CA2084737A1 - Water-dilutable, urethane-modified and hydroxyl group-containing self-crosslinking binder and formulations thereof - Google Patents
Water-dilutable, urethane-modified and hydroxyl group-containing self-crosslinking binder and formulations thereofInfo
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- CA2084737A1 CA2084737A1 CA002084737A CA2084737A CA2084737A1 CA 2084737 A1 CA2084737 A1 CA 2084737A1 CA 002084737 A CA002084737 A CA 002084737A CA 2084737 A CA2084737 A CA 2084737A CA 2084737 A1 CA2084737 A1 CA 2084737A1
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- 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
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4263—Polycondensates having carboxylic or carbonic ester groups in the main chain containing carboxylic acid 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4676—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing sulfur
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- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4684—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing phosphorus
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- 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
- C09D175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- 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
- C08G2170/00—Compositions for adhesives
- C08G2170/80—Compositions for aqueous adhesives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Paper (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Abstract Water-dilutable, urethane-modified and hydroxyl group-containing self-crosslinking binder and formulations thereof Water-dilutable, urethane-modified and hydroxyl group-containing binder, prepared by reaction of a polyester containing hydroxyl groups and neutralized and/or neutra-lizable acid groups with substoichiometric amounts (with respect to the number of free hydroxyl groups) of a partially blocked polyisocyanate.
These binders are suitable for the production of coating films and other coatings of this type.
These binders are suitable for the production of coating films and other coatings of this type.
Description
208~737 Water-dilutable, urethane-modified and hydroxyl group-containing self-crosslinking bin~er and formu~ations thereof The present invention relates to novel, urethane resin-modified, hydroxyl group-containing binders, which are dispersed and/or dissolved in a (predominantly) aqueous medium, and the use thereof, preferably as stoving coating compositions for the production of coating films and coatings.
Conventional stoving systems are frequently based on the combination of a binder with a corresponding crosslinking component. Incompatibilities between these components can ,arise. An additional factor in the case of aqueous systems is that the crosslinking component as a rule also has to be compatible with water or is stabilized in the aqueous phase by the emulsifier action of the binder.
In the present invention the incompatibility between crosslinking agents (polyisocyanates in the invention) and binders (polyester-polyol containing anionic groups in the invention) is prevented by partial covalent bonding of the isocyanate components to the polyester resin, so that a self-crosslinking one-component stoving system is obtained.
The storage stability of the binder of the present invention, which is predominantly dispersed in water, is consequently considerably greater than that of a combina-tion of the polyester-polyol with the correspondingly completely capped polyisocyanate. In detail, the subject of the invention is a water-dilutable, urethane-modified and hydroxyl group-containing binder which is prepared by reacting a polyester containing free hydroxyl groups and neutralized and/or neutralizable acid groups with sub-stoichiometric amounts (with respect to the number of - 2 - 208~737 free hydroxyl groups) of a partially blocked polyiso-cyanate. The binder according to the invention preferably contains hydroxyl groups of 3-350, in particular 5-170 milliequivalents OHJloo g of binder solid resin.
The proportion of capped isocyanate groups (expressed as NCO) is preferably between 0.5 and 10% by weight, with respect to solid resin, and that of the urethane groups is preferably between 0.5 and 20% by weight, with respect to solid resin (expressed as -NH-C(O)O-). In order to obtain the dilutability with water, the resin contains neutraliæable and/or neutralized acid groups, generally carboxylic acid, sulfonic acid or phosphonic acid groups.
The content of these groups is customarily between 5 and 200, preferably between 10 and 90 milliequivalents of sulfonate and/or carboxylate and/or phosphonate in 100 g of binder solid resin.
The polyester-polyols used as starting material are prepared by conventional processes by a condensation reaction of polycarboxylic acids, polyalcohols and hydroxy carboxylic acids, all of which can optionally contain further carboxylic acid, sulfonic acid or phos-phonic acid groups.
The polycarboxylic acids can be of aliphatic, cyclo-aliphatic, aromatic and/or heterocyclic type and can optionally be substituted, for example, by halogen atoms.
Examples which may be mentioned of such carboxylic acids and their derivatives are: succinic acid, adipic acid, suberic acid, aæelaic acid, sebacic acid, phthalic acid, terephthalic acid, sulfoterephthalic acid, sulfoiso-phthalic acid, sulfophthalic acid, isophthalic acid,trimellitic acid, pyromelli~ic acid, tetrahydrophthalic acid, hexahydrophthalic acid, di- and tetra-chlorophthalic acid, endomethylenetetrahydrophthalic acid and its hexachloro derivative, glutaric acid, maleic acid, fumaric acid and fatty acid dimers and trimers. In place of these acids it is also possible to use their anhydrides, insofar as these exist.
Conventional stoving systems are frequently based on the combination of a binder with a corresponding crosslinking component. Incompatibilities between these components can ,arise. An additional factor in the case of aqueous systems is that the crosslinking component as a rule also has to be compatible with water or is stabilized in the aqueous phase by the emulsifier action of the binder.
In the present invention the incompatibility between crosslinking agents (polyisocyanates in the invention) and binders (polyester-polyol containing anionic groups in the invention) is prevented by partial covalent bonding of the isocyanate components to the polyester resin, so that a self-crosslinking one-component stoving system is obtained.
The storage stability of the binder of the present invention, which is predominantly dispersed in water, is consequently considerably greater than that of a combina-tion of the polyester-polyol with the correspondingly completely capped polyisocyanate. In detail, the subject of the invention is a water-dilutable, urethane-modified and hydroxyl group-containing binder which is prepared by reacting a polyester containing free hydroxyl groups and neutralized and/or neutralizable acid groups with sub-stoichiometric amounts (with respect to the number of - 2 - 208~737 free hydroxyl groups) of a partially blocked polyiso-cyanate. The binder according to the invention preferably contains hydroxyl groups of 3-350, in particular 5-170 milliequivalents OHJloo g of binder solid resin.
The proportion of capped isocyanate groups (expressed as NCO) is preferably between 0.5 and 10% by weight, with respect to solid resin, and that of the urethane groups is preferably between 0.5 and 20% by weight, with respect to solid resin (expressed as -NH-C(O)O-). In order to obtain the dilutability with water, the resin contains neutraliæable and/or neutralized acid groups, generally carboxylic acid, sulfonic acid or phosphonic acid groups.
The content of these groups is customarily between 5 and 200, preferably between 10 and 90 milliequivalents of sulfonate and/or carboxylate and/or phosphonate in 100 g of binder solid resin.
The polyester-polyols used as starting material are prepared by conventional processes by a condensation reaction of polycarboxylic acids, polyalcohols and hydroxy carboxylic acids, all of which can optionally contain further carboxylic acid, sulfonic acid or phos-phonic acid groups.
The polycarboxylic acids can be of aliphatic, cyclo-aliphatic, aromatic and/or heterocyclic type and can optionally be substituted, for example, by halogen atoms.
Examples which may be mentioned of such carboxylic acids and their derivatives are: succinic acid, adipic acid, suberic acid, aæelaic acid, sebacic acid, phthalic acid, terephthalic acid, sulfoterephthalic acid, sulfoiso-phthalic acid, sulfophthalic acid, isophthalic acid,trimellitic acid, pyromelli~ic acid, tetrahydrophthalic acid, hexahydrophthalic acid, di- and tetra-chlorophthalic acid, endomethylenetetrahydrophthalic acid and its hexachloro derivative, glutaric acid, maleic acid, fumaric acid and fatty acid dimers and trimers. In place of these acids it is also possible to use their anhydrides, insofar as these exist.
