/80—Masked polyisocyanates
  • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
  • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
  • C08G18/8074—Lactams
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/80—Masked polyisocyanates
  • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
  • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
  • C08G18/8077—Oximes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/005—Stabilisers against oxidation, heat, light, ozone
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
  • Y10T428/249933—Fiber embedded in or on the surface of a natural or synthetic rubber matrix
  • Y10T428/249937—Fiber is precoated

Definitions

• the invention relates to novel, water-dispersible or water-soluble blocked polyisocyanates stabilized against thermal yellowing, their preparation and
• aqueous one-component (1K) and two-component (2K) polyurethane systems are increasingly being used in combination with blocked isocyanates. Due to the blocking agents, there is often a thermal yellowing of the coatings produced, which is undesirable.
• Blocking agents which cause only very little thermal yellowing are known from the prior art, e.g. 3,5-dimethylpyrazole,
• 1,2,4-triazole or ⁇ -caprolactam have the disadvantage that they are either too expensive or cannot be used generally due to certain product properties.
• the blocking of polyisocyanates based on HDI with 1,2,4-triazole leads to strongly crystallizing products which are therefore unsuitable for use in paints and coatings.
• ⁇ -Caprolactam has a significantly higher deblocking temperature and is therefore not suitable for all areas of application.
• a stabilizing agent is known from US Pat. No. 5,216,078 which significantly reduces the thermal yellowing of blocked, in particular of butanone oxime, blocked isocyanates and which is a hydrazine adduct.
• EP-A 0 829 500 describes a combination of compounds as stabilizing agents for blocked polyisocyanates, one of the compounds at least one 2,2,6,6-telxame ylpiperidinyl residue, the so-called HALS (hindered amine light stabilizer) residue and the other has a hydrazide structure.
• HALS hindered amine light stabilizer
• a disadvantage of the stabilized blocked polyisocyanates mentioned above, however, is that they are only suitable for solvent-based paints and coating systems and not for aqueous systems.
• the object of the present invention was therefore to provide isocyanates which, on the one hand, are blocked and water-dispersible or water-soluble and, on the other hand, are sufficiently stabilized against possible thermal yellowing and are suitable for crosslinking aqueous 1-component and 2-component binders or paints, in particular on polyurethane and or Polyacrylate base are suitable.
• Hydrazides and certain sterically hindered amines can be significantly protected from thermal yellowing.
• the present invention relates to a water-dispersible crosslinking agent composition
• At least one stabilizing agent comprising a) at least one amine with the Sfruktaeiriheit of general formula CO,
• Component A) of the crosslinker composition according to the invention is a reaction product of at least one organic polyisocyanate Al) with aliphatic, cycloaliphatic, araliphatic and / or aromatically bound isocyanate groups, an ionic or potentially ionic and / or nonionic compound A2) and one Blocking agent A3).
• organic polyisocyanate Al aliphatic, cycloaliphatic, araliphatic and / or aromatically bound isocyanate groups
• an ionic or potentially ionic and / or nonionic compound A2 an ionic or potentially ionic and / or nonionic compound A2
• Blocking agent A3 Blocking agent
• the crosslinking composition according to the invention contains 78.0 to 99.8% by weight, preferably 84.0 to 99.6% by weight, particularly preferably 90.0 to 99.0% by weight of component A), 0 , 2 to 22.0% by weight, preferably 0.4 to 16.0% by weight, particularly preferably 1.0 to 10.0% by weight of component B), the sum of the
• the present invention also relates to an aqueous solution or dispersion comprising the crosslinking agent composition according to the invention, characterized in that the solution or dispersion has a solids content between 10 to 70% by weight, preferably from 20 to 60% by weight and particularly preferably from 25 to 50 wt .-% and the proportion of C) in the total composition is preferably less than 15 wt .-% and particularly preferably less than 5 wt .-%.
