NO302034B1 - Water-dilutable, urethane-modified and hydroxyl group-containing, self-crosslinking one-component binder, binder composition comprising this and the use thereof - Google Patents

Water-dilutable, urethane-modified and hydroxyl group-containing, self-crosslinking one-component binder, binder composition comprising this and the use thereof Download PDF

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NO302034B1
NO302034B1 NO924923A NO924923A NO302034B1 NO 302034 B1 NO302034 B1 NO 302034B1 NO 924923 A NO924923 A NO 924923A NO 924923 A NO924923 A NO 924923A NO 302034 B1 NO302034 B1 NO 302034B1
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acid
binder
groups
binder according
hydroxyl group
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NO924923L (en
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Reiner Exner
Heinz-Peter Klein
Michael Schwab
Gerd Walz
Udo Frank
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Hoechst Ag
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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
    • 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
    • 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
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Paper (AREA)

Abstract

A water-dilutable, urethane-modified and hydroxyl-containing binder prepared by reacting a polyester containing hydroxyl groups and neutralised and/or neutralisable acid groups with substoichiometric amounts (based on the number of free hydroxyl groups) of a partially blocked polyisocyanate. This binder is suitable for the production of paint films and other coatings of this type.

Description

Foreliggende oppfinnelse vedrører nye, vannfortynnbare, uretanmodifiserte og hydroksylgruppeholdige, selvtverrbindende enkomponent-bindemidler, som er dispergert og/eller oppløst i et (overveiende) vandig medium, bindemiddelblandinger omfatten-de disse og deres anvendelse, fortrinnsvis som innbrenningslak-ker ved fremstilling av lakkfilmer og besjiktninger. The present invention relates to new, water-dilutable, urethane-modified and hydroxyl group-containing, self-crosslinking one-component binders, which are dispersed and/or dissolved in a (predominantly) aqueous medium, binder mixtures comprising these and their use, preferably as burn-in lacquers in the production of paint films and charges.

Vanlige innbrenningssystemer er ofte basert på kombinasjon av et bindemiddel med en tilsvarende tverrbindingskomponent. Det kan derved komme til uforenligheter mellom disse komponentene. Ved vandige systemer kommer i tillegg at tverrbindingskompo-nentene som regel også må være vannforenlige eller stabili-seres i vandig fase ved emulgatorvirkningen av bindemiddelet. Common burning-in systems are often based on the combination of a binder with a corresponding cross-linking component. This can lead to incompatibilities between these components. In the case of aqueous systems, in addition, the cross-linking components must as a rule also be water-compatible or stabilized in the aqueous phase by the emulsifying effect of the binder.

TJS-patent nr. 4 507 427 vedrører fremstillingen av blokkerte isocyanater med spesielle blokkeringsmidler. Disse blokkerte isocyanatene kan kombineres med oppløsninger eller dispersjoner av overfor isocyanat reaktive grupper som to-komponent-system. TJS patent no. 4 507 427 relates to the production of blocked isocyanates with special blocking agents. These blocked isocyanates can be combined with solutions or dispersions of isocyanate-reactive groups as a two-component system.

Ved foreliggende oppfinnelse unngås uforenligheten mellom tverrbinder (ifølge oppfinnelsen polyisocyanater) og bindemiddel (ifølge oppfinnelsen polyesterpolyolinneholdende anioniske grupper) ved den delvis kovalente binding av isocyanat-komponentene til polyesterharpiksen, slik at det foreligger et selvtverrbindende enkomponents-innbrenningssystem. In the present invention, the incompatibility between crosslinker (according to the invention polyisocyanates) and binder (according to the invention polyester polyoline containing anionic groups) is avoided by the partially covalent binding of the isocyanate components to the polyester resin, so that there is a self-crosslinking one-component burn-in system.

Lagringsstabiliteten for det overveiende i vann dispergerte bindemiddelet ifølge foreliggende oppfinnelse er derved vesentlig større enn den for en kombinasjon av polyesterpolyolen med det tilsvarende, fullstendig endeavsluttede polyisocyanatet. The storage stability of the predominantly water-dispersed binder according to the present invention is thereby substantially greater than that of a combination of the polyester polyol with the corresponding, completely end-capped polyisocyanate.

Foreliggende oppfinnelse vedrører følgelig et vannfortynnbart, uretanmodifi sert og hydroksylgruppeholdig, selvtverrbindende enkomponent-bindemiddel, kjennetegnet ved at det er fremstilt ved omsetning av en polyester inneholdende hydroksylgrupper og nøytraliserte og/eller nøytraliserbare syregrupper og et delvis blokkert polyisocyanat, hvorved polyisocyanatet anvendes i slike mengder at hydroksylgruppeinnholdet i fastharpiksen utgjør 3 til 350 mmol/100 g, og blokkeringsgraden av isocyanatet velges slik at masseandelen av blokkerte iso-cyanatgrupper (beregnet som NCO, molar masse = 42 g/mol) i fastharpiksen utgjør mellom 0,5 og 15$. The present invention therefore relates to a water-dilutable, urethane-modified and hydroxyl group-containing, self-crosslinking one-component binder, characterized in that it is produced by reaction of a polyester containing hydroxyl groups and neutralized and/or neutralizable acid groups and a partially blocked polyisocyanate, whereby the polyisocyanate is used in such quantities that the hydroxyl group content in the solid resin is 3 to 350 mmol/100 g, and the degree of blocking of the isocyanate is chosen so that the mass proportion of blocked isocyanate groups (calculated as NCO, molar mass = 42 g/mol) in the solid resin is between 0.5 and 15$.

Bindemiddelet ifølge oppfinnelsen inneholder fortrinnsvis hydroksylgrupper i en mengde på 5 - 170 mmol i 100 g fastharpiks. Andelen av uretangrupper ligger fortrinnsvis mellom 0,5 og 20$, på basis av den faste harpiksen (som -NH-C(O)O-). For å oppnå fortynnbarheten med vann inneholder harpiksen nøytraliserbare og /eller nøytraliserte sure grupper, generelt karboksyl-, sulfon- eller fosfonsyregrupper. Innholdet av disse gruppene ligger vanligvis mellom 5 og 200, fortrinnsvis mellom 10 og 90 mmol i 100 g fastharpiks. The binder according to the invention preferably contains hydroxyl groups in an amount of 5 - 170 mmol in 100 g of solid resin. The proportion of urethane groups is preferably between 0.5 and 20%, based on the solid resin (such as -NH-C(O)O-). To achieve the dilutability with water, the resin contains neutralizable and/or neutralized acid groups, generally carboxylic, sulfonic or phosphonic acid groups. The content of these groups is usually between 5 and 200, preferably between 10 and 90 mmol in 100 g of solid resin.

De som utgangsmaterial tjenende polyesterpolyolene fremstilles ved vanlig fremgangsmåte med kondensasjon av polykarboksyl-syrer, polyalkoholer og hydroksylkarboksylsyrer, som alle eventuelt kan inneholde ytterligere karboksylsyre-, sulfonsyre-eller fosfonsyregrupper. The polyester polyols serving as starting material are produced by the usual method of condensation of polycarboxylic acids, polyalcohols and hydroxyl carboxylic acids, all of which may possibly contain additional carboxylic acid, sulphonic acid or phosphonic acid groups.