3 208~737 The polyalcohols used are preferably low-molecular polyols, polyhydroxy-polyethers, polylactone-polyols and polycarbonate-polyols. Suitable low-molecular polyols are, for example, ethanediol, the various propanediols, butanediols and hexanediols, dimethylolcyclohexane, 2,2-bis(4-hydroxycyclohex~l)propane, diethylene glycol, triethylene glycol, glycerol, trimethylolethane or trimethylolpropane, hexanetriol, pentaerythritol, dipentaerythritol or sorbitol; in addition, low-molecular polyols, preferably diols, which also contain an ionic group in the form of the carboxylic acid, sulfonic acid or phosphonic acid group are also used. These acid groups can be free and/or present in salt form. Examples of this group of monomers are a-C2-C1O-bishydroxy carboxylic acids, such as, for example, dihydroxypropionic acid, di-methylolpropionic acid, dihydroxyethylpropionic acid, dimethylolbutyric acid, tartaric acid, dihydroxymaleic acid, dihydroxybenzoic acid or 3-hydroxy-2-hydroxymethyl-propanesulfonic acid and dihydroxybutanesulfonic acids.
Suitable polyhydroxy-polyethers are compounds of the formula H -[- O - (CHR)n-]~ OH
in which R is hydrogen or a lower alkyl radical, optionally carrying diverse substituents, n is a number from 2 to 6 and m is a number from 10 to 120.
Examples are poly~oxytetramethylene)glycols, poly-(oxyethylene)glycols and poly(oxypropylene)glycols. The preferred polyhydroxy-polyethers are poly(oxypropylene)-glycols having a molecular weight in the range from 400 to 5,000.
The polylactone-polyols derived from lactones are obtained, for example, by reaction an ~-caprolactone with a polyol. Products of this type are described in 208~737 US Patent 3,169,945.
The polylactone-polyols, which are obtained by this reaction, are characterized by the presence of a terminal hydroxyl group and by recurring polyester fractions which S are derived from the lactone. These recurring molecule ractions can have the formula - C -- ( CHR ) n ~ CH20 in which n is preferably 4 to 6 and the substituent R is hydrogen, an alkyl radical, a cycloalkyl radical or an alkoxy radical, no substituent containing more than 12 carbon atoms.
The lactone used as starting material can be any lactone or any combination of lactones and this lactone should contain at least 6 carbon atoms in the ring, for example 6 to 8 carbon atoms, and 2 hydrogen substituents should be present on the carbon atom which is bonded to the oxygen group of the ring. The lactone used as starting material can be represented by the fcllowing general formula:
CH2(CR2)n 1 in which n and R have the meaning already indicated.
The lactones preferred in the case of the invention are ~-caprolactones, in which n has the value 4. The most preferred lactone is unsubstituted ~-caprolactone, in which n has the value 4 and all R substituents are hydrogen. This lactone is particularly preferred since it is available in large amounts and gives coatings which have excellent properties. In addition, various other lactones can be used on their own or in combination.
.
208~737 Examples of aliphatic polyols suitable for the reaction with the lactone are ethylene glycol, 1,3-propanediol, 1,4-butanediol, hexane-1,6-diol, dimethylolcyclohexane, trimethylolpropane and pentaerythritol.
The polycarbonate-polyols or polycarbonate-diols are compounds which have the general formula HO-R-~ O-C-O-R-)~-OH
in which R is an alkylene radical. These OH-functional polycarbonates can be prepared by reacting polyols, such as propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol, diethylene glycol, triethylene glycol, 1,4-bishydroxy-methylcyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane, neopentyl glycol, trimethylolpropane or pentaerythritol, with dicarbonates, such as dimethyl carbonate, diethyl carbonate or diphenyl carbonate, or phosgene. ~ixtures of such polyols can also be used.
The following may be mentioned as preferred examples of hydroxy carboxylic acids: salicylic acid, sulfosalicylic acid and salts thereof.
~he polyester-polyols are prepared by known methods in a multistage process depending on the rate of esterifi-cation of the carboxylic acids. For the preferred case of the preparation of a polyester-polyol from a mixture of aromatic and aliphatic dicarboxylic acids, the aromatic carboxylic acids are first esterified with the hydroxy-functional components in the presence of a catalyst and the aliphatic carboxyl group-containing reactants are then introduced, since, as is known, the rate of esterification of aromatic carboxylic acids, such as, for example, isophthalic acid, is considerably slower than that of dimethylolpropionic acid and the latter, in turn, is slower than, for example, that of adipic acid.
2~8~737 In the case of the polyester-polyols containing sulfonic acid groups it can be necessary, in order to achieve as ~uantitative as possible a condensation reaction of the sulfo monomer, to carry out the synthesis also in a ~ultistage process. To this end, the entire hydroxyl-functional components are first reacted with the sulfo monomers and optionally with the aromatic, carboxylic acid-containing components in the presence of catalysts, so that 95% of the amount of distillate calculated for a quantitative conversion is obtained from the condensation reaction. The aliphatic carboxylic acid components are then reacted, where appropriate, the condensation reac-tion being carried out until a free acid group content of less than 18 meq (COOH)/100 g is obtained.
The polycondensation reaction takes place at temperatures between 150 and 230C, preferably between 160 and 21~C.
Suitable catalysts are, preferably, organometallic com-pounds, in particular zinc-, tin- or titanium-containing compounds, such as, for example, zinc acetate, dibutyltin oxide or tetrabutyl titanate. The amount of catalyst is preferably 0.1 to 1.5% by weight of the total batch.
The polyester-polyols obtained in this way are then reacted with a partially capped polyisocyanate. Suitable polyisocyanates are all compounds of this type known here, for example trimethylene diisocyanate, tetra-methylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylene diisocyanate, 2,3-dimethylene diisocyanate, l-methyl-trimethylene diisocyanate, l,3-cyclopentylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,2-cyclo-hexylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, 4,4'-biphenylene diiso-cyanate, 1,5-naphthalene diisocyanate, 1,4-naphthalene diisocyanate, 1-isocyanatomethyl-5-isocyanato-1,3,3,3-trimethylcyclohexane, bis(4-isocyanatocyclo-hexyl)methane, bis(4-isocyanatocyclophenyl)methane, 4,4'-diisocyanatodiphenyl ether, 2,3-bis(8-isocyanato-octyl)-4-octyl-5-hexylcyclohexene, trimethylxylylene diisocyanate or tetramethylxylylene diisocyanate or mixtures of these compounds.
In addition to these simple polyisocyanates, those which contain hetero-atoms in the radical linked to the iso-cyanate groups are also suitable. Examples of such compounds are polyisocyanates which contain carbodiimide groups, allophonate groups, isocyanurate groups, urethane groups, acylated urea groups or biuret groups.
Suitable polyisocyanates are, finally, also those higher functional isocyanates which are prepared by reacting a diisocyanate with a polyol (for example trimethylol-propane or pentaerythritol), as well as the ethoxylated and/or propoxylated derivatives thereof having a degree of alkoxylation of 0.5 to 4.5 ethylene oxide and/or propylene oxide per hydroxyl functional group.
