EP1409565A1 - Aqueous and/or water-dilutable polyisocyanate cross-linking agents which are blocked by a diisopropylamine, and the use of said agents - Google Patents

Aqueous and/or water-dilutable polyisocyanate cross-linking agents which are blocked by a diisopropylamine, and the use of said agents

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Publication number
EP1409565A1
EP1409565A1 EP02784829A EP02784829A EP1409565A1 EP 1409565 A1 EP1409565 A1 EP 1409565A1 EP 02784829 A EP02784829 A EP 02784829A EP 02784829 A EP02784829 A EP 02784829A EP 1409565 A1 EP1409565 A1 EP 1409565A1
Authority
EP
European Patent Office
Prior art keywords
water
blocked
aqueous
diisopropylamine
polyisocyanate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02784829A
Other languages
German (de)
French (fr)
Inventor
Eberhard König
Jan Mazanek
Heino Müller
Joachim Petzoldt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Bayer MaterialScience AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Publication of EP1409565A1 publication Critical patent/EP1409565A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C08G18/808—Monoamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3275—Hydroxyamines containing two hydroxy 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8048—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/34
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Definitions

  • the invention relates to aqueous and / or water-dilutable polyisocyanate crosslinking agents blocked with diisopropylamine, their preparation and use in one-component stoving lacquers, e.g. as a filler in automotive painting.
  • isocyanate blocking agents that meet these requirements. Butanone oxime is such a blocking agent, but it needs baking conditions of at least 30 minutes / 140 ° C to ensure the crosslinking of the blocked polyisocyanate.
  • 3,5-Dimethylpyrazole is also a suitable blocking agent and already leads to crosslinking of the blocked polyisocyanate under baking conditions of 30 minutes / 130 ° C, e.g. is discussed in patent applications WO97 / 12924 and EP-A 0942 023.
  • the disadvantage of 3,5-dimethylpyrazole is its relatively complex preparation. 3,5-Dimethylpyrazole is accessible on an industrial scale by condensation of acetylacetone and hydrazine hydrate, which is due to e.g. the properties of hydrazine hydrate is complex.
  • a readily accessible isocyanate blocking agent is diisopropylamine. From the patent literature it is known that it is used in powder coatings and coil coating coatings, see EP-A 0096 210 and EP-A 900814. It has surprisingly been found that polyisocyanates blocked with diisopropylamine are stable in storage in the aqueous phase and do not continuously secrete CO 2 , as is the case for example with polyisocyanates blocked with diethyl malonate or 1,2,4-triazole.
  • the object of the invention is to provide storage-stable and easily accessible aqueous or water-dilutable blocked polyisocyanate crosslinkers with a lower crosslinking or baking temperature than butanone oxime-blocked polyisocyanate crosslinkers.
  • the invention relates to aqueous and / or water-dilutable blocked polyisocyanate crosslinkers
  • the proportions of the reactants being chosen so that the equivalent ratio of NCO groups of component a) to isocyanate-reactive groups of components b), c), and d) is from 1: 0.8 to 1: 1.2 lies, and optionally additives and auxiliaries.
  • the invention also relates to a process for the preparation of the blocked aqueous and / or water-dilutable polyisocyanate crosslinking agent, characterized in that the polyisocyanate component a) and optionally 30% by weight, moved to the delivery form of the blocked polyisocyanate crosslinker, a water-miscible solvent, are reacted in a first reaction stage at approx. 80 ° C with the monohydroxycarboxylic acid intended for hydrophilization, then cooled to approx. 50 ° C and the remaining NCO- Groups can be blocked by adding diisopropylamine.
  • the blocked aqueous / water-dilutable polyisocyanate crosslinker according to the invention can be prepared in stages, e.g. the polyisocyanate component a) and optionally 30% by weight, based on the delivery form of the crosslinking agent, of a water-miscible solvent, e.g. N-methylpyrrolidone, are introduced and reacted in a first reaction stage at about 80 ° C. with the monohydroxycarboxylic acid provided for the hydrophilization. The mixture is then cooled to about 50 ° C. and the remaining NCO groups, about 80%, are completely reacted with diisopropylamine.
  • a water-miscible solvent e.g. N-methylpyrrolidone
  • the hydrophilization is to be achieved with a dihydroxycarboxylic acid or a mixture of di- and monohydroxycarboxylic acid, e.g. conversely, the blocking reaction with diisopropylamine is carried out first at approx. 40-70 ° C; the remaining NCO groups are then used to react with the hydrophilization component. In this way, the formation of networked
  • tertiary amine for example dimethylethanolamine
  • the carboxylic acid groups are converted into hydrophilic carboxylate anions.
  • a water-dilutable blocked polyisocyanate crosslinker with approx. 65% solids content and a viscosity (at 23 ° C) of approx. 10,000 mPas, for example by adding further water-miscible solvent or by adding water to a water-dispersed blocked crosslinker with approx 30% solids content and a viscosity (at 23 ° C) of approx. 400 mPas.
  • the invention also relates to the use of the aqueous and / or water-dilutable blocked polyisocyanate crosslinking agent according to the invention in combination with water-soluble and / or dispersible polyhydroxy compounds for the preparation of aqueous stoving lacquers which optionally contain the conventional auxiliaries and additives of coating technology , They are preferably used in automotive painting.
  • the polyisocyanates a) on which the blocked polyisocyanates according to the invention are based are lacquer polyisocyanates known per se with aliphatic and / or cycloaliphatic isocyanate groups and an isocyanate content of 7 to 30, preferably 12 to 25,% by weight.
  • HDI 1,6-diisocyanatohexane
  • LPDI 1-isocyanato-3,3, 5-trimethyl-5-isocyanatomethyl-cyclohexane
  • H 12 MDI bis- (4-isocyanatocyclohexyl) methane
  • polyisocyanates or short-chain NCO prepolymers based on aromatic diisocyanates such as, for example, diisocyanatotoluene (TDI) or 4,4-diisocyanatodiphenylmethane (MDI).