• the crosslinking agent composition according to the invention contains 0.1 to 11.0% by weight, preferably 0.2 to 8.0% by weight, particularly preferably 0.5 to 4.0% by weight of amines ( a) with the structural unit of the formula (I), 0.1 to 11.0% by weight, preferably 0.2 to 8.0% by weight, particularly preferably 0.5 to 4.0% by weight Compounds (b) with the stocking unit of the formula (LT) and optionally 0 to 5.0% by weight of other stabilizers c) different from a) and b).
• the polyisocyanate component A) has an (average) NCO functionality from 2.0 to 5.0, preferably from 2.3 to 4.5, an isocyanate group content (unblocked and blocked) from 5.0 to 27, 0% by weight, preferably from 14.0 to 24.0% by weight and a monomeric diisocyanate content of less than 1% by weight, preferably less than 0.5% by weight.
• A) of the composition according to the invention is at least 50%, preferably at least 60% and particularly preferably at least 70% in blocked form.
• Suitable polyisocyanates AI are any polyisocyanates made from at least two diisocyanates and having a uretdione, isocyanurate, allophanate, biuret, jjxunooxadiazinedione and / or oxadiazinione structure and produced by modifying simple aliphatic, cycloaliphatic, araliphatic and / or aromatic diisocyanates for example in J. Prakt. Chem. 336 (1994) page 185-200 are described by way of example.
• Suitable diisocyanates for the preparation of the polyisocyanates AI are any diisocyanates of the molecular weight range 140 to 400 accessible by phosgenation or by phosgene-free processes, for example by thermal urethane cleavage, with aliphatic, cycloaliphatic, araliphatic and / or aromatically bound isocyanate groups, such as, for example, 1,4-diisocyanatobutane, 1,6-diisocyanatohexane (HDI), 2-
• the starting components AI) are preferably polyisocyanates or polyisocyanate mixtures of the type mentioned with exclusively aliphatic and / or cycloaliphatic isocyanate groups.
• Particularly preferred starting components AI are polyisocyanates or polyisocyanate mixtures with isocyanurate and / or biuret structure based on HDI, LPDI and / or 4,4'-diisocyanatodicyclohexylmethane.
• Suitable compounds for component A2) are ionic or potentially ionic and / or nonionic compounds.
• Nonionic compounds are, for example, monovalent polyalkylene oxide polyether alcohols having a statistical average of 5 to 70, preferably 7 to 55, ethylene oxide units per molecule, as are obtainable in a manner known per se by alkoxylation of suitable starter molecules (for example in Ullmann's Encyclopedia of Industrial Chemistry, 4 Edition, Volume 19, Verlag Chemie, Weinheim pp. 31-38).
• Suitable starter molecules are, for example, saturated monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomers pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n -Hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols or hydroxymethylcyclohexane, 3-ethyl-3-hydroxymethyloxetane, or Diethylene glycol monoalkyl ethers such as diethylene glycol monobutyl ether; unsaturated alcohols such as allyl alcohol, 1,1-dimethylallyl alcohol or oleic alcohol, aromatic alcohols such
• Preferred starter molecules are saturated monoalcohols and diethylene glycol monoalkyl ethers.
• Diethylene glycol monobutyl ether is particularly preferably used as the starter molecule.
• Alkylene oxides suitable for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be used in the alkoxylation reaction in any order or in a mixture.
• the polyalkylene oxide polyether alcohols are either pure polyethylene oxide polyethers or mixed polyalkylene oxide polyethers whose alkylene oxide units consist of at least 30 mol%, preferably at least 40 mol%, of ethylene oxide units.
• Preferred nonionic compounds are monofunctional mixed polyalkylene oxide polyethers which have at least 40 mol% of ethylene oxide and at most 60 mol% of propylene oxide units.