Suitable capping agents are aliphatic, cycloaliphatic or alkyl-aromatic (monohydric) alcohols, for example lower aliphatic alcohols, such as methyl alcohol or ethyl alcohol, the various propyl, butyl and hexyl alcohols, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol and the like, and also unsaturated alcohols such as propargyl alcohol or allyl alcohols, cycloaliphatic alcohols, such as cyclopentanol or cyclohexanol, alkyl-aromatic alcohols, such as benzyl alcohol, p-methylbenzyl alcohol, p-methoxybenzyl alcohol and p-nitrobenzyl alcohol, and monoethers of glycols, such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether and the like. ~urther capping agents are phenols, ketoximes, expediently having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, such as acetone oxime, methyl ethyl ketone oxime (= butanone oxime), hexanone oxime (such as methyl butyl ketone oxime), heptanone oxime (such as methyl n-amyl ketone oxime), octanone oxime and cyclohexanone oxime, CH-acid compounds, such as 208~737 malonic acid alkyl esters, acetoacetates and also cyano-acetates, in each case having 1 to 4 carbon atoms in the ester group, NH-acid compounds, such as caprolactam and amino alcohols, such as diethylethanolamine.
The polyisocyanates are re~cted in accordance with methods known per se with an amount of a capping agent such that the ratio of free isocyanate groups to capped isocyanate groups is 1:4 to 1:0.5.
These partially capped polyisocyanates are then reacted in accordance with known methods with the polyester-polyol described above, specifically in proportions by weight such that the end product has the parameters defined initially. Any free acid groups present are then finally completely or partially neutralized. Aqueous solutions of alkali metal hydroxides or amines, for example trimethylamine, triethylamine, dimethylaniline, diethylaniline, triphenylamine, dimethylethanolamine, aminomethylpropanol, dimethylisopropanolamine or ammonia, are used for this purpose.
If the relative reactivities of the polyester-polyol and the capping agent with respect to the polyisocyanate permit, there are also the following two process possibilities:
- the polyisocyanate is added to the capping agent, which has been initially introduced with the polyester-polyol, if appropriate in the presence of a catalyst, and, in the case of appropriate selec-tivity, the claimed binder can also be obtained in this way.
0 - the polyester-polyol is reacted with the polyiso-cyanate, if appropriate in the presence of a catalyst, until only the required free OH equiva-lents are still present. The capping agent is then added to this NCO-functional polymer and in this way 2~737 it is possible to block the isocyanate groups in order to obtain the claimed binder.
The aqueous dispersions of the binders according to the invention can be used to prepare coating systems, as binders for water-dilutable adhesives or as resins for printing inks.
In the case of appropriate compatibility, they can also optionally be combined with other aqueous plastic disper-sions and/or solutions, for example acrylic polymers and/or methacrylic polymers, polyurethane, polyurea resins, polyester resins and epoxy resins, thermoplastics based on polyvinyl acetate, polyvinyl chloride, polyvinyl ether, polychloroprene or polyacrylonitrile and ethylene-butadiene-styrene copolymers.
IThe binders according to the invention can be applied to very diverse substrates, for example ceramics, wood, glass, concrete and preferably plastics, such as polycarbonate, polystyrene, polyvinyl chloride, polyester, poly(meth)acrylates, acrylonitrile-butadiene-styrene polymers and the like, as well as also preferablymetals and alloys, such as iron, copper, aluminum, steel, tin, zinc, titanium, magnesium, brass, bronze and the like.
The binders according to the invention are suitable, for example, for the production of coating films, coatings and/or intermediate coatings for very diverse fields of application. After adding conventional coating additives, such as flow auxiliaries, wetting auxiliaries and dis-persing auxiliaries, as well as conventional pigment formulations (TiO2, BaSO~), they are suitable, in par-ticular, as aqueous stoving filler coatings, which -especially in the automobile industry - are applied as intermediate coating between primer and top coat, stoving or forced drying being carried out at temperatures of 70 to 200C, in particular of 100 to 180C, under otherwise 208~737 customary stoving conditions. Compared with aqueous filler coatings used on the market, they are distin-guished by very good protection against flying stones, very good resistance to warm and humid conditions and very good optical properties (gloss, surface structure).
Although it is not absolutely essential to add a cross-linking component when formulating water-dilutable coating compositions containing the binders according to the invention, it is nevertheless possible to add further crosslinking agents customary in coating technology, such as, for example, water-soluble or water-emulsifiable melamine or benzoguanamine resins, water-emulsifiable polyisocyanates or water-emulsifiable prepolymers con-taining terminal isocyanate groups, water-soluble or water-dispersible polyaziridines and b~ocked polyiso-cyanates, provided these are compatible.
Because of the high gloss, a good top coat quality can also be achieved using the binders according to the invention if suitable pigments are chosen. A prerequisite is then, however, the use of non-yellowing polyiso-cyanates (for example aliphatic isocyanates). Short-term weathering tests show very good results.
A particular advantage of the binders according to the invention is their storage stability (Table 3).
Examples 1. Polyesters The preparation of the polyester-polyol~ is carried out under a Nz atmosphere in a 4 1 four-necked round-bottomed flask provided with an anchor stirrer, a N2 inlet, a temperature sensor and a packed column (about 20 cm long and 3 cm in diameter) fitted with a top thermometer and a descending condenser.
Polyester 1 1,241 g of hexanediol (HD), 365 g of neopentyl glycol 20~4737 (NPG), 440 g of trimethylolpropane (TMP), 312 g of sulfoisophthalic acid dimethyl ester sodium salt (5-SIP-DME-Na) and 3 g of anhydrous zinc acetate are subjected to a condensation reaction at 170C to 220C
and a ma~imum top temperature of 65C until 50 g of distillate are obtained. The reaction mixture is cooled to 140C, 445 g of terephthalic acid (TPA), 891 g of isophthalic acid (IPA) and 2.6 g of dibutyltin oxide (DBTO) are added and the condensation reaction is carried out at 200C until a carboxyl group content of 26 meq (COOH)/100 g is obtained. The reaction mixture is cooled to 140C, 706 g of adipic acid (ADPA) are added and the condensation reaction is carried out at temperatures of 165 to 220C (maximum top temperature 100C) until the carboxyl group content is 7 meq (COOH)/100 g.
Polyester 2 665 g of hexanediol, 195 g of neopentyl glycol and 235 g of trimethylolpropane are melted, 210 g of terephthalic acid and 1.2 g of DBTO are then added at 100C and the condensation reaction is carried out at 220C and a maximum top temperature of 100C until a clear melt is obtained. The reaction mixture is cooled to 160C, 455 g of isophthalic acid and a further 1.2 g of DBTO are added and the condensation reaction is carried out until a carboxyl group content of 35 meq (COOH)/100 g is obtained. The reaction is then cooled to 130C and 910 g of adipic acid and 505 g of dimethylolpropionic acid (DMPA) are added and the condensation reaction is carried out at 160C to 200C (maximum top temperature 100C) until a value of 90 meq (COOH)/100 g is obtained.
Polyester 3 500 g of hexanediol, 520 g of neopentyl glycol and 235 g of trimethylolpropane are melted and 300 g of tere-phthalic acid, 450 g of isophthalic acid and 2.5 g of DBTO are then added at 100C. The condensation reaction is carried out at 190C to 200C until a carboxyl group content of 14 meq (COOH)/100 g is obtained, the reaction mixture is cooled to 140C, 900 g of adipic acid are added and the condensation reaction is carried out at 190C to 200~C until a value of 133 meq (COOH~/100 g is obtained. The reaction mixture is then cooled to 140C, 300 g of dimethylolpropionic acid are added and the condensation reaction is carried out at 170C to 180C
Imaximum top temperature 100C) until the carboxyl group content is 100 meq (COOHj/100 g.