  • TDI diisocyanatotoluene
  • MDI 4,4-diisocyanatodiphenylmethane
  • component a Particularly preferred as component a), however, are polyisocyanates based on HDI or H 12 MDI and containing isocyanurate groups.
  • Diisopropylamine is suitable according to the invention as a blocking agent from the series of secondary amines. Under the technically required baking conditions of 130 ° C / 30 minutes, it is substituted or deblocked and blocked in aqueous varnishes, just like butanone oxime or 3,5-dimethylpyrazole, isocyanate groups without the release of CO 2 as a result of hydrolysis. Monohydroxy- and di-hydroxycarboxylic acids which carry one or two ⁇ -methyl groups are preferred as the hydrophilization component c). Hydroxypivalic acid (hydroxymethyldimethylacetic acid) and mixtures of hydroxypivalic acid with dimethylolpropionic acid are particularly preferred.
  • Suitable difunctional chain extension components d) are diamines, diols and also hydroxyamines in the molecular weight range from 32 to 300.
  • Examples are hydrazine, ethylenediamine, isophoronediamine, the bisketimine from isophorondiamine and methyl isobutyl ketone, 1,4-dihydroxybutane, ethanolamine, N-methylethanolamine, hydroxyethylethylenediamine, the adduct of 2 mol propylene carbonate and 1 mol hydrazine of the formula (I)
  • Suitable neutralizing agents are e.g. Dimethylethanolamine, methyldiethanolamin, triethylamine, N-methylmo holin or 2-amino-2-methylpropanol.
  • stabilizers e.g. Hydrazides and HALS amines (hindered amines
  • Light Stabilizers of the type Tinuvin® 770 DF. Additives and other auxiliaries can also be added.
  • crosslinking agents according to the invention can either be up to 80% pure in a water-dilutable solvent or up to 50% pure mainly in water
  • water-dilutable solvents e.g. Butyl diglycol acetate, butly diglycol, N-methylpyrrolidone, or any mixture thereof.
  • the polyisocyanate crosslinkers according to the invention have the following advantages:
  • the crosslinkers and the aqueous stoving enamels formulated with them are stable on storage for at least 3 months.
  • the blocking agent diisopropylamine is an inexpensive industrial chemical.
  • the baking temperature of the aqueous varnish is 30 minutes / 130 ° C and thus 10 ° C lower than that of a butanone oxime-blocked crosslinker.
  • NCO content of 21.4% by weight, a viscosity at 23 ° C of approx. 3000 mPas and a functionality of approx. 3.5
  • Polyisocyanate, N-methylpyrrolidone and hydroxypivalic acid are heated at intervals to 80 ° C. with stirring. At this temperature, stirring is continued for about 2 hours until the NCO content has dropped to about 9.1%. Then leave on approx.
  • Polyisocyanate is introduced and stirred. To do this, carefully drop diisopropylamine starting from room temperature. The implementation is exothermic, whereby keeping the temperature at 70 ° C. The addition of diisopropylamine is complete after about 1 hour.
  • the solution of hydroxypivalic acid, dimethylolpropionic acid and N-methylpyrrolidone is added, the mixture is heated to 80 ° C. and stirred at this temperature for about 2 hours until NCO groups are no longer detectable by IR spectroscopy. Thereafter, the supply of heat is stopped, dimethylethanolamine is added, the mixture is stirred for a further 10 minutes and water, at 50 ° C., is stirred. A dispersion is formed, which is stirred at about 50 ° C for 3 hours. The mixture is then cooled to room temperature with stirring and stirring is continued for 3 hours.
  • the dispersed blocked polyisocyanate crosslinker has the above characteristics.
  • This crosslinker blocked with butanone oxime is constructed analogously to that described in Example 2. It is characterized as follows:
  • Solids content 41% viscosity at 23 ° C: approx. 5700 mPas Blocked NCO content: 3.9
  • the paint components in the overview above are mixed intimately using a stirrer.
  • the OH components and the blocked crosslinkers are metered in an equivalent ratio of 1: 1.
  • the addition of melamine resin improves the smooth surface quality.
  • the three above lacquers are applied to the following substrates in a resulting dry film thickness of 25-35 ⁇ m using a flow cup spray gun with a nozzle (diameter 1.5 mm) and an atomizing pressure of 5 bar.
  • the wet paint films are flashed off at 23 ° C. for 5 minutes and then baked in a forced air oven.
  • the substrates are glass plates, in the case of adhesion / cross cut, Erichsen cupping and salt spray test, degreased steel sheets:
  • Pendulum hardness Vibration test according to König DIN 53 157
  • lacquers 1 and 2 with the crosslinkers according to the invention are more reactive than lacquer 3 with the butanone oxime-blocked polyisocyanate crosslinker.
  • the higher reactivity which is based on the blocking agent diisopropylamine, is evident from the higher paint hardness, the better resistance to solvents and the improved corrosion resistance (less paint infiltration of the salt solution).

Abstract

The invention relates to aqueous and/or water-dilutable polyisocyancate cross-linking agents which are blocked by a diisopropylamine, to the production thereof, and to the use of the same in single-component stove enamel, e.g. as a filler in car paint.

Description

Wässrige und/oder λvasserverdünnbare mit Diisopropylamin blockierte Poly- isocyanat- Vernetzer und deren VerwendungAqueous and / or water-dilutable polyisocyanate crosslinking agents blocked with diisopropylamine and their use
Die Erfindung betrifft wässrige und/oder wasserverdünnbare, mit Diisopropylamin blockierte Polyisocyanat-Vemetzer, deren Herstellung und Verwendung in Einkomponenten-Einbrennlacken, z.B. als Füller in der Automobillackierung.The invention relates to aqueous and / or water-dilutable polyisocyanate crosslinking agents blocked with diisopropylamine, their preparation and use in one-component stoving lacquers, e.g. as a filler in automotive painting.