• Suitable compounds for component A2) are also ionic or potentially ionic compounds which can be used in addition to or instead of the nonionic compounds, such as, for example, mono- and dihydroxycarboxylic acids, mono- and diaminocarboxylic acids, mono- and dihydroxysulfonic acids, mono- and diaminosulfonic acids and Mono- and dihydroxyphosphonic acids or
• Mono- and diaminophosphonic acids and their salts such as dimethylolpropionic acid, hydroxypivalic acid, N- (2-aminoethyl) -ß-alanine, 2- (2-aminoethylamino) ethanesulfonic acid, ethylenediamine propyl or butyl sulfonic acid, 1,2- or 1,3-propylene-diamine-ß-ethylsulfonic acid, lysine, 3,5-diaminobenzoic acid, the hydroplating agent according to Example 1 from EP-A 0 916 647 and its alkali and / or
• Ammonium salts the adduct of sodium bisulfite with butene-2-diol-1,4, polyether sulfonate, the propoxylated addul t of 2-butenediol and NaHSO 3 (for example in DE-A 24 46 440, page 5-9, formula I-III ) and building blocks which can be converted into cationic groups, such as N-methyl-diethanolamine, are used as hydrophilic structural components.
• Preferred ionic or potential ionic compounds A2) are those which have carboxy or carboxylate and / or sulfonate groups and / or ammonium groups.
• Particularly preferred ionic compounds A2) are those which contain carboxyl and / or sulfonate groups as ionic or potentially ionic groups, such as the salts of N- (2-aminoethyl) -ß-alanine, 2- (2-aminoethylamino) - ethanesulfonic acid, the hydrophilizing agent according to Example 1 from EP-A 0 916 647 and dimethylolpropionic acid.
• Component A2) is preferably a combination of nonionic and ionic hydrophilizing agents. Combinations of nonionic and anionic hydrophilizing agents are particularly preferred.
• Suitable blocking agents A3) are known from the prior art, for example alcohols, lactams, oximes, malonic esters, alkylacetoacetates, triazoles, phenols, imidazoles, pyrazoles and amines, such as e.g. Butanone oxime, diisopropylamine, 1,2,4-triazole, dimethyl-l, 2,4-triazole, imidazole,
• blocking agents A3 Diethyl malonate, acetoacetic ester, acetone oxime, 3,5-dimethylpyrazole, ⁇ -capro lactam or any mixture of these blocking agents.
• Butanone oxime, 3,5-dimethylpyrazole and ⁇ -caprolactam are preferably used as blocking agents A3).
• Particularly preferred blocking agents A3) are butanone oxime and / or ⁇ -caprolactam.
• compositions according to the invention contain a stabilizer mixture B) which a) contains an amine with the structural unit of the general formula (I).
• Suitable compounds a) are those which have a 2,2,6,6-tetramethylpiperidinyl radical (HALS ring).
• HALS ring 2,2,6,6-tetramethylpiperidinyl radical
• Preferred compounds a) are the following:
• the stabilizing agent B) of the compositions according to the invention also contains a compound b) of the general formula (II).
• Suitable compounds b) are, for example, acid hydrazides and dihydrazides, such as e.g. Acetic acid hydrazide adipic acid hydrazide or adipic acid dihydrazide or also hydrazine adducts of hydrazine and cyclic carbonates, as are mentioned, for example, in EP-A 654 490 (page 3, line 48 to page 4 line 3).
• Adipic acid dihydrazide or an adduct of 2 moles of propylene carbonate and 1 mole of hydrazine is preferred
• Suitable compounds c) are, for example antioxidants such as 2,6-di-tert-butyl-4-methylphenol, UV absorbers of the 2-hydroxyphenyl-benzotriazole or light stabilizers of the type substituted on the nitrogen atom HALS compounds such as Tinuvin ® 292 ( Ciba specialties GmbH, Lampertheim, DE) or other commercially available stabilizers, such as those found in "Light stabilizers for paints" (A. Valet, Vincentz Verlag, Hanover, 1996 and “Stabilization of Polymeric Materials” (H. Doubt, Springer Verlag, Berlin, 1997, Appendix 3, pp. 181-213)
• Preferred compounds c) are those given in Table 2:
• Suitable organic solvents C) are the conventional paint solvents, such as ethyl acetate, butyl acetate, 1-methoxypropyl-2-acetate, 3-methoxy-n-butyl acetate, acetone, 2-butanone, 4-methyl-2-pentanone, cyclohexanone , Toluene, xylene, chlorobenzene or white spirit.