Polyester 4 500 g of hexanediol, 400 g of neopentyl glycol and 350 g of trimethylolpropane are melted. 300 g of terephthalic acid, 450 g of isophthalic acid and 2.5 g of DBTO are added at 100C and the condensation reaction is carried out at 190C to 200C until the carboxyl group content is 7 meq (COOH)~100 g. ~he reaction mixture is cooled to 140C, 900 g of adipic acid and 300 g of dimethylol-propionic acid are added and the condensation reaction is carried out at 160 to 170C until the free carboxyl group content is 128 meq (COOH)/100 g. The reaction mixture is then cooled to 140C and a vacuum of 100 mbar is applied until a value of 110 meq (COOH)/100 g is reached (about 30 min).
2. Self-crosslinking - urethane-~odified - binders ( S~B) ~he synthesis of the binders according to the invention is carried out in a 2 1 four-necked round-bottomed flask fitted with a reflux condenser and a temperature sensor.
S~B 1 75.0 g of diphenylmethane 4,4'-diisocyanate (MDI) are added in the course of 7 min to 43.2 g of diethyl malonate, 0.8 g of sodium methylate and 74.0 g of methyl ethyl ketone and the mixture is stirred at 45C, with cooling, until a NCO content of 5.5% is obtained. A
solution of 269.5 g of polyester 1 in 92.5 g of methyl ethyl ketone is then added in the course of 2 min, the temperature is raised to 50C and the reaction mixture is , 208~737 _ 13 -stirred until the NCO content is < 0.1%. After further dilution with 54.4 g of butyl glycol/isopropanol (weight ratio 3/1), the mixture is dispersed with 675 g of demineralized water heated to 50C. 170 g of methyl ethyl ketone are distilled off from the aqueous phase under 250 mbar and at 60C.
66.6 g of isophorone diisocyanate (IPDI) are metered, in the course of 2 min, into 27.5 g of methyl ethyl ketoxime (ME~ oxime), 0.4 g of dibutyltin dilaurate (DBTDL) and 55.6 g of methyl ethyl ketone and the mixture is stirred at 35C, with cooling, until a NCO content of 8.5% is obtained. A solution of 294 g of polyester 2 in 110 g of methyl ethyl ketone i then added in the course of 3 min, the temperature is raised to 50C and the reaction mixture is stirred until the NCO content is < 0.1%. After further dilution with 54.4 g of butyl glycol~isopropanol (weight ratio 3/1), the mixture is neutralized with 20.0 g of triethylamine (TE~) and then dispersed with 675 g of demineralized water heated to 60. 170 g of methyl ethyl ketone are distilled off from the aqueous phase under 200 mbar and at 60~C.
435 g of methyl eth.yl ketoxime are added to 1,110 g of isophorone diisocyanate and 0.75 g of DETDL at 25C to 30C, with cooling, over a period of 75 min, the tempera-ture is then raised to 40C and the reaction mixture is stirred for a further 1 h. Isophorone diisocyanate capped on one side by methyl ethyl ketoxime is thus obtained.
55 g of n-methylpyrrolidone, 237.6 g of polyester 3 and 186.9 g of isophorone diisocyanate capped on one side, as described above, are stirred at 60C until a NCO content of 0.4% is obtained. 21.1 g of dimethylethanolamine (DNEA) are then added and the reaction mixture is stirred for a further one hour at 60C and dispersed with 715 g of demineralized water heated to 60C.
.
- 14 - 208~737 42.0 g of n-methylpyrrolidone, 220.0 g of polyester 4 and 92.0 g of isophorone diisocyanate capped on one side with methyl ethyl ketoxime are stirred at 60C until a NCO
content of 0.1% is obtained. 21.6 g of dimethylethanol-amine are then added and the reaction mixture is s~irred for a further one hour at 60C and dispersed with 460 g of demineralized water heated to 60C.
435 g of methyl ethyl ketoxime are added to 1,220 g of tetramethylxylylene diisocyanate (TMXDI) and 0.75 g of DBTL at 25C to 30C, with cooling, over a period of 75 min, the temperature is then raised to 40C and the reaction mixture is stirred for a further 1 h. TMXDI
capped on one side with methyl ethyl ketoxime is obtained in this way.
45.0 g of n-methylpyrrolidone, 219.6 g of polyester 4 and 102.2 g of trimethylxylylene diisocyanate capped on one side with methyl ethyl ketoxime are stirred at 60C until a NCO content of 0.1% is obtained. 36.2 g of triethanol-amine tTOLA) are then added and the reaction mixture is stirred for a further one hour at 60C and dispersed with 400g of demineralized water heated to 60C.
230.0 g of polyester 4, 44.0 g of N-methylpyrrolidone, 27.4 g of methyl ethyl ketoxime and O.OS g of dibutyltin dilaurate are stirred homogeneously at 35-40C and 69.8 g of isophorone diisocyanate are metered in at such a rate that the temperature does not rise above 65C. The reaction mixture is stirred at 65C until a NCO content of < 0.10% is obtained. 22.6 g of dimethylethanolamine are then added at 65C and the reaction mixture is stirred for a further hour and dispersed with 490 g of demineralized water heated to 65C~
Comparison example:
119.0 g of methyl ethyl ketoxime-capped isophorone diisocyanate (reaction of 1 mol of isophorone diiso-cyanate with 2 mol of methyl ethyl ketoxime in the presence of 0 15 g of dibutyltin dilaurate) are stirred homogeneously with 42.0 g of N-methylpyrrolidone and 220 0 g of polyester 4 at 60C and 21 6 g of dimethyl-ethanolamine are added at this temperature. The reaction mixture is stirred for a further hour at 60C and dis-persed with 515 0 g of demineralized water heated to60C.
3. Example of a stoving filler coating composition based on SUB 4 (colour shade light gray) Parts by weight Wetting and dispersing auxiliaries (-Additol XL 250) 0.3 Flow agent (-Additol XW 390) 0.4 Titanium dioxide 12.0 20 Blanc fixe micro 10 0 Talc, Naintsch E 7 2 0 Flame soot 101 0 1 Deionized water 9 5 Test results: see Table 4 4. Example of a water-dilutable top coating composition based on SUB 5 Parts by weight SUB 5 68.6 Wetting and dispersing auxiliaries (-Additol XL 250) 0.2 Flow agent ('Additol XW 390) 25~ in H200.5 Light stabilizers (-Sanduvor 3212) 50% in butyl glycol 1.7 10 Titanium dioxide 23.5 Deionized water 5.5 100.O
Test results for SUB_5 in the top coat Test 20' 130C20' 150C
.
Coating thickness in ~m 31 31 , Gloss < 20 76% 75%
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Erichsen deep drawing in mm 6 .
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Suitable polyhydroxy-polyethers are compounds of the formula H -[- O - (CHR)n-]~ OH
in which R is hydrogen or a lower alkyl radical, optionally carrying diverse substituents, n is a number from 2 to 6 and m is a number from 10 to 120.
Examples are poly~oxytetramethylene)glycols, poly-(oxyethylene)glycols and poly(oxypropylene)glycols. The preferred polyhydroxy-polyethers are poly(oxypropylene)-glycols having a molecular weight in the range from 400 to 5,000.
The polylactone-polyols derived from lactones are obtained, for example, by reaction an ~-caprolactone with a polyol. Products of this type are described in 208~737 US Patent 3,169,945.