Polykarboksylsyrene kan være av alifatisk, cykloalifatisk, aromatisk og/eller heterocyklisk natur og eventuelt være substituert, f.eks. med halogenatomer. Som eksempler på slike karboksyl syrer og deres derivater skal nevnes: ravsyre, adipinsyre, korksyre, aselainsyre, sebacinsyre, ftalsyre, tereftalsyre sulfotereftalsyre, sulfoisoftalsyre, sulfof-talsyre, isoftalsyre, trimelittsyre, pyromelittsyre, tetrahyd-roftalsyre, heksahydroftalsyre, di- og tetraklorftalsyre, endometylentetrahydroftalsyre og deres heksaklorderivat, glutarsyre, maleinsyre, fumarsyre, dimere og trimere fettsyrer. Istedenfor disse syrene kan også deres anhydrider, såfremt de eksisterer, anvendes. The polycarboxylic acids can be of aliphatic, cycloaliphatic, aromatic and/or heterocyclic nature and optionally be substituted, e.g. with halogen atoms. Examples of such carboxylic acids and their derivatives should be mentioned: succinic acid, adipic acid, cormic acid, azelaic acid, sebacic acid, phthalic acid, terephthalic acid, sulfoterephthalic acid, sulfoisophthalic acid, sulfophthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, di- and tetrachlorophthalic acid, endomethylenetetrahydrophthalic acid and their hexachloro derivative, glutaric acid, maleic acid, fumaric acid, dimeric and trimeric fatty acids. Instead of these acids, their anhydrides, if they exist, can also be used.

Som polyalkoholer anvendes fortrinnsvis lavmolekylære polyoler, polyhydroksy-polyeter, polylakton-polyoler og polykarbonat-polyoler. Som lavmolekylære polyoler kommer f.eks. på tale etandiol, de forskjellige propan-, butan-, heksandiolene, dimetylolcykloheksan, 2, 2-bis(4-hydroksycykloheksyl) propan , dietylenglykol, trietylenglykol, glyserol, trimetyloletaneller Low molecular weight polyols, polyhydroxy polyethers, polylactone polyols and polycarbonate polyols are preferably used as polyalcohols. As low-molecular polyols, e.g. in terms of ethanediol, the various propane, butane, hexanediols, dimethylolcyclohexane, 2, 2-bis(4-hydroxycyclohexyl) propane, diethylene glycol, triethylene glycol, glycerol, trimethylolethanes

-propan, heksantriol, pentaerytrit, dipentaerytrit eller sorbit, videre anvendes lavmolekylære polyoler, fortrinnsvis dioler, som også inneholder en ionisk gruppe i form av karboksylsyre-, sulfonsyre- eller fosfonsyregrupper. Disse syregruppene kan være frie og/eller foreligge i saltform. Eksempler på disse gruppene av monomerer er a-C2-C-^Q-bishydrok-sykarboksylsyre som f.eks. dihydroksypropionsyre, dimetylol-syre, dihydroksyetylpropionsyre, dimetylolsmørsyre, vinsyre, dihydroksymaleinsyre, dihydroksybenzosyre eller 3-hydroksy-2-hydroksymetylpropansulfonsyre, dihydroksybutansulfonsyrer. Som polyhydroksy-polyeter kommer forbindelser med formelen -propane, hexanetriol, pentaerythritol, dipentaerythritol or sorbitol, low molecular polyols are also used, preferably diols, which also contain an ionic group in the form of carboxylic acid, sulphonic acid or phosphonic acid groups. These acid groups can be free and/or present in salt form. Examples of these groups of monomers are a-C2-C-^Q-bishydroxy-sycarboxylic acid such as e.g. dihydroxypropionic acid, dimethylolic acid, dihydroxyethylpropionic acid, dimethylolbutyric acid, tartaric acid, dihydroxymaleic acid, dihydroxybenzoic acid or 3-hydroxy-2-hydroxymethylpropanesulfonic acid, dihydroxybutanesulfonic acids. As polyhydroxy polyether compounds come with the formula

på tale, hvori in speech, in which

R er et hydrogen eller en lavere alkylrest, eventuelt med R is a hydrogen or a lower alkyl residue, optionally with

forskjellige substituenter, different substituents,

n er et tall fra 2 til 6 og n is a number from 2 to 6 and

m er et tall fra 10 til 120. m is a number from 10 to 120.

Eksempeler på polyhydroksypolyetere er poly(oksy-tetra metylen)glykoler, poly(oksyetylen)glykoler og poly(oksy-propylen)glykoler. De foretrukne polyhydroksy-polyeterne er poly(oksypropylen)glykoler med en molekylvekt i området fra 400 til 5000. Examples of polyhydroxy polyethers are poly(oxy-tetramethylene) glycols, poly(oxyethylene) glycols and poly(oxy-propylene) glycols. The preferred polyhydroxy polyethers are poly(oxypropylene) glycols with a molecular weight in the range from 400 to 5000.

De fra laktoner avledede plylaktonpolyolene oppnår man eksempelvis ved omsetningen av et E-caprolakton med en polyol. Slike produkter er beskrevet i US-PS 3 169 945. Polylaktonpolyolene, som man oppnår ved denne omsetningen utmerker seg ved nærvær av endestående hydroksylgruppe og ved gjentagende polyesterandeler som er avledet fra lakton. Disse gjentagende molekylandelene kan tilsvare formelen The plylactone polyols derived from lactones are obtained, for example, by reacting an E-caprolactone with a polyol. Such products are described in US-PS 3,169,945. The polylactone polyols, which are obtained by this reaction, are distinguished by the presence of a terminal hydroxyl group and by repeating polyester parts which are derived from lactone. These repeating molecular parts can correspond to the formula

hvori n fortrinnsvis er 4 til 6 og substituenten R er hydrogen, en alkylrest, en cykloalkylrest eller en alkoksyrest, hvorved ingen substituent inneholder mer enn 12 karbonatomer. wherein n is preferably 4 to 6 and the substituent R is hydrogen, an alkyl residue, a cycloalkyl residue or an alkoxy acid residue, whereby no substituent contains more than 12 carbon atoms.

Det som utgangsmateriale anvendte laktonet kan være et hvilket som helst lakton eller en hvilken som helst kombinasjon av laktoner, hvorved dette laktonet skal inneholde minst 6 karbonatomer i ringen f.eks. 6 til 8 karbonatomer og hvorved det skal være tilstede 2 hydrogensubstituenter på karbonatomet som er bundet til oksygengruppen av ringen. Det som utgangsmateriale anvendte laktonet kan angis ved den følgende generelle formelen: The lactone used as starting material can be any lactone or any combination of lactones, whereby this lactone must contain at least 6 carbon atoms in the ring, e.g. 6 to 8 carbon atoms and whereby 2 hydrogen substituents must be present on the carbon atom which is bound to the oxygen group of the ring. The lactone used as starting material can be expressed by the following general formula:

hvori n og R har den allerede angitte betydningen. wherein n and R have the meaning already indicated.