• solvents are, for example, carbonic acid esters, such as dimethyl carbonate, diethyl carbonate, 1,2-ethylene carbonate and 1,2-propylene carbonate, lactones, such as ß-propiolactone, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -methylcaprolactone, propylene glycol diacetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, Dietliylene glycol ethyl and butyl ether acetate, N-methylpyrrolidone and
• solvents are 2-butanone, l-methoxypropyl-2-acetate, containing acetone, xylene, toluene, mixtures, especially higher-substituted aromatics, such as, for example, under the names Solvent Naphtha, Solvesso ® (Exxon Chemicals, Houston, USA) , Cypar ® (Shell Chemicals, Eschborn, DE), cyclo Sol ®
• the water-dispersible crosslinking agent compositions according to the invention can be prepared by known methods of the prior art (for example in DE-A 24 564 69, columns 7-8, examples 1-5 and DE-A 28 539 37 pp. 21-26) , Example 1-9).
• the water-dispersible crosslinking agent compositions according to the invention are obtained by reacting components AI), A2), A3), a), b) and optionally c) in any order, if appropriate with the aid of an organic solvent C).
• AI is preferably first reacted with component b) and, if appropriate, a nonionic part of component A2). Then the
• component A3 Blocking with component A3) and then the reaction with a) and optionally the part of component A2) containing ionic groups. If appropriate, organic solvents C) can be added to the reaction mixture. In a further step, component c) is optionally added.
• the aqueous solution or dispersion is then prepared by converting the water-dispersible crosslinker composition into an aqueous dispersion or solution by adding water.
• the organic solvent C) which may be used can be removed by distillation after the dispersion.
• the resulting dispersions or solutions have a solids content of 10 to 70% by weight, preferably 20 to 60% by weight and particularly preferably 25 to 50% by weight.
• crosslinker compositions according to the invention can be used in combination with suitable reactants which are reactive towards isocyanate groups
• aqueous binders such as polyurethane and / or polyacrylate dispersions or mixtures thereof or hybrids are used.
• Suitable reaction partners are also low molecular weight amines which can be processed in water to give heat-crosslinkable coating compositions which can be processed from the aqueous phase.
• Crosslinker compositions can also be incorporated into 1K binders such as polyurethane and / or polyacrylate dispersions and polyurethane-polyacrylate hybrid dispersions.
• aqueous solutions or dispersions containing the crosslinking compositions according to the invention without the addition of a further reaction partner, for example for impregnating substrates which have hydrogen atoms which are reactive toward isocyanate groups.
• the present invention further provides an aqueous coating composition comprising the crosslinking agent compositions according to the invention.
• the coating compositions containing the crosslinking agent compositions according to the invention are prepared by the methods known in the art, such as e.g. with the help of Rakehnessem, spray or roller applicators, or wire doctor blades applied to a suitable substrate.
• Suitable substrates are selected, for example, from the group metal, wood,
• Textiles, leather, paper, hard fibers, straw and bitumen before coating if necessary, can also be provided with customary primers.
• Preferred substrates are glass fibers, carbon fibers, metals, textiles and leather.
• a particularly preferred substrate is glass fiber.
• the invention also relates to the use of the invention
• crosslinking compositions according to the invention in glass fiber sizes is preferred.
• the dispersions can be used alone or preferably with binders such as e.g. Polyurethane dispersions, polyacrylate dispersions,
• Polyurethane-polyacrylate hybrid dispersions polyvinyl ether or polyvinyl ester dispersions, polystyrene or polyacrylanitrile dispersions, also in combination with other blocked polyisocyanates and amino crosslinking resins such as Melamine resin can be used.
• the crosslinking compositions according to the invention or the sizes produced with them can contain the usual auxiliaries, such as e.g. Defoamers, thickeners, leveling 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,
• auxiliaries such as e.g. Defoamers, thickeners, leveling 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.
• 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. after being applied before winding. 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 80 to 250 ° C. Under
• Drying is not just the removal of other volatile substances to understand components, but also, for example, the setting of the size components.
• the proportion of the size, based on the sized glass fibers, is 0.1 to 4% by weight, preferably 0.2 to 2% by weight.
• thermoplastic and thermoset polymers can be used as matrix polymers.
• the present invention also relates to glass fibers coated with a coating composition comprising the crosslinking compositions according to the invention.
• crosslinking compositions listed below are applied to test sheets coated with a commercially available white basecoat, e.g. from the company Spies & Hecker, coated, applied in a wet layer thickness of 120 ⁇ m.
• the test panels are dried for 30 minutes at room temperature and then baked in the drying cabinet at 170 ° C. for 30 minutes.
• the color measurement is then carried out using the CIELAB method. The larger the positive b * value determined, the more yellow the coating of the crosslinking composition has changed color.
• the stirring time at 40 ° C is 1 h.
• a storage-stable aqueous dispersion of the blocked polyisocyanate with a solids content of 30% is obtained.
• a storage-stable aqueous dispersion of the blocked polyisocyanate with a solids content of 31.4% is obtained.
• a storage-stable aqueous dispersion of the blocked polyisocyanate with a solids content of 30.0% is obtained.
• Tinuvin 765 1.7 g are added, stirring is continued for 10 mm and the reaction mixture is cooled to 60.degree.
• the dispersion is carried out by adding 726.0 g of water (20 ° C.) at 60 ° C. within 30 minutes.
• the stirring time at 40 ° C is 1 h.
• a storage-stable aqueous dispersion of the blocked polyisocyanate with a solids content of 30% is obtained.
• the crosslinking composition according to the invention from Example 1 (cf. Table 3) has a significantly improved yellowing resistance in comparison to that of Examples 2-5.
• Example 8 (comparative example):
• the crosslinking composition according to the invention from Example 10 (cf. Table 5) has a significantly improved yellowing resistance in comparison to Examples 11.

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• 2002
  • 2002-01-17 DE DE2002101545 patent/DE10201545A1/de not_active Withdrawn
• 2003
  • 2003-01-07 CN CNB038059924A patent/CN100349942C/zh not_active Expired - Fee Related
  • 2003-01-07 CA CA 2473603 patent/CA2473603A1/en not_active Abandoned
  • 2003-01-07 KR KR10-2004-7011138A patent/KR20040077740A/ko not_active Application Discontinuation
  • 2003-01-07 JP JP2003560074A patent/JP2005514501A/ja active Pending
  • 2003-01-07 RU RU2004125180/04A patent/RU2324707C2/ru not_active IP Right Cessation
  • 2003-01-07 MX MXPA04006831A patent/MXPA04006831A/es not_active Application Discontinuation
  • 2003-01-07 EP EP03729424A patent/EP1468031A1/de not_active Withdrawn
  • 2003-01-07 BR BR0306920A patent/BR0306920A/pt not_active IP Right Cessation
  • 2003-01-07 AU AU2003235699A patent/AU2003235699A1/en not_active Abandoned
  • 2003-01-07 WO PCT/EP2003/000056 patent/WO2003059976A1/de active Application Filing
  • 2003-01-14 US US10/341,977 patent/US20030198796A1/en not_active Abandoned
  • 2003-01-16 TW TW092100831A patent/TW200307735A/zh unknown
• 2006
  • 2006-01-04 HK HK06100161.7A patent/HK1080096B/zh not_active IP Right Cessation

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