The polylactone-polyols, which are obtained by this reaction, are characterized by the presence of a terminal hydroxyl group and by recurring polyester fractions which S are derived from the lactone. These recurring molecule ractions can have the formula - C -- ( CHR ) n ~ CH20 in which n is preferably 4 to 6 and the substituent R is hydrogen, an alkyl radical, a cycloalkyl radical or an alkoxy radical, no substituent containing more than 12 carbon atoms.
The lactone used as starting material can be any lactone or any combination of lactones and this lactone should contain at least 6 carbon atoms in the ring, for example 6 to 8 carbon atoms, and 2 hydrogen substituents should be present on the carbon atom which is bonded to the oxygen group of the ring. The lactone used as starting material can be represented by the fcllowing general formula:
CH2(CR2)n 1 in which n and R have the meaning already indicated.
The lactones preferred in the case of the invention are ~-caprolactones, in which n has the value 4. The most preferred lactone is unsubstituted ~-caprolactone, in which n has the value 4 and all R substituents are hydrogen. This lactone is particularly preferred since it is available in large amounts and gives coatings which have excellent properties. In addition, various other lactones can be used on their own or in combination.
.
208~737 Examples of aliphatic polyols suitable for the reaction with the lactone are ethylene glycol, 1,3-propanediol, 1,4-butanediol, hexane-1,6-diol, dimethylolcyclohexane, trimethylolpropane and pentaerythritol.
The polycarbonate-polyols or polycarbonate-diols are compounds which have the general formula HO-R-~ O-C-O-R-)~-OH
in which R is an alkylene radical. These OH-functional polycarbonates can be prepared by reacting polyols, such as propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol, diethylene glycol, triethylene glycol, 1,4-bishydroxy-methylcyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane, neopentyl glycol, trimethylolpropane or pentaerythritol, with dicarbonates, such as dimethyl carbonate, diethyl carbonate or diphenyl carbonate, or phosgene. ~ixtures of such polyols can also be used.
The following may be mentioned as preferred examples of hydroxy carboxylic acids: salicylic acid, sulfosalicylic acid and salts thereof.
~he polyester-polyols are prepared by known methods in a multistage process depending on the rate of esterifi-cation of the carboxylic acids. For the preferred case of the preparation of a polyester-polyol from a mixture of aromatic and aliphatic dicarboxylic acids, the aromatic carboxylic acids are first esterified with the hydroxy-functional components in the presence of a catalyst and the aliphatic carboxyl group-containing reactants are then introduced, since, as is known, the rate of esterification of aromatic carboxylic acids, such as, for example, isophthalic acid, is considerably slower than that of dimethylolpropionic acid and the latter, in turn, is slower than, for example, that of adipic acid.
2~8~737 In the case of the polyester-polyols containing sulfonic acid groups it can be necessary, in order to achieve as ~uantitative as possible a condensation reaction of the sulfo monomer, to carry out the synthesis also in a ~ultistage process. To this end, the entire hydroxyl-functional components are first reacted with the sulfo monomers and optionally with the aromatic, carboxylic acid-containing components in the presence of catalysts, so that 95% of the amount of distillate calculated for a quantitative conversion is obtained from the condensation reaction. The aliphatic carboxylic acid components are then reacted, where appropriate, the condensation reac-tion being carried out until a free acid group content of less than 18 meq (COOH)/100 g is obtained.
The polycondensation reaction takes place at temperatures between 150 and 230C, preferably between 160 and 21~C.
Suitable catalysts are, preferably, organometallic com-pounds, in particular zinc-, tin- or titanium-containing compounds, such as, for example, zinc acetate, dibutyltin oxide or tetrabutyl titanate. The amount of catalyst is preferably 0.1 to 1.5% by weight of the total batch.
The polyester-polyols obtained in this way are then reacted with a partially capped polyisocyanate. Suitable polyisocyanates are all compounds of this type known here, for example trimethylene diisocyanate, tetra-methylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylene diisocyanate, 2,3-dimethylene diisocyanate, l-methyl-trimethylene diisocyanate, l,3-cyclopentylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,2-cyclo-hexylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, 4,4'-biphenylene diiso-cyanate, 1,5-naphthalene diisocyanate, 1,4-naphthalene diisocyanate, 1-isocyanatomethyl-5-isocyanato-1,3,3,3-trimethylcyclohexane, bis(4-isocyanatocyclo-hexyl)methane, bis(4-isocyanatocyclophenyl)methane, 4,4'-diisocyanatodiphenyl ether, 2,3-bis(8-isocyanato-octyl)-4-octyl-5-hexylcyclohexene, trimethylxylylene diisocyanate or tetramethylxylylene diisocyanate or mixtures of these compounds.
In addition to these simple polyisocyanates, those which contain hetero-atoms in the radical linked to the iso-cyanate groups are also suitable. Examples of such compounds are polyisocyanates which contain carbodiimide groups, allophonate groups, isocyanurate groups, urethane groups, acylated urea groups or biuret groups.
Suitable polyisocyanates are, finally, also those higher functional isocyanates which are prepared by reacting a diisocyanate with a polyol (for example trimethylol-propane or pentaerythritol), as well as the ethoxylated and/or propoxylated derivatives thereof having a degree of alkoxylation of 0.5 to 4.5 ethylene oxide and/or propylene oxide per hydroxyl functional group.
Suitable capping agents are aliphatic, cycloaliphatic or alkyl-aromatic (monohydric) alcohols, for example lower aliphatic alcohols, such as methyl alcohol or ethyl alcohol, the various propyl, butyl and hexyl alcohols, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol and the like, and also unsaturated alcohols such as propargyl alcohol or allyl alcohols, cycloaliphatic alcohols, such as cyclopentanol or cyclohexanol, alkyl-aromatic alcohols, such as benzyl alcohol, p-methylbenzyl alcohol, p-methoxybenzyl alcohol and p-nitrobenzyl alcohol, and monoethers of glycols, such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether and the like. ~urther capping agents are phenols, ketoximes, expediently having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, such as acetone oxime, methyl ethyl ketone oxime (= butanone oxime), hexanone oxime (such as methyl butyl ketone oxime), heptanone oxime (such as methyl n-amyl ketone oxime), octanone oxime and cyclohexanone oxime, CH-acid compounds, such as 208~737 malonic acid alkyl esters, acetoacetates and also cyano-acetates, in each case having 1 to 4 carbon atoms in the ester group, NH-acid compounds, such as caprolactam and amino alcohols, such as diethylethanolamine.
The polyisocyanates are re~cted in accordance with methods known per se with an amount of a capping agent such that the ratio of free isocyanate groups to capped isocyanate groups is 1:4 to 1:0.5.
These partially capped polyisocyanates are then reacted in accordance with known methods with the polyester-polyol described above, specifically in proportions by weight such that the end product has the parameters defined initially. Any free acid groups present are then finally completely or partially neutralized. Aqueous solutions of alkali metal hydroxides or amines, for example trimethylamine, triethylamine, dimethylaniline, diethylaniline, triphenylamine, dimethylethanolamine, aminomethylpropanol, dimethylisopropanolamine or ammonia, are used for this purpose.
If the relative reactivities of the polyester-polyol and the capping agent with respect to the polyisocyanate permit, there are also the following two process possibilities:
- the polyisocyanate is added to the capping agent, which has been initially introduced with the polyester-polyol, if appropriate in the presence of a catalyst, and, in the case of appropriate selec-tivity, the claimed binder can also be obtained in this way.
0 - the polyester-polyol is reacted with the polyiso-cyanate, if appropriate in the presence of a catalyst, until only the required free OH equiva-lents are still present. The capping agent is then added to this NCO-functional polymer and in this way 2~737 it is possible to block the isocyanate groups in order to obtain the claimed binder.