De ved oppfinnelsen foretrukne laktonene er E-kaprolaktonene, hvorved n har verdien 4. Det mest foretrukne laktonet er det usubstituerte E- kaprolaktonet, hvorved n har verdien 4 og alle R-substituentene er hydrogener. Dette lakton foretrekkes spesielt, idet det står til disposisjon i store mengder og gir overtrekk med utmerkede egenskaper. Dessuten kan forskjellige andre laktoner anvendes enkeltvis eller i kombinasjoner. The lactones preferred by the invention are the E-caprolactones, whereby n has the value 4. The most preferred lactone is the unsubstituted E-caprolactone, whereby n has the value 4 and all the R-substituents are hydrogens. This lactone is particularly preferred, as it is available in large quantities and provides coatings with excellent properties. In addition, various other lactones can be used singly or in combinations.

Eksempler på polyoler som er egnet for omsetning med laktonet er etylenglykol, 1,3-propandiol, 1,4-butandiol,heksandiol-1,6, dimetylolcykloheksan, trimetylolpropan og pentaerytritt. Examples of polyols which are suitable for reaction with the lactone are ethylene glycol, 1,3-propanediol, 1,4-butanediol, hexanediol-1,6, dimethylolcyclohexane, trimethylolpropane and pentaerythritol.

Polykarbonatpolyolene, henholdsvis polykarbonatdiolene er forbindelser som tilsvarer den generelle formelen The polycarbonate polyols, respectively the polycarbonate diols, are compounds corresponding to the general formula

hvori R betyr en alkylrest. Disse OH-funksjonelle polykarbonat-ene lar seg fremstille ved omsetning av polyoler som propandiol-1,3, butandiol-1,4, heksandiol-1,6, dietylenglykol, trietylenglykol, 1,4- bishydroksymetylcykloheksan, 2,2-bis(4-hydroksycykloheksyl)propan neopentylglykol, trimetylolpropan, pentaerytrit, med dikarbonater som dimetyl-, dietyl- eller difenylkarbonat, eller fosgen. Blandinger av slike polyoler kan også anvendes. wherein R represents an alkyl residue. These OH-functional polycarbonates can be produced by reacting polyols such as propanediol-1,3, butanediol-1,4, hexanediol-1,6, diethylene glycol, triethylene glycol, 1,4-bishydroxymethylcyclohexane, 2,2-bis(4 -hydroxycyclohexyl)propane neopentylglycol, trimethylolpropane, pentaerythritol, with dicarbonates such as dimethyl, diethyl or diphenyl carbonate, or phosgene. Mixtures of such polyols can also be used.

Som foretrukne eksempler på hydroksykarboksyl skal nevnes salisylsyre, sulfosalisylsyre og deres salter. Preferred examples of hydroxycarboxyl are salicylic acid, sulfosalicylic acid and their salts.

Fremstillingen av polyesterpolyolene foregår ved kjente fremgangsmåter i en flertrinnsfremgangsmåte avhengig av forestringshastigheten for karboksylsyrene. For det foretrukne tilfellet med fremstilling av en polyesterpolyol av en blanding av aromatiske og alifatiske dikarboksylsyrer forestres først den aromatiske karboksylsyren i nærvær av en katalysator med de hydroksyfunksjonelle komponentene og deretter innføres de alifatiske karboksylsyreholdige reaktantene, idet som bekjent forestringshastigheten for aromatiske karboksylsyrer, som f.eks. isoftalsyre, er vesentlig lavere enn den for dimetylolpropionsyre og denne igjen lavere enn f.eks. for adipinsyre. The production of the polyester polyols takes place by known methods in a multi-step process depending on the rate of esterification of the carboxylic acids. For the preferred case of producing a polyester polyol from a mixture of aromatic and aliphatic dicarboxylic acids, the aromatic carboxylic acid is first esterified in the presence of a catalyst with the hydroxy-functional components and then the aliphatic carboxylic acid-containing reactants are introduced, as the esterification rate for aromatic carboxylic acids, such as e.g. isophthalic acid, is significantly lower than that of dimethylolpropionic acid and this in turn lower than e.g. for adipic acid.

For polyesterpolyolene med sulfonsyregrupper kan det, for å oppnå en mulig kvantitativ kondensasjon av sulfomonomerene, være påkrevet også å gjennomføre syntesen i en flertrinnsfremgangsmåte. For dette formålet omsettes i nærvær av katalysato-rer først de samlede hydroksylfunksjonelle komponentene med sulfomonomerene og eventuelt med de aromatiske, karboksylsyre holdige komponentene, slik at det ved kondensasjonen kan oppnås 95% av den for en kvantitativ omsetning beregnede destillat-mengden. Deretter kommer eventuelt de alifatiske karboksylsyre-komponentene til reaksjon, hvorved kondensasjonen gjennomføres inntil et innhold av frie syregrupper på mindre enn 18 mekv. For the polyester polyols with sulphonic acid groups, in order to achieve a possible quantitative condensation of the sulphomonomers, it may also be required to carry out the synthesis in a multi-step process. For this purpose, in the presence of catalysts, the total hydroxyl-functional components are first reacted with the sulphomonomers and possibly with the aromatic, carboxylic acid-containing components, so that 95% of the amount of distillate calculated for a quantitative reaction can be obtained during the condensation. Then, if necessary, the aliphatic carboxylic acid components react, whereby the condensation is carried out until a content of free acid groups of less than 18 meq.

(COOH)/100 g. (COOH)/100 g.

Polykondensasjonsreaksjonen finner sted ved temperaturer mellom 150 og 230°C, fortrinnsvis mellom 160 og 210°C. Som katalysa-torer kommer fortrinnsvis organometallforbindelser i betrakt-ning, spesielt sink-, tinn-, eller titanholdige forbindelser, som f.eks. sinkacetat, dibutyltinnoksyd eller tetrabutyl-titanat. Mengden av katalysator utgjør fortrinnsvis 0,1 til 1,5 vekt-# av den samlede blandingen. The polycondensation reaction takes place at temperatures between 150 and 230°C, preferably between 160 and 210°C. As catalysts, organometallic compounds are preferably taken into consideration, especially zinc-, tin- or titanium-containing compounds, such as e.g. zinc acetate, dibutyltin oxide or tetrabutyl titanate. The amount of catalyst preferably amounts to 0.1 to 1.5% by weight of the total mixture.

De derved oppnådde polyesterpolyolene omsettes så med et delvis endeavsluttet polyisocyanat. Som polyisocyanater kommer alle kjente forbindelser av denne typen på tale, eksempelvis trimetylendiisocyanat, tetrametylendiisocyanat, pentametylendi-isocyanat, heksametylendiisocyanat, propylendiisocyanat, etylendiisocyanat, 2,3-dimetylendiisocyanat, 1-metyltrimetylen-diisocyanat, 1,3-cyklopentylendiisocyanat, 1,4-cykloheksylendiisocyanat, , 1,2-cykloheksylendiisocyanat, 1,3-fenylendiisocyanat, 1,4-fenylendiisocyanat, 2,4-toluylendiisocyanat, 2,6-toluylendiisocyanat, 4,4'-bifenylendiisocyanat, 1,5-naftylendiisocyanat, 1,4-naftylendiisocyanat, l-isocyanatometyl-5-isocyanato-1,3,3-trimetylcykloheksan, bis-(4-isocyanatocyklo-heksyl)metan, bis-(4-isocyanatocyklofenyl )-metan, 4,4'-diisocyanatodifenyleter, 2,3-bis-(8-isocyanatooktyl)-4-oktyl-5-heksylcykloheksen, tri- eller tetrametylxylylendiisocyanat eller blandinger av disse forbindelsene. The polyester polyols thus obtained are then reacted with a partially end-capped polyisocyanate. Polyisocyanates include all known compounds of this type, for example trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylene diisocyanate, 2,3-dimethyl diisocyanate, 1-methyltrimethylene diisocyanate, 1,3-cyclopentylene diisocyanate, 1,4-cyclohexylene diisocyanate. . , l-isocyanatomethyl-5-isocyanato-1,3,3-trimethylcyclohexane, bis-(4-isocyanatocyclohexyl)methane, bis-(4-isocyanatocyclophenyl)-methane, 4,4'-diisocyanatodiphenyl ether, 2,3-bis -(8-isocyanatooctyl)-4-octyl-5-hexylcyclohexene, tri- or tetramethylxylylene diisocyanate or mixtures of these compounds.