Die Formulierung von blockierten Polyisocyanatvernetzern und ggf. Melamin-For- maldehyd-Harzen mit beispielsweise Hydroxylgruppen enthaltenden Polyacrylaten zu sogenannten „Einkomponenten"-Einbrennlacken gehört zum Stand der Technik. Handelt es sich dabei um wässrige Lacke, so müssen die genannten Einzelkomponenten wasserdispergierbar und mindestens 6 Monate in der wässrigen Phase lagerstabil sein.The formulation of blocked polyisocyanate crosslinking agents and, where appropriate, melamine-formaldehyde resins with, for example, hydroxyl group-containing polyacrylates to form “one-component” stoving lacquers is part of the prior art. If these are aqueous lacquers, the individual components mentioned must be water-dispersible and at least 6 Stable for months in the aqueous phase.
Es gibt nur wenige Isocyanat-Blockierungsmittel, die diese Anforderungen erfüllen. Butanonoxim ist ein solches Blockierungsmittel, aber es benötigt Einbrennbedingungen von mindestens 30 Minuten/140°C, um die Vernetzung des damit blockierten Polyisocyanates zu gewährleisten. Auch 3,5-Dimethylpyrazol ist ein geeignetes Blo- ckierungsmittel und fuhrt bereits zur Vernetzung des damit blockierten Polyisocyanates bei Einbrennbedingungen von 30 Minuten/130°C, wie z.B. in den Patentanmeldungen WO97/12924 und EP-A 0942 023 erörtert wird. Der Nachteil von 3,5-Di- methylpyrazol ist seine relativ aufwendige Herstellung. 3,5-Dimethylpyrazol ist im technischen Maßstab durch Kondensation von Acetylaceton und Hydrazinhydrat zugänglich, was aufgrund z.B. der Eigenschaften von Hydrazinhydrat aufwendig ist.There are few isocyanate blocking agents that meet these requirements. Butanone oxime is such a blocking agent, but it needs baking conditions of at least 30 minutes / 140 ° C to ensure the crosslinking of the blocked polyisocyanate. 3,5-Dimethylpyrazole is also a suitable blocking agent and already leads to crosslinking of the blocked polyisocyanate under baking conditions of 30 minutes / 130 ° C, e.g. is discussed in patent applications WO97 / 12924 and EP-A 0942 023. The disadvantage of 3,5-dimethylpyrazole is its relatively complex preparation. 3,5-Dimethylpyrazole is accessible on an industrial scale by condensation of acetylacetone and hydrazine hydrate, which is due to e.g. the properties of hydrazine hydrate is complex.
Ein gut zugängliches Isocyanatblockierungsmittel stellt Diisopropylamin dar. Aus der Patentliteratur ist bekannt, dass es bei Pulverlacken und Coil Coating-Lacken eingesetzt wird, vergl. EP-A 0096 210 und EP-A 900814. Überraschend wurde gefunden, dass mit Diisopropylamin blockierte Polyisocyanate in wässriger Phase lagerstabil sind und nicht etwa, wie dies beispielsweise bei mit Malonsäurediethylester oder 1,2,4-Triazol blockierten Polyisocyanaten der Fall ist, ständig CO2 absondern.A readily accessible isocyanate blocking agent is diisopropylamine. From the patent literature it is known that it is used in powder coatings and coil coating coatings, see EP-A 0096 210 and EP-A 900814. It has surprisingly been found that polyisocyanates blocked with diisopropylamine are stable in storage in the aqueous phase and do not continuously secrete CO 2 , as is the case for example with polyisocyanates blocked with diethyl malonate or 1,2,4-triazole.
Aufgabe der Erfindung ist es, lagerstabile und einfach zugängliche wässrige bzw. wasserverdünnbare blockierte Polyisocyanat-Vemetzer mit einer niedrigeren Vernet- zungs- bzw. Einbrenntemperatur als butanonoximblockierte Polyisocyanat- Vernetzer zur Verfügung zu stellen.The object of the invention is to provide storage-stable and easily accessible aqueous or water-dilutable blocked polyisocyanate crosslinkers with a lower crosslinking or baking temperature than butanone oxime-blocked polyisocyanate crosslinkers.
Diese Aufgabe wurde mit den erfindungsgemäßen blockierten wässrigen/wasserver- dünnbaren Polyisocyanat- Vernetzern gelöst.This object was achieved with the blocked aqueous / water-dilutable polyisocyanate crosslinking agents according to the invention.
Gegenstand der Erfindung sind wässrige und/oder wasserverdünnbare blockierte Polyisocyanat-Vemetzer ausThe invention relates to aqueous and / or water-dilutable blocked polyisocyanate crosslinkers
a) 100 Äquivalent-% einer Polyisocyanatkomponente, b) 50-85 Äquivalent-% an Diisopropylamin, c) 15-40 Äquivalent-% einer Monohydroxy- und/oder einer Dihydroxycarbonsäure als Hydrophilierungsmittel und gegebenenfalls d) 0-15 Äquivalent-% einer difunktionellen, HO- und/oder NH2-Gruppen tragenden Kettenverlängerungskomponente,a) 100 equivalent% of a polyisocyanate component, b) 50-85 equivalent% of diisopropylamine, c) 15-40 equivalent% of a monohydroxy- and / or a dihydroxycarboxylic acid as a hydrophilizing agent and optionally d) 0-15 equivalent% of a difunctional , HO and / or NH 2 group-carrying chain extension component,
wobei die Mengenverhältnisse der Reaktionspartner so gewählt werden, dass das Äquivalentverhältnis von NCO-Gruppen der Komponente a) zu gegenüber Isocya- naten reaktionsfähigen Gruppen der Komponenten b), c), und d) bei 1:0,8 bis 1:1,2 liegt, sowie gegebenenfalls Zuschlagstoffe und Hilfsstoffe.the proportions of the reactants being chosen so that the equivalent ratio of NCO groups of component a) to isocyanate-reactive groups of components b), c), and d) is from 1: 0.8 to 1: 1.2 lies, and optionally additives and auxiliaries.
Gegenstand der Erfindung ist auch ein Verfahren zur Herstellung der blockierten wässrigen und/oder wasserverdünnbaren Polyisocyanat-Vemetzer, dadurch gekennzeichnet, dass die Polyisocyanatkomponente a) und gegebenenfalls 30 Gew.-%, be- zogen auf die Lieferform des blockierten Polyisocyanat-Vemetzers, eines wassermischbaren Lösemittels vorgelegt werden, in einer ersten Reaktionsstufe bei ca. 80°C mit der für die Hydrophilierung vorgesehenen Monohydroxycarbonsäure umgesetzt wird, anschließend auf ca. 50°C abgekühlt wird und die verbleibenden NCO-Gruppen durch Zugabe von Diisopropylamin blockiert werden.The invention also relates to a process for the preparation of the blocked aqueous and / or water-dilutable polyisocyanate crosslinking agent, characterized in that the polyisocyanate component a) and optionally 30% by weight, moved to the delivery form of the blocked polyisocyanate crosslinker, a water-miscible solvent, are reacted in a first reaction stage at approx. 80 ° C with the monohydroxycarboxylic acid intended for hydrophilization, then cooled to approx. 50 ° C and the remaining NCO- Groups can be blocked by adding diisopropylamine.
Die Herstellung der erfindungsgemäßen blockierten wässrigen/wasserverdünnbaren Polyisocyanat-Vemetzer kann stufenweise erfolgen, wobei z.B. die Polyisocyanatkomponente a) und gegebenenfalls 30 Gew.-%, bezogen auf die Lieferform des Ver- netzers, eines wassermischbaren Lösemittels, z.B. N-Methylpyrrolidon, vorgelegt werden und in einer ersten Reaktionsstufe bei ca. 80°C mit der für die Hydrophilierung vorgesehenen Monohydroxycarbonsäure umgesetzt wird. Danach kühlt man auf ca. 50°C ab und setzt die verbleibenden NCO-Gruppen, ca. 80 %, mit Diisopropylamin vollständig um.The blocked aqueous / water-dilutable polyisocyanate crosslinker according to the invention can be prepared in stages, e.g. the polyisocyanate component a) and optionally 30% by weight, based on the delivery form of the crosslinking agent, of a water-miscible solvent, e.g. N-methylpyrrolidone, are introduced and reacted in a first reaction stage at about 80 ° C. with the monohydroxycarboxylic acid provided for the hydrophilization. The mixture is then cooled to about 50 ° C. and the remaining NCO groups, about 80%, are completely reacted with diisopropylamine.
Soll die Hydrophilierung mit einer Dihydroxycarbonsäure bzw. einem Gemisch aus Di- und Monohydroxycarbonsäure erreicht werden, so kann z.B. umgekehrt zuerst die Blockierungsreaktion mit Diisopropylamin bei ca. 40-70°C vorgenommen werden; danach erfolgt mit den restlichen NCO-Gruppen die Umsetzung mit der Hydrophilierungskomponente. Auf diese Weise kann die Bildung von vernetztenIf the hydrophilization is to be achieved with a dihydroxycarboxylic acid or a mixture of di- and monohydroxycarboxylic acid, e.g. conversely, the blocking reaction with diisopropylamine is carried out first at approx. 40-70 ° C; the remaining NCO groups are then used to react with the hydrophilization component. In this way, the formation of networked
Gelteilchen vermieden werden.Gel particles can be avoided.
Nach der Zugabe des neutralisierenden, tertiären Amins, z.B. Dimethylethanolamin, verwandeln sich die Carbonsäuregruppen in hydrophile Carboxylatanionen. Man hat jetzt die Möglichkeit z.B. durch Zugabe von weiterem wassermischbarem Lösemittel einen wasserverdünnbaren blockierten Polyisocyanat-Vemetzer mit ca. 65 % Festkörpergehalt und einer Viskosität (bei 23°C) von ca. 10 000 mPas oder durch Zugabe von Wasser einen wasserdispergierten blockierten Vemetzer mit ca. 30 % Festkörpergehalt und einer Viskosität (bei 23°C) von ca. 400 mPas herzustellen. Gegenstand der Erfindung ist auch die Verwendung der erfindungsgemäßen wäs- srigen und/oder wasserverdünnbaren blockierten Polyisocyanat-Vemetzer in Kombination mit in Wasser löslichen und/oder dispergierbaren Polyhydroxylverbindungen zur Herstellung von, gegebenenfalls die üblichen Hilfs- und Zusatzmittel der Be- schichtungstechnologie enthaltenden, wässrigen Einbrennlacken. Vorzugsweise finden sie in der Automobillackierung Einsatz.After the neutralizing, tertiary amine, for example dimethylethanolamine, has been added, the carboxylic acid groups are converted into hydrophilic carboxylate anions. It is now possible to add a water-dilutable blocked polyisocyanate crosslinker with approx. 65% solids content and a viscosity (at 23 ° C) of approx. 10,000 mPas, for example by adding further water-miscible solvent or by adding water to a water-dispersed blocked crosslinker with approx 30% solids content and a viscosity (at 23 ° C) of approx. 400 mPas. The invention also relates to the use of the aqueous and / or water-dilutable blocked polyisocyanate crosslinking agent according to the invention in combination with water-soluble and / or dispersible polyhydroxy compounds for the preparation of aqueous stoving lacquers which optionally contain the conventional auxiliaries and additives of coating technology , They are preferably used in automotive painting.