The aqueous dispersions of the binders according to the invention can be used to prepare coating systems, as binders for water-dilutable adhesives or as resins for printing inks.
In the case of appropriate compatibility, they can also optionally be combined with other aqueous plastic disper-sions and/or solutions, for example acrylic polymers and/or methacrylic polymers, polyurethane, polyurea resins, polyester resins and epoxy resins, thermoplastics based on polyvinyl acetate, polyvinyl chloride, polyvinyl ether, polychloroprene or polyacrylonitrile and ethylene-butadiene-styrene copolymers.
IThe binders according to the invention can be applied to very diverse substrates, for example ceramics, wood, glass, concrete and preferably plastics, such as polycarbonate, polystyrene, polyvinyl chloride, polyester, poly(meth)acrylates, acrylonitrile-butadiene-styrene polymers and the like, as well as also preferablymetals and alloys, such as iron, copper, aluminum, steel, tin, zinc, titanium, magnesium, brass, bronze and the like.
The binders according to the invention are suitable, for example, for the production of coating films, coatings and/or intermediate coatings for very diverse fields of application. After adding conventional coating additives, such as flow auxiliaries, wetting auxiliaries and dis-persing auxiliaries, as well as conventional pigment formulations (TiO2, BaSO~), they are suitable, in par-ticular, as aqueous stoving filler coatings, which -especially in the automobile industry - are applied as intermediate coating between primer and top coat, stoving or forced drying being carried out at temperatures of 70 to 200C, in particular of 100 to 180C, under otherwise 208~737 customary stoving conditions. Compared with aqueous filler coatings used on the market, they are distin-guished by very good protection against flying stones, very good resistance to warm and humid conditions and very good optical properties (gloss, surface structure).
Although it is not absolutely essential to add a cross-linking component when formulating water-dilutable coating compositions containing the binders according to the invention, it is nevertheless possible to add further crosslinking agents customary in coating technology, such as, for example, water-soluble or water-emulsifiable melamine or benzoguanamine resins, water-emulsifiable polyisocyanates or water-emulsifiable prepolymers con-taining terminal isocyanate groups, water-soluble or water-dispersible polyaziridines and b~ocked polyiso-cyanates, provided these are compatible.
Because of the high gloss, a good top coat quality can also be achieved using the binders according to the invention if suitable pigments are chosen. A prerequisite is then, however, the use of non-yellowing polyiso-cyanates (for example aliphatic isocyanates). Short-term weathering tests show very good results.
A particular advantage of the binders according to the invention is their storage stability (Table 3).
Examples 1. Polyesters The preparation of the polyester-polyol~ is carried out under a Nz atmosphere in a 4 1 four-necked round-bottomed flask provided with an anchor stirrer, a N2 inlet, a temperature sensor and a packed column (about 20 cm long and 3 cm in diameter) fitted with a top thermometer and a descending condenser.
Polyester 1 1,241 g of hexanediol (HD), 365 g of neopentyl glycol 20~4737 (NPG), 440 g of trimethylolpropane (TMP), 312 g of sulfoisophthalic acid dimethyl ester sodium salt (5-SIP-DME-Na) and 3 g of anhydrous zinc acetate are subjected to a condensation reaction at 170C to 220C
and a ma~imum top temperature of 65C until 50 g of distillate are obtained. The reaction mixture is cooled to 140C, 445 g of terephthalic acid (TPA), 891 g of isophthalic acid (IPA) and 2.6 g of dibutyltin oxide (DBTO) are added and the condensation reaction is carried out at 200C until a carboxyl group content of 26 meq (COOH)/100 g is obtained. The reaction mixture is cooled to 140C, 706 g of adipic acid (ADPA) are added and the condensation reaction is carried out at temperatures of 165 to 220C (maximum top temperature 100C) until the carboxyl group content is 7 meq (COOH)/100 g.
Polyester 2 665 g of hexanediol, 195 g of neopentyl glycol and 235 g of trimethylolpropane are melted, 210 g of terephthalic acid and 1.2 g of DBTO are then added at 100C and the condensation reaction is carried out at 220C and a maximum top temperature of 100C until a clear melt is obtained. The reaction mixture is cooled to 160C, 455 g of isophthalic acid and a further 1.2 g of DBTO are added and the condensation reaction is carried out until a carboxyl group content of 35 meq (COOH)/100 g is obtained. The reaction is then cooled to 130C and 910 g of adipic acid and 505 g of dimethylolpropionic acid (DMPA) are added and the condensation reaction is carried out at 160C to 200C (maximum top temperature 100C) until a value of 90 meq (COOH)/100 g is obtained.
Polyester 3 500 g of hexanediol, 520 g of neopentyl glycol and 235 g of trimethylolpropane are melted and 300 g of tere-phthalic acid, 450 g of isophthalic acid and 2.5 g of DBTO are then added at 100C. The condensation reaction is carried out at 190C to 200C until a carboxyl group content of 14 meq (COOH)/100 g is obtained, the reaction mixture is cooled to 140C, 900 g of adipic acid are added and the condensation reaction is carried out at 190C to 200~C until a value of 133 meq (COOH~/100 g is obtained. The reaction mixture is then cooled to 140C, 300 g of dimethylolpropionic acid are added and the condensation reaction is carried out at 170C to 180C
Imaximum top temperature 100C) until the carboxyl group content is 100 meq (COOHj/100 g.
Polyester 4 500 g of hexanediol, 400 g of neopentyl glycol and 350 g of trimethylolpropane are melted. 300 g of terephthalic acid, 450 g of isophthalic acid and 2.5 g of DBTO are added at 100C and the condensation reaction is carried out at 190C to 200C until the carboxyl group content is 7 meq (COOH)~100 g. ~he reaction mixture is cooled to 140C, 900 g of adipic acid and 300 g of dimethylol-propionic acid are added and the condensation reaction is carried out at 160 to 170C until the free carboxyl group content is 128 meq (COOH)/100 g. The reaction mixture is then cooled to 140C and a vacuum of 100 mbar is applied until a value of 110 meq (COOH)/100 g is reached (about 30 min).
2. Self-crosslinking - urethane-~odified - binders ( S~B) ~he synthesis of the binders according to the invention is carried out in a 2 1 four-necked round-bottomed flask fitted with a reflux condenser and a temperature sensor.
S~B 1 75.0 g of diphenylmethane 4,4'-diisocyanate (MDI) are added in the course of 7 min to 43.2 g of diethyl malonate, 0.8 g of sodium methylate and 74.0 g of methyl ethyl ketone and the mixture is stirred at 45C, with cooling, until a NCO content of 5.5% is obtained. A
solution of 269.5 g of polyester 1 in 92.5 g of methyl ethyl ketone is then added in the course of 2 min, the temperature is raised to 50C and the reaction mixture is , 208~737 _ 13 -stirred until the NCO content is < 0.1%. After further dilution with 54.4 g of butyl glycol/isopropanol (weight ratio 3/1), the mixture is dispersed with 675 g of demineralized water heated to 50C. 170 g of methyl ethyl ketone are distilled off from the aqueous phase under 250 mbar and at 60C.