Ved siden av disse enkle polyisocyanatene er også slike egnede som inneholder heteroatomer i resten som knyttes sammen i isocyanatgruppene. Eksempler på dette er polyisocyanater som oppviser karbodiimidgrupper, allofanatgrupper, isocyanurat- grupper, uretangrupper, acylerte ureagrupper eller biuret-grupper. In addition to these simple polyisocyanates, those which contain heteroatoms in the residue which are linked together in the isocyanate groups are also suitable. Examples of this are polyisocyanates which have carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups, acylated urea groups or biuret groups.

Egnede polyisocyanater er endelig også slike høyere funksjonelle isocyanater som oppnås ved omsetning av et diisocyanat med en polyol (f.eks. trimetylolpropan, pentaerytrit), samt deres etoksylerte og/eller propoksylerte derivater med en alkoksyleringsgrad på 0,5 til 4,5 etylenoksyd og/eller propylenoksyd pr. hydroksylfunksjon. Finally, suitable polyisocyanates are those higher functional isocyanates which are obtained by reacting a diisocyanate with a polyol (e.g. trimethylolpropane, pentaerythritol), as well as their ethoxylated and/or propoxylated derivatives with a degree of alkoxylation of 0.5 to 4.5 ethylene oxide and /or propylene oxide per hydroxyl function.

Som endeavslutningsmiddel egner seg alifatiske, cykloalifatiske eller alkylaromatiske (enverdige) alkoholer, f.eks. lavere alifatiske alkoholer som metyl-, etylalkohol, de forskjellige propyl-, butyl- og heksylalkoholene, heptyl-, octyl-, nonyl-, decylalkohol o.l. Videre umettede alkoholer som propargyl-alkohol eller allylalkoholer, cykloalifatiske alkoholer som cyklopentanol, cykloheksanol, alkylaromatiske alkoholer som benzylalkohol, p-metyl-, p-metoksy- og p-nitrobenzylalkohol og monoeter av glykoler som etylenglykomonoetyleter, -monobuty-leter og lignende. Ytterligere avslutningsmidler er fenoler, ketoksimer, hensiktsmessig med 3 til 20 C-atomer, fortrinnsvis 3-10 C-atomer, som acetonoksim, metyletylketonoksim (=butanon-oksim), heksanonoksim (som metyl -butylketonoksim), heptanon-oksim (som metyl-n-amylketonoksim), oktanonoksim og cykloheksa-nonoksim, CH-sure forbindelser som malonsyrealkylester, aceteddikester samt cyaneddikester med i et hvert tilfelle 1 til 4 C-atomer i estergruppen, NH-sure forbindelser som kaprolaktam, aminoalkoholer som dietyletanolamin. Suitable terminating agents are aliphatic, cycloaliphatic or alkylaromatic (monovalent) alcohols, e.g. lower aliphatic alcohols such as methyl, ethyl alcohol, the various propyl, butyl and hexyl alcohols, heptyl, octyl, nonyl, decyl alcohol etc. Furthermore, unsaturated alcohols such as propargyl alcohol or allyl alcohols, cycloaliphatic alcohols such as cyclopentanol, cyclohexanol, alkylaromatic alcohols such as benzyl alcohol, p-methyl-, p-methoxy- and p-nitrobenzyl alcohol and monoethers of glycols such as ethylene glycomonoethyl ether, -monobutyl ether and the like. Further terminating agents are phenols, ketoximes, suitably with 3 to 20 C atoms, preferably 3-10 C atoms, such as acetone oxime, methyl ethyl ketone oxime (=butanone oxime), hexanone oxime (as methyl -butyl ketone oxime), heptanone oxime (as methyl- n-amylketonoxime), octanonoxime and cyclohexanoneoxime, CH-acidic compounds such as malonic acid alkyl esters, acetic acid esters and cyanoacetic acid esters with in each case 1 to 4 C atoms in the ester group, NH-acidic compounds such as caprolactam, amino alcohols such as diethylethanolamine.

Polyisocyantene omsettes ved i og for seg kjente fremgangsmåter med en slik mengde av endeavslutningsmiddelet at forholdet mellom frie isocyanatgrupper og endeavsluttede isocyantgrupper utgjør 1:4 til 1:0,5. The polyisocyanates are reacted by methods known per se with such an amount of the end capping agent that the ratio between free isocyanate groups and end-capped isocyanate groups amounts to 1:4 to 1:0.5.

Disse delvis endeavsluttede polyisocyanatene omsettes ved i og for seg kjente fremgangsmåter med den ovenfor omtalte polyesterpolyolen og nærmere bestemt i slikt forhold at sluttproduk- tet oppviser de innledningsvis definerte parametrene. Eventuelt tilstedeværende frie syregrupper nøytraliseres så avslutnings-vis helt eller delvis. For dette formålet tjener vandige oppløsninger av alkalihydroksider eller aminer, f.eks. trimetylamin, trietylamin, dimetylanilin, dietylanilin, trifenylamin, dimetyletanolamin, aminometylpropanol, dimetyl-isopropanolamin eller ammoniakk. These partially end-capped polyisocyanates are reacted by methods known per se with the above-mentioned polyester polyol and more specifically in such a ratio that the final product exhibits the parameters defined at the outset. Free acid groups that may be present are then completely or partially neutralized. For this purpose, aqueous solutions of alkali hydroxides or amines, e.g. trimethylamine, triethylamine, dimethylaniline, diethylaniline, triphenylamine, dimethylethanolamine, aminomethylpropanol, dimethylisopropanolamine or ammonia.

Dersom de relative reaktivitetene av polyesterpolyolen og endeavslutningsmiddelet overfor polyisocyanatet tillater det, "består også de to følgende fremgangsmåtemulighetene: til det med polyesterpolyolen anbrakte endeavslutnings middelet tilsetter man polyisocyanatet, eventuelt i nærvær av en katalysator, og kan deretter, ved tilsvarende selektivitet, også oppnå bindemiddelet ifølge oppfinnelsen . If the relative reactivities of the polyester polyol and the end capping agent towards the polyisocyanate allow it, "the following two process possibilities also exist: to the end capping agent placed with the polyester polyol to the agent, the polyisocyanate is added, possibly in the presence of a catalyst, and then, with corresponding selectivity, the binder according to the invention can also be obtained.

polyesterpolyolen omsettes, eventuelt i nærvær av en katalysator, med polyisocyanatet inntil bare de påkrevde frie OH-ekvivalentene foreligger. Til denne NCO-funksjonelle polymeren tilsetter man så endeavslutningsmiddelet og kan derved blokkere isocyanatgruppene for å oppnå bindemiddelet ifølge oppfinnelsen. the polyester polyol is reacted, optionally in the presence of a catalyst, with the polyisocyanate until only the required free OH equivalents are present. The end capping agent is then added to this NCO-functional polymer and can thereby block the isocyanate groups to obtain the binder according to the invention.