Bei den, den erfindungsgemäß blockierten Polyisocyanaten zugrundeliegenden Poly- isocyanaten a), handelt es sich um an sich bekannte Lackpolyisocyanate mit alipha- tisch und/oder cycloaliphatisch gebundenen Isocyanatgruppen und einem Isocyanat- gehalt von 7 bis 30, vorzugsweise 12 bis 25 Gew.-%. In Betracht kommen insbesondere die an sich bekannten Biuret-, Isocyanurat-, Aminooxadiazindion (asymmetrische Trimerisat-)-, Urethan- und/oder Uretdiongruppen aufweisenden Lackpolyisocyanate auf Basis von 1,6-Diisocyanatohexan (HDI), 1- Isocyanato-3,3,5-tri- methyl-5-isocyanatomethyl-cyclohexan (LPDI) und/oder Bis-(4-isocyanatocyclohe- xyl)-methan (H12MDI). Ebenso können beliebige Prepolymere aus diesen Polyisocyanaten und diversen Polyolen, wie Polyestern, Polyethem, Polyacrylaten bzw. deren Gemischen, eingesetzt werden.The polyisocyanates a) on which the blocked polyisocyanates according to the invention are based are lacquer polyisocyanates known per se with aliphatic and / or cycloaliphatic isocyanate groups and an isocyanate content of 7 to 30, preferably 12 to 25,% by weight. , In particular, the well-known biuret, isocyanurate, aminooxadiazinedione (asymmetric trimer) -, urethane and / or uretdione-containing lacquer polyisocyanates based on 1,6-diisocyanatohexane (HDI), 1-isocyanato-3,3, 5-trimethyl-5-isocyanatomethyl-cyclohexane (LPDI) and / or bis- (4-isocyanatocyclohexyl) methane (H 12 MDI). Any prepolymers made from these polyisocyanates and various polyols, such as polyesters, polyethers, polyacrylates or mixtures thereof, can also be used.
Weiterhin können auch Polyisocyanate oder kurzkettige NCO-Prepolymere auf Basis von aromatischen Diisocyanaten, wie beispielsweise Dusocyanatotoluol (TDI) oder 4,4-Diisocyanatodiphenylmethan (MDI) eingesetzt werden.It is also possible to use polyisocyanates or short-chain NCO prepolymers based on aromatic diisocyanates, such as, for example, diisocyanatotoluene (TDI) or 4,4-diisocyanatodiphenylmethane (MDI).
Besonders bevorzugt als Komponente a) sind jedoch Isocyanuratgruppen aufwei- sende Polyisocyanate auf Basis von HDI oder H12MDI.Particularly preferred as component a), however, are polyisocyanates based on HDI or H 12 MDI and containing isocyanurate groups.
Als Blockierungsmittel aus der Reihe der sekundären Amine eignet sich erfindungsgemäß Diisopropylamin. Unter den technisch geforderten Einbrennbedingungen von 130°C/30 Minuten wird es substituiert bzw. deblockiert und blockiert in wässrigen Lacken, ebenso wie Butanonoxim oder 3,5-Dimethylpyrazol, Isocyanatgruppen stabil, ohne dass infolge Hydrolyse CO2 freigesetzt wird. Als Hydrophilierungskomponente c) kommen vorzugsweise Monohydroxy- und Di- hydroxycarbonsäuren in Betracht, die eine oder zwei α-ständige Methylgruppen tragen. Besonders bevorzugt ist Hydroxypivalinsäure (Hydroxymethyldimethylessig- säure) und Gemische aus Hydroxypivalinsäure mit Dimethylolpropionsäure.Diisopropylamine is suitable according to the invention as a blocking agent from the series of secondary amines. Under the technically required baking conditions of 130 ° C / 30 minutes, it is substituted or deblocked and blocked in aqueous varnishes, just like butanone oxime or 3,5-dimethylpyrazole, isocyanate groups without the release of CO 2 as a result of hydrolysis. Monohydroxy- and di-hydroxycarboxylic acids which carry one or two α-methyl groups are preferred as the hydrophilization component c). Hydroxypivalic acid (hydroxymethyldimethylacetic acid) and mixtures of hydroxypivalic acid with dimethylolpropionic acid are particularly preferred.
Als difunktionelle Kettenverlängerungskomponente d) kommen Diamine, Diole und auch Hydroxyamine im Molekulargewichtsbereich von 32 bis 300 in Betracht. Beispiele sind Hydrazin, Ethylendiamin, Isophorondiamin, das Bisketimin aus Isopho- rondiamin und Methylisobutylketon, 1,4-Dihydroxybutan, Ethanolamin, N-Methy- lethanolamin, Hydroxyethylethylendiamin, das Addukt von 2 mol Propylencarbonat und 1 mol Hydrazin der Formel (I)Suitable difunctional chain extension components d) are diamines, diols and also hydroxyamines in the molecular weight range from 32 to 300. Examples are hydrazine, ethylenediamine, isophoronediamine, the bisketimine from isophorondiamine and methyl isobutyl ketone, 1,4-dihydroxybutane, ethanolamine, N-methylethanolamine, hydroxyethylethylenediamine, the adduct of 2 mol propylene carbonate and 1 mol hydrazine of the formula (I)
CH, O O CH,CH, O O CH,
I 3 II II I (T)I 3 II II I (T)
HO-CH CH2 O— C— NH NH C— O CH2 CH OH w> HO-CH CH 2 O— C— NH NH C— O CH 2 CH OH w>
Geeignete Neutralisationsmittel sind z.B. Dimethylethanolamin, Methyldiethano- lamin, Triethylamin, N-Methylmo holin oder 2-Amino-2-methylpropanol.Suitable neutralizing agents are e.g. Dimethylethanolamine, methyldiethanolamin, triethylamine, N-methylmo holin or 2-amino-2-methylpropanol.
Zum Schutz vor Thermovergilbung können den erfindungsgemäßen Vemetzem als Hilfsstoff auch Stabilisatoren, z.B. Hydrazide und HALS-Amine (Hindered AmineTo protect against thermal yellowing, stabilizers, e.g. Hydrazides and HALS amines (hindered amines
Light Stabilizers) vom Typ Tinuvin® 770 DF, beigemischt werden. Weiterhin können Zuschlagsstoffe und weitere Hilfsstoffe zugegeben werden.Light Stabilizers) of the type Tinuvin® 770 DF. Additives and other auxiliaries can also be added.
Die erfindungsgemäßen Vemetzer können entweder bis zu 80%ig in einem wasser- verdünnbaren Lösemittel oder bis zu 50%ig in überwiegend in Wasser dispergierterThe crosslinking agents according to the invention can either be up to 80% pure in a water-dilutable solvent or up to 50% pure mainly in water
Form in den Verkehr gebracht werden. An wasserverdünnbaren Lösemitteln kommen z.B. Butyldiglycolacetat, Butlydiglycol, N-Methylpyrrolidon oder deren beliebige Gemische in Betracht.Form to be placed on the market. On water-dilutable solvents e.g. Butyl diglycol acetate, butly diglycol, N-methylpyrrolidone, or any mixture thereof.
Die erfindungsgemäßen Polyisocyanat-Vemetzer haben folgende Vorteile: Die Vemetzer sowie die damit formulierten wässrigen Einbrennlacke sind mindestens 3 Monate lagerstabil.The polyisocyanate crosslinkers according to the invention have the following advantages: The crosslinkers and the aqueous stoving enamels formulated with them are stable on storage for at least 3 months.
- Das Blockierungsmittel Diisopropylamin ist eine preiswerte großtechnische Chemikalie.- The blocking agent diisopropylamine is an inexpensive industrial chemical.
- Die Einbrenntemperatur der wässrigen Lacke liegt bei 30 Minuten/130°C und damit 10°C niedriger als bei einem butanonoximblockierten Vemetzer.- The baking temperature of the aqueous varnish is 30 minutes / 130 ° C and thus 10 ° C lower than that of a butanone oxime-blocked crosslinker.
Der einfache Aufbau und die gute Korrosionsschutzwirkung (Salzsprühtest) werden anhand der folgenden Beispiele demonstriert. The simple structure and the good corrosion protection (salt spray test) are demonstrated using the following examples.
BeispieleExamples
Beispiel 1 (erfindungsgemäß)Example 1
Es wird die Herstellung eines wasserverdünnbaren blockierten Polyisocyanat-Ver- netzers beschriebenThe production of a water-dilutable blocked polyisocyanate crosslinker is described
a) Ansatza) Approach
196 g (1,0 val) eines handelsüblichen isocyanurathaltigen Lackpolyisocya- nates auf Basis von 1,6- Diisocyanatohexan (HDI) mit einem196 g (1.0 val) of a commercially available lacquer polyisocyanate containing isocyanurate based on 1,6-diisocyanatohexane (HDI) with a
NCO-Gehalt von 21,4 Gew.-%, einer Viskosität bei 23°C von ca. 3000 mPas und einer Funktionalität von ca. 3,5NCO content of 21.4% by weight, a viscosity at 23 ° C of approx. 3000 mPas and a functionality of approx. 3.5
80,8 g (0,8 Mol) Diisopropylamin 23,6 g (0,2 Mol) Hydroxypivalinsäure 16,0 g (0,18 Mol) Dimethylethanolamin 146,0 g N-Methylpyrrolidon80.8 g (0.8 mol) diisopropylamine 23.6 g (0.2 mol) hydroxypivalic acid 16.0 g (0.18 mol) dimethylethanolamine 146.0 g N-methylpyrrolidone
462,4 g (0,8 vol) blockierte NCO-Gruppen462.4 g (0.8 vol) blocked NCO groups
Festkörpergehalt: 65 Gew.-% (Ber.) Viskosität bei 23°C: ca. 9000 mPas Blockierter NCO-Gehalt: 7,3 Gew.-% (Ber.) 1 val block. NCO-Gruppen: 575 gSolids content: 65% by weight (range) Viscosity at 23 ° C: approx. 9000 mPas Blocked NCO content: 7.3% by weight (range) 1 val block. NCO groups: 575 g
b) Durchführung:b) Implementation:
Polyisocyanat, N-Methylpyrrolidon und Hydroxypivalinsäure werden unter Rühren in Intervallen bis auf 80°C erwärmt. Bei dieser Temperatur wird ca. 2 Stunden nach- gerührt, bis der NCO-Gehalt auf ca. 9,1 % gefallen ist. Danach lässt man auf ca.Polyisocyanate, N-methylpyrrolidone and hydroxypivalic acid are heated at intervals to 80 ° C. with stirring. At this temperature, stirring is continued for about 2 hours until the NCO content has dropped to about 9.1%. Then leave on approx.
40°C abkühlen und tropft Diisopropylamin hinzu, wobei die Temperatur bei ca. 60°C gehalten wird. Nach beendeter Zugabe von Diisopropylamin wird 15 Minuten bei 60°C nachgerührt. IR-spektroskopisch lassen sich danach keine NCO-Gmppen mehr feststellen. Man gibt Dimethylethanolamin hinzu, lässt abkühlen und erhält die anwendungsfertige, blassgelbe Lösung eines mit Wasser mischbaren blockierten Poly- isocyanates mit dem eingangs genannten Kennzeichen.Cool to 40 ° C. and add diisopropylamine while keeping the temperature at approx. 60 ° C. After the addition of diisopropylamine has ended, the mixture is stirred for 15 minutes 60 ° C stirred. Afterwards, no more NCO groups can be determined by IR spectroscopy. Dimethylethanolamine is added, the mixture is allowed to cool and the ready-to-use, pale yellow solution of a water-miscible blocked polyisocyanate with the characteristic mentioned at the beginning is obtained.