66.6 g of isophorone diisocyanate (IPDI) are metered, in the course of 2 min, into 27.5 g of methyl ethyl ketoxime (ME~ oxime), 0.4 g of dibutyltin dilaurate (DBTDL) and 55.6 g of methyl ethyl ketone and the mixture is stirred at 35C, with cooling, until a NCO content of 8.5% is obtained. A solution of 294 g of polyester 2 in 110 g of methyl ethyl ketone i then added in the course of 3 min, the temperature is raised to 50C and the reaction mixture is stirred until the NCO content is < 0.1%. After further dilution with 54.4 g of butyl glycol~isopropanol (weight ratio 3/1), the mixture is neutralized with 20.0 g of triethylamine (TE~) and then dispersed with 675 g of demineralized water heated to 60. 170 g of methyl ethyl ketone are distilled off from the aqueous phase under 200 mbar and at 60~C.
435 g of methyl eth.yl ketoxime are added to 1,110 g of isophorone diisocyanate and 0.75 g of DETDL at 25C to 30C, with cooling, over a period of 75 min, the tempera-ture is then raised to 40C and the reaction mixture is stirred for a further 1 h. Isophorone diisocyanate capped on one side by methyl ethyl ketoxime is thus obtained.
55 g of n-methylpyrrolidone, 237.6 g of polyester 3 and 186.9 g of isophorone diisocyanate capped on one side, as described above, are stirred at 60C until a NCO content of 0.4% is obtained. 21.1 g of dimethylethanolamine (DNEA) are then added and the reaction mixture is stirred for a further one hour at 60C and dispersed with 715 g of demineralized water heated to 60C.
.
- 14 - 208~737 42.0 g of n-methylpyrrolidone, 220.0 g of polyester 4 and 92.0 g of isophorone diisocyanate capped on one side with methyl ethyl ketoxime are stirred at 60C until a NCO
content of 0.1% is obtained. 21.6 g of dimethylethanol-amine are then added and the reaction mixture is s~irred for a further one hour at 60C and dispersed with 460 g of demineralized water heated to 60C.
435 g of methyl ethyl ketoxime are added to 1,220 g of tetramethylxylylene diisocyanate (TMXDI) and 0.75 g of DBTL at 25C to 30C, with cooling, over a period of 75 min, the temperature is then raised to 40C and the reaction mixture is stirred for a further 1 h. TMXDI
capped on one side with methyl ethyl ketoxime is obtained in this way.
45.0 g of n-methylpyrrolidone, 219.6 g of polyester 4 and 102.2 g of trimethylxylylene diisocyanate capped on one side with methyl ethyl ketoxime are stirred at 60C until a NCO content of 0.1% is obtained. 36.2 g of triethanol-amine tTOLA) are then added and the reaction mixture is stirred for a further one hour at 60C and dispersed with 400g of demineralized water heated to 60C.
230.0 g of polyester 4, 44.0 g of N-methylpyrrolidone, 27.4 g of methyl ethyl ketoxime and O.OS g of dibutyltin dilaurate are stirred homogeneously at 35-40C and 69.8 g of isophorone diisocyanate are metered in at such a rate that the temperature does not rise above 65C. The reaction mixture is stirred at 65C until a NCO content of < 0.10% is obtained. 22.6 g of dimethylethanolamine are then added at 65C and the reaction mixture is stirred for a further hour and dispersed with 490 g of demineralized water heated to 65C~
Comparison example:
119.0 g of methyl ethyl ketoxime-capped isophorone diisocyanate (reaction of 1 mol of isophorone diiso-cyanate with 2 mol of methyl ethyl ketoxime in the presence of 0 15 g of dibutyltin dilaurate) are stirred homogeneously with 42.0 g of N-methylpyrrolidone and 220 0 g of polyester 4 at 60C and 21 6 g of dimethyl-ethanolamine are added at this temperature. The reaction mixture is stirred for a further hour at 60C and dis-persed with 515 0 g of demineralized water heated to60C.
3. Example of a stoving filler coating composition based on SUB 4 (colour shade light gray) Parts by weight Wetting and dispersing auxiliaries (-Additol XL 250) 0.3 Flow agent (-Additol XW 390) 0.4 Titanium dioxide 12.0 20 Blanc fixe micro 10 0 Talc, Naintsch E 7 2 0 Flame soot 101 0 1 Deionized water 9 5 Test results: see Table 4 4. Example of a water-dilutable top coating composition based on SUB 5 Parts by weight SUB 5 68.6 Wetting and dispersing auxiliaries (-Additol XL 250) 0.2 Flow agent ('Additol XW 390) 25~ in H200.5 Light stabilizers (-Sanduvor 3212) 50% in butyl glycol 1.7 10 Titanium dioxide 23.5 Deionized water 5.5 100.O
Test results for SUB_5 in the top coat Test 20' 130C20' 150C
.
Coating thickness in ~m 31 31 , Gloss < 20 76% 75%
< 60 88% 89 Pendulum hardness in sec 153 144 Cross-hatch on sheet steel C-H 0 C-H 0 : 25 Erichsen deep drawing on sheet steel in mm 9.9 9.9 Resistance to solvents acetone ~ 20 sec< 20 sec xylene 1 min 1 min ethanol/water (1:1)9 min15 min Test in total process (Gathodic electrocoat~filler/top coa~) Cross-hatch C-H O
Erichsen deep drawing in mm 6 .
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Claims (10)
1. A water-dilutable, urethane-modified and hydroxyl group-containing binder, prepared by reaction of a polyester containing hydroxyl groups and neutralized and/or neutralizable acid groups with substoichio-metric amounts (with respect to the number of free hydroxyl groups) of a partially blocked polyisocyanate.
2. The binder as claimed in claim 1, which contains hydroxyl groups of 3-350, preferably 5-170 milli-equivalents (OH)/100 g of solid resin.
3. The binder as claimed in at least one of the preced-ing claims, wherein the content of capped isocyanate groups, calculated as -NCO, is between 0.5 and 15%
by weight, with respect to solid resin.
by weight, with respect to solid resin.
4. The binder as claimed in at least one of the preced-ing claims, wherein the content of urethane groups, calculated as NH-C(O)O- is between 0.5 and 20% by weight, with respect to solid resin.
5. The binder as claimed in at least one of the preced-ing claims, which contains neutralizable and/or neutralized carboxylic acid and/or sulfonic acid and/or phosphonic acid groups.
6. The binder as claimed in claim 5, wherein the amount of neutralized carboxylic acid and/or sulfonic acid and/or phosphonic acid groups is between 5 and 200, preferably 10-90, milliequivalents of sulfonate, carboxylate or phosphonate per 100 g of solid resin.
7. The binder as claimed in at least one of the preced-ing claims, which contains further coating agents and/or further binder components.
8. Use of the binder as claimed in at least one of the preceding claims in coating systems.
9. Use of the binder as claimed in at least one of the preceding claims as a stoving filler coating com-position for coating automobiles.