De vandige dispersjonene av bindemiddelet ifølge oppfinnelsen kan finne anvendelse for fremstilling av besjiktningssystemer, som bindemiddel for vannfortynnbare klebestoffer eller som harpikser for trykkfarger. The aqueous dispersions of the binder according to the invention can be used for the production of coating systems, as a binder for water-dilutable adhesives or as resins for printing inks.

De er eventuelt, ved tilsvarende forenlighet, kombinerbare med andre vandige kunststoffdispersjoner og/eller oppløsninger, f.eks. akryl- og/eller metakrylpolymerisater, polyuretan, polyurea-, polyester- samt epoksydharpikser, termoplaster på basis av polyvinylacetat, -vinylklorid, -vinyleter, - kloro-pren, -akrylnitril, etylen-butadien-styren-kopolymerisater. Bindemidlene ifølge oppfinnelsen kan påføres på de mest forskjelligartede substrater, f.eks. keramiske materialer, tre, glass, betong, fortrinnsvis plaster som polykarbonat, polystyren, polyvinylklorid, poyestere, poly(met)akrylater, akrylnitril-butadien-styren-polymerisater og lignende, samt likeledes fortrinnsvis metaller og legeringer som jern, kobber, aluminium, stål, tinn, sink, titan, magnesium, messing, bronse og lignende. They can optionally, if compatible, be combined with other aqueous plastic dispersions and/or solutions, e.g. acrylic and/or methacrylic polymers, polyurethane, polyurea, polyester and epoxy resins, thermoplastics based on polyvinyl acetate, vinyl chloride, vinyl ether, chloroprene, acrylonitrile, ethylene-butadiene-styrene copolymers. The binders according to the invention can be applied to the most diverse substrates, e.g. ceramic materials, wood, glass, concrete, preferably plastics such as polycarbonate, polystyrene, polyvinyl chloride, polyesters, poly(meth)acrylates, acrylonitrile-butadiene-styrene polymers and the like, as well as preferably metals and alloys such as iron, copper, aluminium, steel , tin, zinc, titanium, magnesium, brass, bronze and the like.

Bindemidlene ifølge oppfinnelsen er f.eks. egnede for fremstilling av lakkfilmer, overtrekk og/eller mellombesjiktninger for de mest forskjelligartede anvendelsesområder. Etter tilsats av vanlig lakkadditiver som flyt-, tverrbindings-, og disperge-ringshjelpemidler samt vanlige pigmentpreparater (Ti02, BaS04), egner de seg fremfor alt som vandige innbrennings-sletter-lakker, som - spesielt innenfor bilindustrien - påføres som mellomsjikt mellom grunning og dekklakk, hvorved det under forøvrig vanlige innbrenningsbetingelser innbrennes henholdsvis tørkes forsert ved 70 til 200°C, spesielt 100 til 180°C. Sammenlignet med på markedet anvendte vandige slettelakker utmerker de seg ved meget god stenslagsbeskyttelse, meget god fuktig varmebestandighet og meget gode optiske egenskaper (glans, overflatestruktur). The binders according to the invention are e.g. suitable for the production of varnish films, coatings and/or intermediate coatings for the most diverse areas of application. After the addition of common lacquer additives such as flow, cross-linking and dispersing aids as well as common pigment preparations (Ti02, BaSO4), they are above all suitable as aqueous burn-in erasers, which - especially in the automotive industry - are applied as an intermediate layer between primer and topcoat, whereby under otherwise normal firing conditions it is fired or forced dried at 70 to 200°C, especially 100 to 180°C. Compared to water-based erasing varnishes used on the market, they are distinguished by very good stone impact protection, very good damp heat resistance and very good optical properties (gloss, surface structure).

Foreliggende oppfinnelse vedrører følgelig også en bindemiddelblanding inneholdende et bindemiddel som omtalt ovenfor. Videre omfatter oppfinnelsen anvendelse av det omtalte bindemiddelet i besj iktningssystemer , anvendelse som innbrennings-sletterlakk for besjiktning av biler og anvendelse som innbrennings-dekklakk. The present invention therefore also relates to a binder mixture containing a binder as discussed above. Furthermore, the invention includes the use of the mentioned binder in coating systems, use as a burn-in clearcoat for coating cars and use as a burn-in top coat.

Selv om tilsatsen av en tverrbindingskomponent ikke er tvingende nødvendig ved sammensetningen av vannfortynnbare lakker med bindemidlene ifølge oppfinnelsen kan, ved gitt forenlighet, også ytterligere, innen lakkteknikken vanlige tverrbindingsmidler tilsettes, f.eks. vannoppløslige eller - emulgerbare melamin- eller benzoguanaminharpikser, vann emulgerbare polyisocyanater eller vannemulgerbare prepolymerer med. endestående isocyanatgrupper, vannoppløslige eller dispergerbare polyaziridiner og blokkerte polyisocyanater. Although the addition of a cross-linking component is not absolutely necessary in the composition of water-dilutable varnishes with the binders according to the invention, given compatibility, cross-linking agents common in lacquer technology can also be added, e.g. water-soluble or - emulsifiable melamine or benzoguanamine resins, water-emulsifiable polyisocyanates or water-emulsifiable prepolymers with. terminal isocyanate groups, water-soluble or dispersible polyaziridines and blocked polyisocyanates.

På grunn av den høye glansen kan det med bindemidlene ifølge oppfinnelsen ved valg av egnede pigmenter også oppnås en god dekklakk-kvalitet. En forutsetning er da riktignok anvendelsen av ikke gulnende polyisocyanater (f.eks. alifatiske isocyanater). Akselererte værpåkjenningstester viser meget gode resultater. Due to the high gloss, a good topcoat quality can also be achieved with the binders according to the invention by choosing suitable pigments. A prerequisite is the use of non-yellowing polyisocyanates (e.g. aliphatic isocyanates). Accelerated weather stress tests show very good results.

En spesiell fordel for bindemiddelet ifølge oppfinnelsen ligger i dets lagringsstabilitet (tabell 3). A particular advantage of the binder according to the invention lies in its storage stability (table 3).

Eksempler Examples

1. Polyester 1. Polyester

Fremstillingen av polyesterpolyolene foregår i en 4 liters-f irehalskolbe med ankerrører, ^-tilførsel, temperaturføler og en fyllegemekolonne (ca. 20 cm lengde, 3 cm diameter) med hodetermometer og nedadgående kjøler under ^-atmosfære. The production of the polyester polyols takes place in a 4 liter four-necked flask with anchor stirrer, ^ supply, temperature sensor and a packed column (approx. 20 cm length, 3 cm diameter) with head thermometer and descending cooler under a ^ atmosphere.

Polyester 1 Polyester 1

1241 g heksandiol (HD), 365 g neopentylglykol (NPG), 440 g trimetylolpropan (TMP), 312 g sulfoisoftalsyredimetylester-natriumsalt (5-SIP-DME-Na) og 3 g vannfritt sinkacetat kondenseres ved 170°C til 220°C og en maksimal topptemperatur på 65°C inntil 50 g destillat oppnås. Det avkjøles til 140°C, tilsettes 445 g tereftalsyre (TPS), 891 g isoftalsyre (IPS) og 2,6 g dibutyltinnoksyd (DBTO) og kondenseres ved 200°C inntil et innhold av karboksylgrupper på 26 mekv (COOH)/100 g er oppnådd. Det avkjøles til 140°C, tilsettes 706 g adipinsyre (ADPS) og kondenseres ved temperaturer på 165 til 220°C (maks. hodetemperatur 100°C) inntil et innhold av karboksylgrupper på 7 mekv (C00H)/100 g. 1241 g of hexanediol (HD), 365 g of neopentyl glycol (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 condensed at 170°C to 220°C and a maximum peak temperature of 65°C until 50 g of distillate is obtained. It is cooled to 140°C, 445 g of terephthalic acid (TPS), 891 g of isophthalic acid (IPS) and 2.6 g of dibutyltin oxide (DBTO) are added and condensed at 200°C until a content of carboxyl groups of 26 meq (COOH)/100 g has been achieved. It is cooled to 140°C, 706 g of adipic acid (ADPS) are added and condensed at temperatures of 165 to 220°C (max. head temperature 100°C) until a content of carboxyl groups of 7 meq (COOH)/100 g.

Polyester 2 Polyester 2

665 g heksandiol, 195 g neopentylglykol og 235 g trimetylolpropan smeltes, deretter tilsetter man ved 100°C 210 g teref tal syre og 1,2 g DBTO og kondenserer ved 220°C og en maksimal hodetemperatur på 100°C inntil det foreligger en klar smelte. Det avkjøles til 160°C, tilsettes 455 g isoftalsyre og ytterligere 1,2 g DBTO og kondenserer inntil et innhold av karboksylgrupper på 35 mekv (COOH)/100 g er oppnådd. Deretter avkjøles det til 130°C og 910 g adipinsyre samt 505 g dimetylolpropionsyre (DMPS) tilsettes og det kondenseres ved 160 til 200°C (maksimal hodetemperatur 100°C) inntil det er oppnådd en verdi på 90 mekv (C00E)/100 g. 665 g of hexanediol, 195 g of neopentyl glycol and 235 g of trimethylolpropane are melted, then 210 g of terephthalic acid and 1.2 g of DBTO are added at 100°C and condensed at 220°C and a maximum head temperature of 100°C until a clear melt. It is cooled to 160°C, 455 g of isophthalic acid and a further 1.2 g of DBTO are added and condensed until a content of carboxyl groups of 35 meq (COOH)/100 g is obtained. It is then cooled to 130°C and 910 g of adipic acid and 505 g of dimethylolpropionic acid (DMPS) are added and it is condensed at 160 to 200°C (maximum head temperature 100°C) until a value of 90 meq (C00E)/100 g is obtained .

Polyester 3 Polyester 3

500 g heksandiol, 520 neopentylglykol og 235 g trimetylolpropan smeltes og deretter tilsettes ved 100°C 300 g tereftalsyre, 450 g isoftalsyre og 2,5 g DBTO. Man kondenserer ved 190°C til 200°C inntil et innhold av karboksylgrupper på 14 mekv (COOE)/100 g, avkjøler til 140°C, tilsetter 900 g adipinsyre og kondenserer ved 190 til 200°C inntil en verdi på 133 mekv (COOH)/100 g. Deretter avkjøles det til 140°C, 300 g dimetylolpropionsyre tilsettes og det kondenseres ved 170 til 180°C (maksimal hodetemperatur 100°C) inntil et innhold av karboksylgrupper på 100 mekv (COOH)/100 g. 500 g of hexanediol, 520 g of neopentyl glycol and 235 g of trimethylolpropane are melted and then 300 g of terephthalic acid, 450 g of isophthalic acid and 2.5 g of DBTO are added at 100°C. It condenses at 190°C to 200°C until a content of carboxyl groups of 14 meq (COOE)/100 g, cools to 140°C, adds 900 g of adipic acid and condenses at 190 to 200°C until a value of 133 meq ( COOH)/100 g. It is then cooled to 140°C, 300 g of dimethylolpropionic acid is added and it is condensed at 170 to 180°C (maximum head temperature 100°C) until a content of carboxyl groups of 100 meq (COOH)/100 g.

Polyester 4 Polyester 4

500 g heksandiol, 400 g neopentylglykol og 350 g trimetylolpropan smeltes. Ved 100°C tilsetter man 300 g tereftalsyre, 450 g isoftalsyre og 2,5 g DBTO og kondenserer ved 190°C til 200°C inntil et innhold av karboksylgrupper på 7 mekv (COOE)/100 g. Man avkjøler til 140°C, tilsetter 900 g adipinsyre og 300 g dimetylolpropionsyre og kondenserer ved 160 til 170°C inntil et innhold av frie karboksylgrupper på 128 mekv (COOH)/100 g. Deretter avkjøles det til 140°C, et vakuum på 100 mbar pålegges inntil en verdi på 110 mekv (COOH)/100 g er oppnådd (ca. 30 min). 2. Selvtverrbindende - uretanmodifiert - bindemiddel (SUB) Syntesen av bindemiddelet ifølge oppfinnelsen foregår i en 2 liters- firehalskolbe med tilbakeløpskjøler og temperaturføler. 500 g of hexanediol, 400 g of neopentyl glycol and 350 g of trimethylolpropane are melted. At 100°C, 300 g of terephthalic acid, 450 g of isophthalic acid and 2.5 g of DBTO are added and condensed at 190°C to 200°C until a content of carboxyl groups of 7 meq (COOE)/100 g. It is cooled to 140°C , add 900 g of adipic acid and 300 g of dimethylolpropionic acid and condense at 160 to 170°C until a content of free carboxyl groups of 128 meq (COOH)/100 g. It is then cooled to 140°C, a vacuum of 100 mbar is applied until a value of 110 meq (COOH)/100 g is achieved (approx. 30 min). 2. Self-crosslinking - urethane-modified - binder (SUB) The synthesis of the binder according to the invention takes place in a 2 liter four-necked flask with reflux cooler and temperature sensor.

SUB 1 SUB 1

Til 43,2 g malonsyredietylester, 0,8 g natriummetylat og 74,0 g metyletylketon tilsettes i løpet av 7 min. 75,0 g difenyl-metan-4,4'-diisocyanat (MDI) og det omrøres under avkjøling ved 45°C inntil et NCO-innhold på 5,5 % er nådd. Deretter tilsetter man oppløsningen av 269,5 g polyester 1 i 92,5 g metyletylketon i løpet av 2 minutter, temperaturen heves til 50°C og det omrøres inntil NCO-innhold på < 0,1$. Etter den ytterligere fortynningen med 54,4 g butylglykol /isopropanol (vektforhold 3/1) dispergeres det med 675 g, til 50°C oppvarmet, avmineralisert vann. Ved 250 mbar og 60°C avdestilleres 170 g metyletylketon fra den vandige fasen. To 43.2 g of malonic acid diethyl ester, 0.8 g of sodium methylate and 74.0 g of methyl ethyl ketone are added over the course of 7 minutes. 75.0 g of diphenyl-methane-4,4'-diisocyanate (MDI) and it is stirred while cooling at 45°C until an NCO content of 5.5% is reached. The solution of 269.5 g of polyester 1 in 92.5 g of methyl ethyl ketone is then added over the course of 2 minutes, the temperature is raised to 50°C and the mixture is stirred until the NCO content is < 0.1$. After further dilution with 54.4 g of butyl glycol/isopropanol (weight ratio 3/1), it is dispersed with 675 g of demineralized water heated to 50°C. At 250 mbar and 60°C, 170 g of methyl ethyl ketone are distilled off from the aqueous phase.

SUB 2 SUB 2

Til 27,5 g metyletylketoksim (MEK-oksim), 0,4 g dibutyltinndilaurat (DBTDL) og 55,6 g metyletylketon tildoseres det i løpet av 2 minutter 66,6 g isoforondiisocyanat (IPDI) og det omrøres under avkjøling ved 35°C inntil det er oppnådd NCO-innhold på 8,5 %. Deretter tilsetter man oppløsningen av 294 g polyester 2 i 110 g metyletylketon i løpet av 3 minutter, hever temperaturen til 50°C og omrører inntil NCO-innhold på < 0,1 %. Etter den ytterligere fortynningen med 54,4 g butylglykol /isopropanol (vektforhold 3/1) nøytraliseres det med 20,0 g trietylamin (TEA) og deretter med 675 g , til 60°C oppvarmet avmineralisert vann. Ved 200 mbar og 60°C avdestilleres 170 g metyletylketon fra den vandig fasen. To 27.5 g of methyl ethyl ketoxime (MEK-oxime), 0.4 g of dibutyltin dilaurate (DBTDL) and 55.6 g of methyl ethyl ketone, 66.6 g of isophorone diisocyanate (IPDI) are dosed within 2 minutes and stirred while cooling at 35°C until an NCO content of 8.5% has been achieved. The solution of 294 g of polyester 2 in 110 g of methyl ethyl ketone is then added over the course of 3 minutes, the temperature is raised to 50°C and stirred until the NCO content is < 0.1%. After the further dilution with 54.4 g of butyl glycol/isopropanol (weight ratio 3/1), it is neutralized with 20.0 g of triethylamine (TEA) and then with 675 g of demineralized water heated to 60°C. At 200 mbar and 60°C, 170 g of methyl ethyl ketone are distilled off from the aqueous phase.

SUB 3 SUB 3

Til 1110 g isoforondiisocyanat og 0,75 g DBTL tilsetter man under avkjøling ved 25°C til 30°C, i løpet av et tidsrom på 75 minutter 435 g metyletylketoksim, forhøyer deretter temperaturen til 40°C og omrører i ytterligere 1 time. Man oppnår derved det halvsidig metyletylketoksimendesluttede isoforondiiso-cyanatet. 55 g n-metylpyrrolidon, 237,6 g polyester 3 og 186,9 g halvsidig endeavsluttet isoforondiisocyanat, som beskrevet tidligere, omrøres ved 60°C inntil det er oppnådd NCO-innhold på 0,4 %>. Deretter tilsetter man 21,1 g dimetyletanolamin DMEA), omrører nok en gang i 1 time ved 60°C og dispergerer med 715 g avmineralisert vann oppvarmet til 60°C. To 1110 g of isophorone diisocyanate and 0.75 g of DBTL, 435 g of methyl ethyl ketoxime are added during cooling at 25°C to 30°C over a period of 75 minutes, then the temperature is raised to 40°C and stirred for a further 1 hour. One thereby obtains the half-sided methyl ethyl oxime-terminated isophorone diisocyanate. 55 g of n-methylpyrrolidone, 237.6 g of polyester 3 and 186.9 g of half-sided end-capped isophorone diisocyanate, as described earlier, are stirred at 60°C until an NCO content of 0.4%> is achieved. 21.1 g of dimethylethanolamine (DMEA) are then added, stirred once more for 1 hour at 60°C and dispersed with 715 g of demineralized water heated to 60°C.

SUB 4 SUB 4

42,0 g n-metylpyrrolidon, 220.0 g polyester 4 og 92,0 g halvsidig, med metyletylketoksim , endeavsluttet isoforondiisocyanat omrøres ved 60°C inntil det er oppnådd NCO-innhold på 0.1 %. Deretter tilsetter man 21,6 g dimetyletylamin, omrører nok en gang i 1 time ved 60°C, og dispergerer med 460 g avmineralisert vann, oppvarmet til 60°C. 42.0 g of n-methylpyrrolidone, 220.0 g of polyester 4 and 92.0 g of half-sided, with methyl ethyl ketoxime, end-capped isophorone diisocyanate are stirred at 60°C until an NCO content of 0.1% is achieved. 21.6 g of dimethylethylamine are then added, stirred once more for 1 hour at 60°C, and dispersed with 460 g of demineralized water, heated to 60°C.

SUB 5 SUB 5

Til 1220 g tetrametylxylylendiisocyanat (TMXDI) og 0,75 g DBTL tilsetter man under avkjøling ved 25°C til 30°C, i løpet av et tidsrom på 75 minutter, 435 g metyletylketoksim, forhøyer deretter temperaturen til 40°C og omrører i ytterligere 1 time. Man oppnår derved det halvsidig metyletylketoksim-endeavsluttede TMXDI. To 1220 g of tetramethylxylylene diisocyanate (TMXDI) and 0.75 g of DBTL, 435 g of methyl ethyl ketoxime are added while cooling at 25°C to 30°C over a period of 75 minutes, then the temperature is raised to 40°C and stirred for a further 1 hour. One thereby obtains the half-sided methyl ethyl ketoxime-terminated TMXDI.

45,0 g n-metylpyrrolidon, 219,6 g polyester 4 og 102,2 g halvsidig med metyletylketoksim endeavsluttet tetrametyl-xylylendi isocyanat omrøres ved 60°C inntil det er oppnådd et NCO-innhold på 0.1 %. Deretter tilsetter men 36,2 g trietanol-amin (TOLA) , omrører nok en gang 1 time ved 60°C og dispergerer med 400 g avmineralisert vann, oppvarmet til 60°C. 45.0 g of n-methylpyrrolidone, 219.6 g of polyester 4 and 102.2 g of tetramethyl-xylylenedi isocyanate half-ended with methyl ethyl ketoxime are stirred at 60°C until an NCO content of 0.1% is achieved. Then add 36.2 g of triethanolamine (TOLA), stir again for 1 hour at 60°C and disperse with 400 g of demineralized water, heated to 60°C.

SUB 6 SUB 6

230,0 g polyester 4, 44,0 g N-metylpyrrolidon, 27,4 g metyletylketoksim samt 0,05 g dibutyltinndilaurat omrøres ved 35 - 40°C homogent og tilsettes 69,8 g isoforondiisocyanat på en 230.0 g of polyester 4, 44.0 g of N-methylpyrrolidone, 27.4 g of methyl ethyl ketoxime and 0.05 g of dibutyltin dilaurate are stirred homogeneously at 35 - 40°C and 69.8 g of isophorone diisocyanate are added to a

slik måte at temperaturen ikke overskrider 65°C. Man omrører ved 65°C inntil et NCO-innhold < 0.10 % er oppnådd. Deretter tilsetter man ved 65°C 22,6 g dimetyletanolamin, omrører 1 ytterligere time og dispergerer med 490 g avmineralisert vann, oppvarmet til 65°C. in such a way that the temperature does not exceed 65°C. Stir at 65°C until an NCO content < 0.10% is achieved. 22.6 g of dimethylethanolamine are then added at 65°C, stirred for a further hour and dispersed with 490 g of demineralized water, heated to 65°C.

Sammenligningseksempel: Comparison example:

119,0 g metyletylketoksim-endeavsluttet isoforondiisocyanat (omsetning av 1 mol isoforondiisocyanat med 2 mol metyletylketoksim i nærvær av 0,15 g dibutyltinndilaurat) omrøres med 42,0 g N-metylpyrrolidon og 220,0 g polyester 4 ved 6()°C til homogent, og blandes ved denne temperaturen med 21,6 g dimetyletanolamin. Man omrører en ytterligere time ved 60°C og dispergerer med 515,0 g avmineralisert vann, oppvarmet til 60°C. 3. Eksempel på en innbrennings-sletter-lakk på basis av SUB 119.0 g of methyl ethyl ketoxime-terminated isophorone diisocyanate (reaction of 1 mol of isophorone diisocyanate with 2 mol of methyl ethyl ketoxime in the presence of 0.15 g of dibutyltin dilaurate) is stirred with 42.0 g of N-methylpyrrolidone and 220.0 g of polyester 4 at 6()°C to homogeneously, and mixed at this temperature with 21.6 g of dimethylethanolamine. The mixture is stirred for a further hour at 60°C and dispersed with 515.0 g of demineralized water, heated to 60°C. 3. Example of a burn-in eraser varnish based on SUB

4 (fargetone lysegrå) 4 (tint light grey)

Resultater av undersøkelsene: kfr. tabell 4 Results of the surveys: see table 4

4. Eksempel på en vannfortynnbar dekklakk på basis av SUB 5 4. Example of a water-dilutable topcoat based on SUB 5

Resultater av undersøkelsen: kfr. tabell 4. Results of the survey: see table 4.

Undersøkelsesresultater av SUB 5 i Dekklakk Examination results of SUB 5 in Topcoat

Undersøkelse 1 totaloppbygning ( KTLVSletter/ dekklakk) Survey 1 total build-up (KTLVSlette/topcoat)

Claims (9)

1. Vannfortynnbart, uretanmodifisert og hydroksylgruppeholdig, selvtverrbindende enkomponent-bindemiddel,karakterisert vedat det er fremstilt ved omsetning av en polyester inneholdende hydroksylgrupper og nøytraliserte og/eller nøytraliserbare syregrupper og et delvis blokkert polyisocyanat, hvorved polyisocyanatet anvendes i slike mengder at hydroksylgruppeinnholdet i fastharpiksen utgjør 3 til 350 mmol/100 g, og blokkeringsgraden av isocyanatet velges slik at masseandelen av blokkerte isocyanatgrupper (beregnet som NCO, molar masse = 42 g/mol) i fastharpiksen utgjør mellom 0,5 og 15 vekt-#.1. Water-dilutable, urethane-modified and hydroxyl group-containing, self-crosslinking one-component binder, characterized in that it is produced by reacting a polyester containing hydroxyl groups and neutralized and/or neutralizable acid groups and a partially blocked polyisocyanate, whereby the polyisocyanate is used in such quantities that the hydroxyl group content in the solid resin amounts to 3 to 350 mmol/100 g, and the degree of blocking of the isocyanate is chosen so that the mass proportion of blocked isocyanate groups (calculated as NCO, molar mass = 42 g/mol) in the solid resin amounts to between 0.5 and 15 wt-#. 2. Bindemiddel ifølge krav 1,karakterisert vedat hydroksylgruppeinnholdet utgjør 5 til 170 mmol i 100 g fastharpiks.2. Binder according to claim 1, characterized in that the hydroxyl group content amounts to 5 to 170 mmol in 100 g of solid resin. 3. Bindemiddel ifølge minst ett av de foregående krav, karak terisert ved at masseandelen av uretangrupper i fastharpiks (beregnet som NH-C(0)0-, molar masse = 59 g/mol) utgjør mellom 0,5 og 20 vekt-#.3. Binder according to at least one of the preceding claims, karak terized in that the mass proportion of urethane groups in solid resin (calculated as NH-C(0)0-, molar mass = 59 g/mol) is between 0.5 and 20 wt-#. 4. Bindemiddel ifølge minst ett av de foregående krav, karak terisert ved at det inneholder nøytraliserbare og/eller nøytraliserte karboksylsyre- og/eller sulfonsyre-og/eller fosfonsyregrupper.4. Binder according to at least one of the preceding claims, karak characterized in that it contains neutralizable and/or neutralized carboxylic acid and/or sulfonic acid and/or phosphonic acid groups. 5. Bindemiddel ifølge krav 4,karakterisert vedat summen av mengdene av nøytraliserte og nøytraliserbare syregrupper ligger mellom 5 og 200 mmol pr. 100 g fastharpiks.5. Binder according to claim 4, characterized in that the sum of the amounts of neutralized and neutralizable acid groups is between 5 and 200 mmol per 100 g solid resin. 6. Bindemiddelblanding,karakterisert vedat den inneholder et bindemiddel ifølge krav 1.6. Binder mixture, characterized in that it contains a binder according to claim 1. 7. Anvendelse av bindemiddel ifølge krav 6 i besjiktningssystemer.7. Use of binder according to claim 6 in coating systems. 8. Anvendelse av bindemiddel ifølge krav 6 som innbrennings-slettelakk for besjiktning av biler.8. Use of a binder according to claim 6 as burn-in erasing lacquer for coating cars. 9. Anvendelse av bindemiddel ifølge krav 6 som innbrennings-dekklakk.9. Use of a binder according to claim 6 as a burn-in topcoat.
NO924923A 1991-12-21 1992-12-18 Water-dilutable, urethane-modified and hydroxyl group-containing, self-crosslinking one-component binder, binder composition comprising this and the use thereof NO302034B1 (en)

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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
DE10031987A1 (en) * 2000-06-30 2002-01-24 Basf Coatings Ag Propargyl alcohol blocked polyisocyanates, process for their preparation and their use
DE10145344A1 (en) * 2001-09-14 2003-04-24 Audi Ag Process for producing a multi-layer coating of a vehicle body and coating material
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EP2370490B1 (en) * 2008-11-26 2018-07-18 Valspar Sourcing, Inc. Coating compositions comprising a polyester polymer
US8367171B2 (en) 2008-11-26 2013-02-05 Valspar Sourcing, Inc. Polymer having polycyclic groups and coating compositions thereof
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ATE164604T1 (en) 1998-04-15
ZA929812B (en) 1993-06-23
CA2084737A1 (en) 1993-06-22
EP0548727A2 (en) 1993-06-30
NO924923D0 (en) 1992-12-18
AU654600B2 (en) 1994-11-10
DE4142734A1 (en) 1993-06-24
NO924923L (en) 1993-06-22
EP0548727A3 (en) 1993-09-01
JP3293914B2 (en) 2002-06-17
EP0548727B1 (en) 1998-04-01
AU3021192A (en) 1993-06-24
MX9207460A (en) 1993-06-01
ES2114546T3 (en) 1998-06-01

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