Beispiel 2 (erfindungsgemäß)Example 2
Es wird die Herstellung eines in Wasser dispergierten blockierten Polyisocyanat- Vernetzers beschrieben.The preparation of a blocked polyisocyanate crosslinking agent dispersed in water is described.
a) Ansatz:a) Approach:
196,0 g (1,0 Val) des bereits in Beispiel 1 beschriebenen HDI-Trimerisates196.0 g (1.0 eq) of the HDI trimer already described in Example 1
80,0 g (0,8 Mol) Diisopropylamin 17,7 g (0,15 Mol) Hydroxypivalinsäure, M 11880.0 g (0.8 mol) diisopropylamine 17.7 g (0.15 mol) hydroxypivalic acid, M 118
3,35 g (0,05Val) Dimethylolpropionsäure, M 1343.35 g (0.05 val) of dimethylol propionic acid, M 134
15,55 g (0,175 Mol) Dimethylethanolamin15.55 g (0.175 mol) of dimethylethanolamine
35,6 g N-Methylpyrrolidon35.6 g of N-methylpyrrolidone
693,0 g Wasser693.0 g water
1042,0 g (0,8 Val) blockierte NCO-Gmppen1042.0 g (0.8 val) blocked NCO groups
Festkörpergehalt: 30 % (Ber.)Solids content: 30% (calc.)
Viskosität bei 23°C: ca. 400 mPas Blockierter NCO-Gehalt: 3,2 % (Ber.)Viscosity at 23 ° C: approx. 400 mPas Blocked NCO content: 3.2% (calc.)
1 Val block. NCO-Gmppen: 1303 g1 Val block. NCO groups: 1303 g
b) Durchführung:b) Implementation:
Polyisocyanat wird vorgelegt und gerührt. Hierzu tropft man, ausgehend von Raumtemperatur, vorsichtig Diisopropylamin. Die Umsetzung verläuft exotherm, wobei man die Temperatur bei 70°C hält. Nach ca. 1 Stunde ist die Diisopropylaminzugabe beendet. Man gibt die Lösung aus Hydroxypivalinsäure, Dimethylolpropionsäure und N-Methylpyrrolidon hinzu, erwärmt auf 80°C und rührt ca. 2 Stunden bei dieser Temperatur, bis IR-spektroskopisch keine NCO-Gmppen mehr nachweisbar sind. Danach stoppt man die Wärmezufuhr, gibt Dimethylethanolamin hinzu, rührt 10 Minuten nach und rührt Wasser, auf 50°C temperiert, hinzu. Es entsteht eine Dispersion, die 3 Stunden bei ca. 50°C nachgerührt wird. Anschließend wird unter Rühren auf Raumtemperatur abgekühlt und 3 Stunden weitergerührt. Der dispergierte blockierte Polyisocyanat-Vemetzer hat die oben genannten Kennzeichen.Polyisocyanate is introduced and stirred. To do this, carefully drop diisopropylamine starting from room temperature. The implementation is exothermic, whereby keeping the temperature at 70 ° C. The addition of diisopropylamine is complete after about 1 hour. The solution of hydroxypivalic acid, dimethylolpropionic acid and N-methylpyrrolidone is added, the mixture is heated to 80 ° C. and stirred at this temperature for about 2 hours until NCO groups are no longer detectable by IR spectroscopy. Thereafter, the supply of heat is stopped, dimethylethanolamine is added, the mixture is stirred for a further 10 minutes and water, at 50 ° C., is stirred. A dispersion is formed, which is stirred at about 50 ° C for 3 hours. The mixture is then cooled to room temperature with stirring and stirring is continued for 3 hours. The dispersed blocked polyisocyanate crosslinker has the above characteristics.
Beispiel 3 (Vergleich)Example 3 (comparison)
Dieser mit Butanonoxim blockierte Vemetzer ist analog, wie in Beispiel 2 beschrieben, aufgebaut. Er ist folgendermaßen charakterisiert:This crosslinker blocked with butanone oxime is constructed analogously to that described in Example 2. It is characterized as follows:
Festkörpergehalt: 41 % Viskosität bei 23°C: ca. 5700 mPas Blockierter NCO-Gehalt: 3,9Solids content: 41% viscosity at 23 ° C: approx. 5700 mPas Blocked NCO content: 3.9
1 Val block. NCO-Gmppen: 10771 Val block. NCO group: 1077
Beispiel 4 (Anwendung)Example 4 (application)
a) Klarlackrezepturena) Clear lacquer formulations
Die Lackkomponenten in der obigen Übersicht werden mittels eines Rührers innig vermischt. Die Dosiemng der OH-Komponenten und der blockierten Vemetzer erfolgt dabei im Äquivalentverhältnis 1:1. Der Zusatz an Melaminharz wirkt sich verbessernd auf eine glatte Oberflächenqualität aus.The paint components in the overview above are mixed intimately using a stirrer. The OH components and the blocked crosslinkers are metered in an equivalent ratio of 1: 1. The addition of melamine resin improves the smooth surface quality.
b) Lagerbeständigkeitsprüfungb) shelf life test
Weder ein signifikanter Viskositätsanstieg noch irgendein Bodensatz kann bei obigenNeither a significant increase in viscosity nor any sediment can occur with the above
Lacken während der Lagerung beobachtet werden. c) LackeigenschaftenLacquers can be observed during storage. c) paint properties
Die drei obigen Lacke werden mittels Fließbecher-Spritzpistole mit einer Düse (Durchmesser 1,5 mm) und einem Zerstäuberdmck von 5 bar auf die nachstehenden Substrate in einer resultierenden Trockenfilmstärke von 25-35 μm aufgetragen. Die Nasslackfilme werden 5 Minuten bei 23°C abgelüftet und anschließend in einem Umluftofen eingebrannt. Die Substrate sind im Falle der Prüfungen von Pendelhärte und Anlösbarkeit Glasplatten, im Falle von Haftung/ Gitterschnitt, Erichsen-Tiefung und Salzsprühtest entfettete Stahlbleche:The three above lacquers are applied to the following substrates in a resulting dry film thickness of 25-35 μm using a flow cup spray gun with a nozzle (diameter 1.5 mm) and an atomizing pressure of 5 bar. The wet paint films are flashed off at 23 ° C. for 5 minutes and then baked in a forced air oven. In the case of tests of pendulum hardness and solubility, the substrates are glass plates, in the case of adhesion / cross cut, Erichsen cupping and salt spray test, degreased steel sheets:
1) Pendelhärte: Schwingungsversuch nach König DIN 53 1571) Pendulum hardness: Vibration test according to König DIN 53 157
2) Lösemittelbeständigkeit 1 Minute abgedeckte Belastung mit Chemikalien (Index 0-5=keine Anlösung, 5=vollständige Auflösung) 3) Erichsentiefung nach DIN EN ISO 15202) Solvent resistance 1 minute covered exposure to chemicals (index 0-5 = no dissolution, 5 = complete dissolution) 3) Erichsen deepening according to DIN EN ISO 1520
4) Gitterschnitt nach DIN EN ISO 24094) Cross cut according to DIN EN ISO 2409
5) Salzsprühnebeltest nach DIN 53 167 Wd= Unterwanderung vom DLN-Schnitt in mm Wie man der obigen Ausprüfung entnehmen kann, sind die Lacke 1 und 2 mit den erfindungsgemäßen Vemetzem reaktiver als Lack 3 mit dem butanonoximblockierten Polyisocyanat-Vemetzer. Die höhere Reaktivität, die auf dem Blockierungsmittel Diisopropylamin beruht, wird an der höheren Lackhärte, der besseren Lösemittelbe- ständigkeit und der verbesserten Korrosionsbeständigkeit (geringere Lackunterwanderung der Salzlösung) sichtbar. 5) Salt spray test according to DIN 53 167 Wd = infiltration from the DLN cut in mm As can be seen from the above test, lacquers 1 and 2 with the crosslinkers according to the invention are more reactive than lacquer 3 with the butanone oxime-blocked polyisocyanate crosslinker. The higher reactivity, which is based on the blocking agent diisopropylamine, is evident from the higher paint hardness, the better resistance to solvents and the improved corrosion resistance (less paint infiltration of the salt solution).

Claims

Patentansprüche claims
1. Wässrige und/oder wasserverdünnbare blockierte Polyisocyanat-Vemetzer aus1. Aqueous and / or water-dilutable blocked polyisocyanate crosslinkers
a) 100 Äquivalent-% einer Polyisocyanatkomponente, b) 50-85 Äquivalent-% an Diisopropylamin, c) 15-40 Äquivalent-% einer Monohydroxy- und/oder eine Dihydroxy- carbonsäure als Hydrophilierungsmittel und gegebenenfalls d) 0-15 Äquivalent-% einer difunktionellen, HO- und/oder NH2-Gmppen tragenden Kettenverlängerungskomponente,a) 100 equivalent% of a polyisocyanate component, b) 50-85 equivalent% of diisopropylamine, c) 15-40 equivalent% of a monohydroxy- and / or a dihydroxycarboxylic acid as hydrophilizing agent and optionally d) 0-15 equivalent% a difunctional chain extension component carrying HO and / or NH 2 groups,
wobei die Mengenverhältnisse der Reaktionspartner so gewählt werden, dass das Äquivalentverhältnis von NCO-Gmppen der Komponente a) zu gegen- über Isocyanaten reaktionsfähigen Gruppen der Komponenten b), c), und d) bei 1:0,8 bis 1:1,2 liegt, sowie Zuschlagstoffe und Hilfsstoffe.the proportions of the reactants being chosen so that the equivalent ratio of NCO groups of component a) to isocyanate-reactive groups of components b), c) and d) is from 1: 0.8 to 1: 1.2 lies, as well as aggregates and auxiliary materials.
2. Verfahren zur Herstellung der blockierten wässrigen und/oder wasserverdünnbaren Polyisocyanat-Vemetzer nach Anspruch 1, dadurch gekennzeich- net, dass die Polyisocyanatkomponente a) und gegebenenfalls 30 Gew.-%, bezogen auf den fertigen blockierten Polyisocyanat-Vemetzer, eines wassermischbaren Lösemittels, vorgelegt werden, in einer ersten Reaktionsstufe bei ca. 80°C mit der für die Hydrophilierung vorgesehenen Monohydroxycarbonsäure umgesetzt wird, anschließend auf ca. 50°C abgekühlt wird und die verbleibenden NCO-Gmppen durch Zugabe von Diisopropylamin blockiert werden.2. A process for the preparation of the blocked aqueous and / or water-dilutable polyisocyanate crosslinker according to claim 1, characterized in that the polyisocyanate component a) and optionally 30% by weight, based on the finished blocked polyisocyanate crosslinker, of a water-miscible solvent, are presented in a first reaction stage at about 80 ° C with the monohydroxycarboxylic acid intended for hydrophilization, then cooled to about 50 ° C and the remaining NCO groups are blocked by adding diisopropylamine.
3. Verwendung der wässrigen oder wasserverdünnbaren blockierten Polyisocyanat- Vernetzter gemäß Anspruch 1 in Kombination mit in Wasser löslichen und/oder dispergierbaren Polyhydroxylverbindungen zur Herstellung von, gegebenenfalls die üblichen Hilfs- und Zusatzmittel der Beschichtungstech- nologie enthaltenden, wässrigen Einbrennlacken.3. Use of the aqueous or water-dilutable blocked polyisocyanate crosslinking agent according to claim 1 in combination with water-soluble and / or dispersible polyhydroxy compounds for the preparation of, if appropriate, the conventional auxiliaries and additives of the coating technology-containing aqueous stoving lacquers.
4. Verwendung nach Anspmch 4 für die AutomobiUackiemng. 4. Use according to Anspmch 4 for AutomobiUackiemng.
EP02784829A 2001-07-13 2002-07-01 Aqueous and/or water-dilutable polyisocyanate cross-linking agents which are blocked by a diisopropylamine, and the use of said agents Withdrawn EP1409565A1 (en)

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DE10134238 2001-07-13
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US6716910B2 (en) 2004-04-06
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