10. Use of the binder as claimed in at least one of claims 1-8 as a stoving top coat.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4142734.3 | 1991-12-21 | ||
| DE4142734A DE4142734A1 (en) | 1991-12-21 | 1991-12-21 | WATER-DISPERSIBLE, URETHANO MODIFIED AND HYDROXYL GROUPS CONTAINING SELF-NETWORKING BINDER AND PREPARATIONS THEREOF |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2084737A1 true CA2084737A1 (en) | 1993-06-22 |
Family
ID=6447994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002084737A Abandoned CA2084737A1 (en) | 1991-12-21 | 1992-12-07 | Water-dilutable, urethane-modified and hydroxyl group-containing self-crosslinking binder and formulations thereof |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0548727B1 (en) |
| JP (1) | JP3293914B2 (en) |
| AT (1) | ATE164604T1 (en) |
| AU (1) | AU654600B2 (en) |
| BR (1) | BR9205063A (en) |
| CA (1) | CA2084737A1 (en) |
| CZ (1) | CZ371892A3 (en) |
| DE (2) | DE4142734A1 (en) |
| ES (1) | ES2114546T3 (en) |
| MX (1) | MX9207460A (en) |
| NO (1) | NO302034B1 (en) |
| ZA (1) | ZA929812B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6221955B1 (en) | 1997-12-09 | 2001-04-24 | Dekro Paints (Proprietary) Limited | Polyurethane resins |
| US6743484B2 (en) | 2000-06-30 | 2004-06-01 | Basf Coatings Ag | Reactive mixtures of substances on the basis of propargyl-alcohol blocked polyisocyanates, method for preparing the same and the use thereof |
| US20120125799A1 (en) * | 2008-11-26 | 2012-05-24 | Valspar Sourcing, Inc. | Polyester Polymer and Coating Compositions Thereof |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19504947C2 (en) * | 1994-06-20 | 2003-07-03 | Bollig & Kemper Gmbh & Co Kg | Multi-layer coating |
| DE19914882A1 (en) † | 1999-04-01 | 2000-10-05 | Bayer Ag | Self-crosslinking polyurethane dispersion for coating applications, e.g. sizing glass fibres, contains blocked isocyanate groups and reactive hydroxyl or amino groups on the polymer or in an extra reaction component |
| DE10145344A1 (en) * | 2001-09-14 | 2003-04-24 | Audi Ag | Process for producing a multi-layer coating of a vehicle body and coating material |
| DE10238349B4 (en) * | 2002-08-16 | 2005-03-17 | Ppg Industries Lacke Gmbh | Polyurethane microgel |
| US8367171B2 (en) | 2008-11-26 | 2013-02-05 | Valspar Sourcing, Inc. | Polymer having polycyclic groups and coating compositions thereof |
| MX341307B (en) | 2008-11-26 | 2016-08-15 | Valspar Sourcing Inc | Polyester-carbamate polymer and coating compositions thereof. |
| AU2010233173B2 (en) | 2009-04-09 | 2014-05-15 | Swimc Llc | Polymer having unsaturated cycloaliphatic functionality and coating compositions formed therefrom |
| EP3176201A1 (en) | 2009-04-09 | 2017-06-07 | Valspar Sourcing, Inc. | Polyester coating composition |
| WO2011010539A1 (en) * | 2009-07-24 | 2011-01-27 | 関西ペイント株式会社 | Water-based coating composition and method for forming multilayer coating film |
| JP5577765B2 (en) * | 2010-03-10 | 2014-08-27 | 東洋インキＳｃホールディングス株式会社 | Laminating adhesive and method for producing the same |
| DE102017131445A1 (en) | 2016-12-30 | 2018-07-05 | Coatings Foreign Ip Co. Llc | Crosslinking component for binder resin |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2729245A1 (en) * | 1977-06-29 | 1979-01-11 | Bayer Ag | PROCESS FOR THE MANUFACTURING OF CARBOXYLATE-BASED POLYISOCYANATE ADDITION PRODUCTS |
| IT1202948B (en) * | 1979-06-29 | 1989-02-15 | Hoechst Sara Spa | VARNISHING PRODUCT CONSTITUTED BY AN ORGANIC BINDER SOLUBLE OR DISPERSIBLE IN WATER AND A SOLVENT MIXTURE |
| DE3326188A1 (en) * | 1983-07-20 | 1985-01-31 | Bayer Ag, 5090 Leverkusen | METHOD FOR THE PRODUCTION OF ORGANIC POLYISOCYANATES WITH AT LEAST PARTLY BLOCKED ISOCYANATE GROUPS, THE COMPOUNDS AVAILABLE AFTER THE METHOD AND THE USE THEREOF FOR THE PRODUCTION OF POLYURETHANES, BURNING LACQUES OR WATER POWDERED POLYURATES. -DISPERSIONS |
| DE3345448A1 (en) * | 1983-12-15 | 1985-06-27 | Bayer Ag, 5090 Leverkusen | AQUEOUS POLYURETHANE BURNING VARNISHES AND THEIR USE FOR THE PRODUCTION OF LACQUER FILMS AND COATINGS |
| AT383820B (en) * | 1985-09-25 | 1987-08-25 | Vianova Kunstharz Ag | METHOD FOR PRODUCING SELF-CROSS-LINKING CATHIONIC LACQUER BINDERS AND THE USE THEREOF |
| DE3606513C2 (en) * | 1986-02-28 | 1998-05-07 | Basf Coatings Ag | Dispersions of crosslinked polymer microparticles in aqueous media and processes for producing these dispersions |
-
1991
- 1991-12-21 DE DE4142734A patent/DE4142734A1/en not_active Withdrawn
-
1992
- 1992-12-07 CA CA002084737A patent/CA2084737A1/en not_active Abandoned
- 1992-12-14 EP EP92121242A patent/EP0548727B1/en not_active Expired - Lifetime
- 1992-12-14 DE DE59209262T patent/DE59209262D1/en not_active Expired - Lifetime
- 1992-12-14 ES ES92121242T patent/ES2114546T3/en not_active Expired - Lifetime
- 1992-12-14 AT AT92121242T patent/ATE164604T1/en not_active IP Right Cessation
- 1992-12-17 JP JP33754592A patent/JP3293914B2/en not_active Expired - Fee Related
- 1992-12-17 AU AU30211/92A patent/AU654600B2/en not_active Ceased
- 1992-12-17 CZ CS923718A patent/CZ371892A3/en unknown
- 1992-12-18 BR BR9205063A patent/BR9205063A/en not_active Application Discontinuation
- 1992-12-18 NO NO924923A patent/NO302034B1/en not_active IP Right Cessation
- 1992-12-18 MX MX9207460A patent/MX9207460A/en unknown
- 1992-12-18 ZA ZA929812A patent/ZA929812B/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6221955B1 (en) | 1997-12-09 | 2001-04-24 | Dekro Paints (Proprietary) Limited | Polyurethane resins |
| US6743484B2 (en) | 2000-06-30 | 2004-06-01 | Basf Coatings Ag | Reactive mixtures of substances on the basis of propargyl-alcohol blocked polyisocyanates, method for preparing the same and the use thereof |
| US20120125799A1 (en) * | 2008-11-26 | 2012-05-24 | Valspar Sourcing, Inc. | Polyester Polymer and Coating Compositions Thereof |
| US8574672B2 (en) * | 2008-11-26 | 2013-11-05 | Valspar Sourcing, Inc. | Polyester polymer and coating compositions thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CZ371892A3 (en) | 1993-09-15 |
| NO924923D0 (en) | 1992-12-18 |
| AU654600B2 (en) | 1994-11-10 |
| EP0548727A2 (en) | 1993-06-30 |
| ATE164604T1 (en) | 1998-04-15 |
| JP3293914B2 (en) | 2002-06-17 |
| DE4142734A1 (en) | 1993-06-24 |
| MX9207460A (en) | 1993-06-01 |
| AU3021192A (en) | 1993-06-24 |
| ZA929812B (en) | 1993-06-23 |
| DE59209262D1 (en) | 1998-05-07 |
| ES2114546T3 (en) | 1998-06-01 |
| NO302034B1 (en) | 1998-01-12 |
| NO924923L (en) | 1993-06-22 |
| EP0548727A3 (en) | 1993-09-01 |
| EP0548727B1 (en) | 1998-04-01 |
| JPH05247170A (en) | 1993-09-24 |
| BR9205063A (en) | 1993-06-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |