WO2009068377A1 - Compositions de polyuréthanes contenant des groupes uretdione, durcissables à basse température et contenant des résines améliorant l'adhérence - Google Patents

Compositions de polyuréthanes contenant des groupes uretdione, durcissables à basse température et contenant des résines améliorant l'adhérence Download PDF

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WO2009068377A1
WO2009068377A1 PCT/EP2008/064357 EP2008064357W WO2009068377A1 WO 2009068377 A1 WO2009068377 A1 WO 2009068377A1 EP 2008064357 W EP2008064357 W EP 2008064357W WO 2009068377 A1 WO2009068377 A1 WO 2009068377A1
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acid
compositions according
alcoholate
hydroxide
polyurethane compositions
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PCT/EP2008/064357
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German (de)
English (en)
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Patrick GLÖCKNER
Volker Weiss
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Evonik Degussa Gmbh
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • 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
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and acids
    • 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
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/68—Unsaturated polyesters
    • C08G18/683—Unsaturated polyesters containing cyclic groups
    • C08G18/686—Unsaturated polyesters containing cyclic groups containing cycloaliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—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
    • C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/20—Compositions for powder coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the invention relates to uretdione group-containing polyurethane compositions which are curable at low temperature and contain adhesion-improving resins, in particular for polyurethane powder coating and adhesive compositions which are curable at low temperature, a process for their preparation and their use.
  • Solid at room temperature, externally or internally blocked polyisocyanates are valuable crosslinkers for thermally crosslinkable polyurethane (PUR) -Pulverlack- and adhesive compositions.
  • PUR thermally crosslinkable polyurethane
  • DE-OS 30 30 539 and DE-OS 30 30 572 describe processes for the preparation of uretdione-containing polyaddition compounds whose terminal
  • Isocyanate groups with monoalcohols or monoamines are irreversibly blocked. Disadvantages are, in particular, the chain-breaking constituents of the crosslinkers which lead to low network densities of the PU powder coating and thus to moderate solvent resistances.
  • Hydroxyl-terminated, polyaddition compounds containing uretdione groups are the subject of EP 669 353. Due to their functionality of two, they have improved resistance to solvents.
  • the powder coating compositions based on these polyisocyanates containing uretdione groups have in common that they do not emit volatile compounds during the curing reaction. However, the baking temperatures are at least 180 0 C at a high level.
  • Certain catalysts greatly reduce the activation energy for the cleavage of uretdione groups, so that when uretdione group-containing curing agents are used, the curing temperature of powder coating or adhesive compositions can be considerably lowered. This is beneficial since This way energy can be saved and it is possible to coat thermosensitive substrates by means of powder coatings. Due to the low curing temperature, there is a high melt viscosity of the applied paint formulation. This leads to development problems and surface defects of the powder coating films. In addition, owing to the high melt viscosity, a significantly lower wetting of the substrate surface is frequently observed, which manifests itself in the reduction of the values for mechanical characteristics and in particular in the deterioration of the substrate adhesion. Course problems and surface defects can, as described in DE 10 2004 020 451, be remedied by addition of hydroxyl-containing (partially) khallins polymers, improved substrate wetting is not achieved, so that the substrate adhesion is still problematic.
  • the object of the present invention was therefore to find highly reactive uretdione-containing polyurethane compositions which can be cured even at very low temperatures and are particularly suitable for the production of light- and weather-stable powder coatings and which have comparable good substrate adhesion values, as correspondingly at higher temperatures hardened Puvehackformulmaschineen.
  • uretdione-containing paint or adhesive compositions can be cured under normal conditions (DBTL catalysis) only from 180 0 C, thereby resulting in coatings, which are usually to the substrate, eg. B. not pretreated steel, have excellent adhesion.
  • inventive low-temperature curing compositions can at 100 to 160 0 C curing not only energy and curing time can be saved, but it can also coat many temperature-sensitive substrates or stick, which would show at 180 0 C undesirable yellowing, decomposition and / or embrittlement phenomena.
  • certain aluminum substrates are also predestined. In the latter case, an excessively high temperature load sometimes leads to an undesired change in the crystal structure and thus to the loss of the desired mechanical properties.
  • the present invention relates to solid, highly reactive uretdione-containing polyurethane compositions having a melting point above 40 0 C, a very good substrate wetting and a very good adhesion, essentially containing
  • Tricyclene and the bridging atoms in addition to carbon may also be heteroatoms having 1 to 18 carbon atoms and each radical R 1 to R 4 additionally one or more alcohol, amino, ester, keto, thio, urethane, urea , Allophanate groups, double bonds, triple bonds or halogen atoms, and R 5 is an alkyl,
  • Aryl, aralkyl, heteroaryl, alkoxyalkyl, linear or branched, having 1 to 18 carbon atoms and additionally one or more alcohol, May have amino, ester, keto, thio, acid, urethane, urea, allophanate, double bonds, triple bonds or halogen atoms,
  • R 1 to R 4 bridged to form cyclen, bicyclic or tricyclic and the bridging atoms in addition to carbon may also be heteroatoms, having 1 to 18 carbon atoms and each radical R 1 to R 4 additionally one or more alcohol, amino , Ester, keto, thio, acid, urethane, urea, allophanate groups, double bonds,
  • R 5 is either OH or F
  • radicals R 1 to R 6 mean independently or independently of one another hydrogen or alkyl, aryl, aralkyl, heteroaryl, alkoxyalkyl radicals having 1 to 8 carbon atoms and the radicals are in each case linear or branched, unbridged or bridged with other radicals, with the formation of cycles, bicyclic or tricyclic compounds and
  • Bridging atoms in addition to carbon may also be heteroatoms and may additionally have one or more alcohol, amino, ester, keto, thio, acid, urethane, urea, allophanate, double bonds, triple bonds or halogen atoms, said catalysts from groups 1 to 3 are contained individually or in mixtures and C) at least one hydroxyl- and carboxyl-containing unsaturated, amorphous polyester, substantially containing at least one ⁇ , ßunsaturated dicarboxylic acid component and an alcohol component, wherein the alcohol component of a Dicidolgemisch the isomeric Compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 2 ' 6 ] decane, 4.8- Bis (hydroxymethyl) tricyclo [5.2.1.0 2 ' 6 ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane, each isomer in an amount of 20 to 40% by weight in the mixture may be contained and the sum of the three isomers
  • Polyester is present, with an OH number between 1 and 100 mg KOH / gram and a COOH number between 1 and 75 mg KOH / gram, wherein the ratio of OH and acid number is always> 1, with a weight fraction based on the total formulation, from 1 to 12%; D) optionally at least one acid group-reactive compound;
  • Total formulation is and the sum of the starting materials A) to H) 100 wt .-% results.
  • Another object of the invention is also a process for the preparation of the polyurethane composition.
  • the invention also provides powder coating compositions and pulverulent adhesive compositions and the use of the polyurethane compositions according to the invention for the production of powder coating coatings on metal, plastic, glass, wood or leather substrates or other heat-sensitive substrates or for the production of powdered adhesive coatings on metallic coatings.
  • Plastic, glass, wood or leather substrates or other heat-sensitive substrates are preferred.
  • the invention likewise relates to powder coating compositions for metal, in particular for automobile bodies, motorcycles and bicycles, building parts and household appliances, powder coating compositions for wood, glass, leather and plastics.
  • Polyisocyanates containing uretdione groups are well known and are described, for example, in US 4,476,054, US 4,912,210, US 4,929,724 and EP 0 417 603.
  • J. Prakt. Chem. 336 (1994) 185-200 J. Prakt. Chem. 336 (1994) 185-200.
  • the reaction of isocyanates to uretdiones in the presence of soluble Dimehs mecanicskatalysatoren such as.
  • dialkylaminopyridines Thalkylphosphinen, phosphorous acid triamides or imidazoles.
  • the reaction - optionally carried out in solvents, but preferably in the absence of solvents - is stopped when a desired conversion is achieved by addition of catalyst poisons. Excess monomeric isocyanate is subsequently separated by short path evaporation. If the catalyst is volatile enough, the reaction mixture can be freed from the catalyst in the course of the monomer separation. The addition of catalyst poisons can be dispensed with in this case.
  • isocyanates is suitable for the preparation of polyisocyanates containing uretdione groups. According to the invention, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI),
  • Uretdione group-containing hardeners A includes the reaction of the free NCO groups with hydroxyl-containing monomers or polymers, such as.
  • polyesters polythioethers, polyethers, polycaprolactams, polyepoxides, polyester amides, polyurethanes or low molecular weight di-, tri- and / or tetra alcohols as chain extenders and optionally monoamines and / or monoalcohols as chain terminators and has been described frequently (EP 669 353, EP 669 354, DE 30 30 572, EP 639 598 or EP 803 524).
  • polyesters having an OH number of 30 to 150 mg KOH / g and an average molecular weight of 500 to 6000 g / mol and low molecular weight dialcohols.
  • Preferred uretdione hardeners A) have a free NCO content of less than 5% by weight and a uretdione group content of 1 to 18% by weight (calculated as C 2 N 2 O 2 , molecular weight 84).
  • the hardeners A) may also have isocyanurate, biuret, allophanate, urethane and / or urea structures.
  • the catalysts B) essential to the invention satisfy 1. the formula [XR 1 R 2 R 3 R 4 I + [R 5 COO] " , where X is N or P, where R 1 to R 4 are simultaneously or independently alkyl-, aryl- , Aralkyl, heteroaryl, alkoxyalkyl radicals, in each case linear or branched, unbridged or bridged with other radicals R 1 to R 4 , forming cyclics, bicyclic or tricyclic radicals and the bridging atoms besides carbon may also be heteroatoms having 1 to 18 carbon atoms and each radical R 1 to R 4 may additionally have one or more alcohol, amino, ester, keto, thio, urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms, and R 5 is an alkyl, , Aryl, aralkyl, heteroaryl, alkoxyalkyl, linear or branched, having 1 to 18 carbon atoms and additionally one or more alcohol
  • Examples of such catalysts under 1. are tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate,
  • Tetraethylammonium benzoate tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium propionate,
  • Tetrabutylammonium benzoate tetrabutylphosphonium acetate, tetrabutylphosphonium formate, ethyltriphenylphosphonium acetate,
  • Trihexyltetradecylphosphoniumdecanoat examples of such catalysts under 2. are methyltributylammonium, methyltriethylammonium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, tetraoctylammonium, Tetradecylammoniumhydroxid, Tetradecyltrihexylammoniumhydroxid, Tetraoctadecylammoniumhydroxid, benzyltrimethylammonium, benzyltriethylammonium, trimethylphenylammonium, Thethylmethylamnnoniunnhydroxid, Trimethylvinylammoniumhydroxid, tetramethylammonium fluoride, tetraethylammonium, te
  • Examples of such catalysts under 3. are lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, aluminum hydroxide, zinc hydroxide, lithium methoxide, sodium methoxide, potassium methoxide, magnesium methoxide, calcium methoxide, barium methoxide, lithium ethoxide, sodium ethanolate, potassium ethanolate, Magnesium ethanolate, calcium ethanolate, barium ethanolate, lithium propyl alcoholate, sodium propyl alcoholate, potassium propyl alcoholate, magnesium propyl alcoholate, calcium propyl alcoholate, barium propyl alcoholate, lithium isopropyl alcoholate, sodium isopropyl alcoholate, potassium isopropyl alcoholate, magnesium isopropyl alcoholate, calcium isopropyl alcoholate, barium isopropyl alcoholate, lithium 1-butyl alcohol
  • the catalysts are contained in an amount of 0.001 to 5 wt .-%, preferably 0.01 to 3 wt .-%, based on the total formulation, in the polyurethane composition.
  • the catalysts may contain water of crystallization, which is not taken into account in the calculation of the amount of catalyst used, d. H. the amount of water is deducted. Particular preference is given to using tetraethylammonium benzoate and tetrabutylammonium hydroxide.
  • a variant according to the invention includes the polymeric attachment of such catalysts B) to the curing agents A) or hydroxyl-containing polymers C) or F).
  • So z. B. free alcohol, thio or amino groups of the ammonium salts with acid, isocyanate, or glycidyl groups of the powder coating hardener A) or hydroxyl-containing polymers C) or F) are reacted to integrate the catalysts B) in the polymeric composite.
  • These catalysts may also be encased in a shell and encapsulated therewith.
  • As component C) is at least one hydroxyl and carboxyl-containing unsaturated, amorphous polyester having an OH number between 1 and 100 mg KOH / gram and a COOH number between 1 and 75 mg KOH / gram, wherein the ratio of OH and Acid number is always> 1, with a
  • Weight fraction based on the total formulation, from 1 to 12% used.
  • Component C) comprises unsaturated polyesters containing amorphous hydroxyl and carboxyl groups, essentially containing at least one ⁇ , ⁇ -unsaturated dicarboxylic acid component and an alcohol component, the alcohol component of a mixture of dicidol of the isomeric compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 2 ' 6 ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane, each isomer may be present in a proportion of 20 to 40 wt .-% in the mixture and the sum of the three isomers 90 to 100 wt .-% results, and the mixture at least 5 wt .-% in the alcohol component of the polyester is present.
  • the unsaturated amorphous polyester resins C) are obtained by reacting the alcohol component and the acid component.
  • the alcohol component according to the invention is a Dicidolgemisch the isomeric compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 2 ' 6 ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane and 5.8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane used, wherein each isomer may be present in a proportion of 20 to 40 wt .-% in the mixture and the sum of the three isomers 90 to 100 wt .-%, preferably 95 to 100% by weight, and the mixture is at least 5% by weight in the alcohol component of the polyester.
  • the isomer content of the Dicidolgemisches can qualitatively and quantitatively z. B.
  • the Dicidolgemisch may contain up to 10 wt .-% further isomers of diclidol and / or trimeric and / or higher isomeric diols of the Diels-Alder reaction product of cyclopentadiene.
  • the alcohol component consists of 20 wt .-%, from 50 wt .-%, preferably from 90 wt .-%, particularly preferably from 100 wt .-% Dicidolgemisch, this more preferably 95 to 100 wt .-% of the above contains three isomeric compounds.
  • the alcohol component may contain further linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic diols and / or polyols.
  • Preferred additional alcohols are ethylene glycol, 1, 2 and / or 1, 3-propanediol, diethylene, dipropylene, ethylene, tetraethylene glycol, 1, 2 and / or 1, 4-butanediol, 1, 3-butylethylpropanediol, 1, 3-methylpropanediol, 1, 5-pentanediol, cyclohexanedimethanol, glycerol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane and / or pentaerythritol and bisphenol A, B, C, F, norbornylene glycol, 1, 4-benzyldimethanol and ethanol, 2, 4-di
  • the unsaturated, amorphous polyester resins C) contain as starting acid component at least one ⁇ , ß-unsaturated dicarboxylic acid.
  • the unsaturated polyester resins preferably contain citraconic, fumaric, itaconic, maleic and / or mesaconic acid.
  • Phthalic acid isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, sebacic acid, methyltetra-, methylhexahydrophthalic acid, hexahydrophthalic acid,
  • Tetrahydrophthalic acid Tetrahydrophthalic acid, dodecanedioic acid, adipic acid, azelaic acid, isononanoic acid, 2-ethylhexanoic acid, pyromellitic acid and / or trimellitic acid.
  • Preference is given to phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, adipic acid and / or azelaic acid.
  • the acid component can consist partly or completely of anhydrides and / or alkyl esters, preferably methyl esters.
  • the alcohol component is contained in the molar ratio of 0.5 to 2.0 to 1 to the acid component, preferably 0.8 to 1, 5 to 1. Particularly preferred is the implementation of the alcohol component in the molar ratio of 1, 0 to 1, 1 to 1 to the acid component instead.
  • the unsaturated, amorphous polyesters C) may have an acid number between 1 and 75 mg KOH / g, preferably between 1 and 50, more preferably between 1 and 35 mg KOH / g and an OH number between 1 and 100 mg KOH / g between 1 and 75, more preferably between 1 and 50 mg KOH / g, wherein the ratio of OH and acid number is always> 1.
  • the Tg of the unsaturated amorphous polyester C) varies from -30 to +80 0 C, preferably from -20 to +50 0 C, more preferably - 10 to + 40 0 C.
  • the unsaturated polyester resins C) consist of an alcohol component having at least 90% by weight, preferably 95% by weight, particularly preferably 100% by weight, of the dicidol mixture of the isomeric compounds 3,8 Bis (hydroxymethyl) tricyclo [5.2.1.0 2 ' 6 ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane and from fumaric acid and / or maleic acid (anhydride).
  • the polyesters C) contain the abovementioned starting components as under I, but additionally an additional acid selected from adipic acid or phthalic acid (anhydride), the ratio of the ⁇ , ⁇ -unsaturated to the additional acid being from 2: 1 to 1: 1 can vary to 4. Ratios of about 1 to 1 to 1 to 2 are preferred.
  • polyesters generally have acid numbers of 1 to 75 mg KOH / g, preferably 1 to 50 mg KOH / g, particularly preferably 1 to 35 mg KOH / g, OH numbers from 1 to 100 mg KOH / g, preferably 1 to 75 mg KOH / g, particularly preferably 1 to 50 mg KOH / g, the ratio of OH and acid number always being> 1, and a Tg of -30 to +80 0 C, preferably -20 to +50 0 C, more preferably -10 to +40 0 C on.
  • the polyesters C) may also contain auxiliaries and additives selected from inhibitors, water and / or organic solvents, neutralizing agents, surface-active substances, oxygen and / or free-radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers, thixotropic agents, anti-skinning agents, defoamers, antistatic agents, thickeners .
  • auxiliaries and additives selected from inhibitors, water and / or organic solvents, neutralizing agents, surface-active substances, oxygen and / or free-radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers, thixotropic agents, anti-skinning agents, defoamers, antistatic agents, thickeners .
  • thermoplastic additives dyes, pigments, fire retardants, internal release agents, fillers and / or blowing agents.
  • the polyesters C) are prepared by (semi) continuous or discontinuous esterification and condensation of the starting acids and alcohols in a one-stage or two-stage procedure.
  • Polyester resins based on dicidol as diol component are also known from DE 924 889, DE 953 117, DE 22 45 110, DE 27 21 989, EP 114 208, EP 934 988, EP 1 492 834.
  • EP 1 398 337 describes adhesion-improving additives of an unsaturated, amorphous polyester.
  • the adhesion-improving additives are polymer-containing in aqueous, solvent-containing (normal, medium, high, very high solids) and / or solvent-free (powder and / or liquid), thermosetting, radiation-curable, air-drying (oxidative and physical) coating materials, fillers and / or sealants and adhesives and are suitable as a modification resin for primers, fillers, basecoats, single-coat finishes, clearcoats, adhesives, sealants, road marking paints, anti-corrosive paints.
  • Polymers according to EP 1 398 337 can carry OH and carboxylic acid groups, wherein both the OH number and the acid number can assume values between 1 and 200 mg KOH / g.
  • the polymers described in EP 1 398 337 can have a high carboxylic acid and low OH functionality.
  • their use would be in highly reactive uretdione-containing polyurethane compositions
  • polyesters, polyethers, polyacrylates, polyurethanes and / or polycarbonates having an OH number of 10 to 500 (in mg KOH / gram) are preferably used in the hydroxyl-containing (partially) khallene polymers G).
  • Particularly preferred are hydroxyl-containing polyesters having an OH number of 15 to 150 and an average molecular weight of 500 to 6,000 g / mol.
  • mixtures of such polymers can be used.
  • the proportion by weight of this (partially) crystalline component G) in the overall formulation A-H can be between 1 and 95% by weight, preferably from 2 to 50% by weight.
  • Preferred (partial) crystalline hydroxyl-containing polyesters G) are prepared by polycondensation.
  • an acid component consisting of 80 to 100 mole percent of a saturated, linear aliphatic or cycloaliphatic dicarboxylic acid having 4 to 14 carbon atoms and 0 to 20 mole percent of another aliphatic or cycloaliphatic or aromatic di- or polycarboxylic acid, having an alcohol component consisting of 80 to 100 Mole percent of a linear aliphatic diol of 2 to 15 carbon atoms and 0 to 20 mole percent of another aliphatic or cycloaliphatic di or polyol of 2 to 15 carbon atoms.
  • the (partially) crystalline hydroxyl-containing polyesters thus produced have an OH number of 15 to 150 mg KOH / g, an acid number ⁇ 5 mg KOH / g and a melting point of 40 to 130 ° C.
  • Succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetrahydrophthalic acid, hexahydrophthalic acid, are preferred carboxylic acids for the preparation of (partly) khallins polyesters G),
  • Hexahydroterephthal Acid endomethylene tetrahydrophthalic acid, glutaric acid or - as far as accessible - their anhydrides.
  • Particularly suitable and preferred is dodecanedioic acid.
  • the following diols are ethylene glycol, propanediol (1, 2) and - (1, 3), 2,2-dimethylpropanediol (1, 3), butanediol (1, 4), pentanediol (1, 5) , Hexanediol (1, 6), 2-methylpentanediol (1, 5), 2,2,4-trimethylhexanediol (1,6), 2,4,4-thymethylhexanediol (1,6), Heptanediol (1, 7), decanediol (1, 10), dodecanediol (1, 12), octadecene-9, 10-diol (1, 12), octadecanediol (1, 18), 2,4- Dimethyl-2-propylheptandiol- (1, 3), butenediol (1, 4), butynediol (1, 4), diethylene glycol,
  • the activity of the catalysts under B) in the presence of acids decreases significantly.
  • the conventional reactants of the uretdione-containing paint or adhesive hardener include hydroxyl-containing polyester. Due to the method of preparation of polyesters, they sometimes carry acid groups to a small extent. In the presence of such acid groups-bearing polyesters, it is advisable to use the catalysts mentioned either in excess, based on the acid groups, or to add reactive compounds which are capable of intercepting acid groups. Both monofunctional and polyfunctional compounds can be used for this purpose.
  • Reactive acid scavenging compounds D are well known in paint chemistry.
  • inorganic salts such as hydroxides, bicarbonates or carbonates
  • triglycidyl ether isocyanurate TGIC
  • EPIKOTE ® 828 diglycidyl ether based on bisphenol A, Schell
  • versatic ethylhexyl glycidyl ether
  • butyl glycidyl ether Polypox R 16 (pentaerythritol tetraglycidyl ether, UPPC AG) as well as other Polypoxtypen having free epoxy groups, .beta.-hydroxyalkylamides (z. B.
  • Acids which are mentioned under E) are all substances, solid or liquid, organic or inorganic, monomeric or polymeric, which have the properties of a Bronsted or a Lewis acid. Examples include: sulfuric acid, acetic acid, benzoic acid, malonic acid, terephthalic acid, but also copolyester or
  • Copolyamides having an acid number of at least 20 mg KOH / g. They are contained, if present, in a proportion by weight, based on the total formulation, of 0.1 to 10%.
  • hydroxyl-containing amorphous polymers F preference is given to using polyesters, polyethers, polyacrylates, polyurethanes and / or polycarbonates having an OH number of 20 to 500 mg KOH / gram. Particularly preferred are hydroxyl-containing polyesters having an OH number of 20 to 150 mg / KOH / g, an average molecular weight of 500 to 6000 g / mol. Of course, mixtures of such polymers can be used. Such amorphous polymers can, if present, be used in a proportion by weight of 1 to 95%, preferably 1 to 90%, based on the total formulation.
  • aliphatic and / or cycloaliphatic and / or aromatic diols and / or polyols can be contained.
  • dicidol ethylene glycol, 1, 2 and / or 1, 3-propanediol, diethylene, dipropylene, ethylene, tetraethylene glycol, 1, 2 and / or 1, 4-butanediol, 1, 3-Butylethylpropandiol, 1, 3-methylpropanediol, 1, 5-pentanediol, cyclohexanedimethanol, glycerol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane and / or pentaerythritol and bisphenol A, B, C, F, norbornylene glycol, 1, 4-benzyldimethanol and ethanol, 2, 4-dimethyl-2
  • the acid component for the preparation of the polyester can linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic monocarboxylic acids and / or dicarboxylic acids and / or polycarboxylic acids may be contained, such as.
  • Phthalic acid isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, sebacic acid, methyltetra-, methylhexahydrophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dodecanedioic acid, adipic acid, azelaic acid, isononanoic acid, 2-ethylhexanoic acid, pyromellitic acid and / or trimellitic acid. Preference is given to phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, adipic acid and / or azelaic acid.
  • the acid component can consist partly or completely of anhydrides and / or alkyl esters, preferably methyl esters.
  • auxiliaries and additives H as leveling agents, for.
  • additional catalysts such as are already known in polyurethane chemistry may be included.
  • organometallic catalysts such as. As dibutyltin dilaurate, or tertiary amines, such as. B. 1, 4-diazabicyclo [2.2.2,] octane, in amounts of 0.001 to 1 wt .-%.
  • the total amount of H) may be from 0.001 to 55% by weight, based on the total formulation.
  • the homogenization of all constituents for the preparation of the polyurethane composition according to the invention can be carried out in suitable aggregates, such. B. heated kneaders, but especially in extruders at temperatures of 40 to 130 0 C, carried out, with upper temperature limits of 120 to 130 0 C not exceeded should be.
  • the well-mixed mass is removed by suitable application, eg. As rollers, spraying, applied to the substrate.
  • suitable application of ready-to-spray powders on suitable substrates can according to the known methods, such. B. by electrostatic powder spraying, vortex sintering, or electrostatic vortex sintering done.
  • the coated workpieces are cured for 4 to 60 minutes at a temperature of 60 to 220 0 C, preferably 6 to 30 minutes at 80 to 150 0 C heated.
  • the comminuted feedstocks according to Table 2 are intimately mixed in a pug mill and then homogenized in the extruder at temperatures up to 130 0 C maximum. After cooling, the extrudate is crushed and ground with a pin mill to a particle size ⁇ 100 microns and sieved by means of a screening machine to ⁇ 63 microns.
  • the powder thus produced is applied with an electrostatic powder spray system at 60 KV on degreased iron sheets and baked in a convection oven for 30 minutes at 150 0 C and 30 minutes at 130 0 C. (Layer thickness 70 to 80 microns). The results of the test data are shown in Tables 3 to 4.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des compositions de polyuréthanes contenant des groupes uretdione, durcissables à basse température et contenant des résines améliorant l'adhérence, en particulier pour des compositions de peintures en poudre et d'adhésifs à base de polyuréthane, qui sont durcissables à basse température, ainsi qu'un procédé pour leur production et leur utilisation.
PCT/EP2008/064357 2007-11-27 2008-10-23 Compositions de polyuréthanes contenant des groupes uretdione, durcissables à basse température et contenant des résines améliorant l'adhérence WO2009068377A1 (fr)

Applications Claiming Priority (2)

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DE102007057057A DE102007057057A1 (de) 2007-11-27 2007-11-27 Uretdiongruppen haltige Polyurethanzusammensetzungen, welche bei niedriger Temperatur härtbar sind und haftungsverbessernde Harze enthalten
DE102007057057.2 2007-11-27

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US8758862B2 (en) 2012-06-26 2014-06-24 Prc Desoto International, Inc. Coating compositions with an isocyanate-functional prepolymer derived from a tricyclodecane polyol, methods for their use, and related coated substrates
EP2977395A1 (fr) * 2014-07-21 2016-01-27 Evonik Degussa GmbH Compositions de polyurethane hautement reactives a base de groupes uretdione contenant des sels carbonate
CN111527118A (zh) * 2017-12-28 2020-08-11 科思创德国股份有限公司 水性分散体
WO2023176641A1 (fr) * 2022-03-17 2023-09-21 三菱ケミカル株式会社 Composition de tricyclodécanediméthanol, composition durcissable aux uv, composition de polymère et procédé de production de composition de tricyclodécanediméthanol

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DE102010041247A1 (de) * 2010-09-23 2012-03-29 Evonik Degussa Gmbh Verfahren zur Herstellung von lagerstabilen Polyurethan-Prepregs und daraus hergestellte Formkörper aus Polyurethanzusammensetzung in Lösung
CN107531019B (zh) * 2015-03-27 2020-05-08 东洋制罐集团控股株式会社 有机树脂被覆的表面处理金属板
CN107810214B (zh) * 2015-06-15 2020-12-08 朗盛德国有限责任公司 用加入的铯盐合成聚合物碳二亚胺的方法、聚合物碳二亚胺及其用途
CN107474778A (zh) * 2017-06-30 2017-12-15 努比亚技术有限公司 一种pur胶的生产方法
CN107936854A (zh) * 2017-11-29 2018-04-20 温州市环球汽车衬垫有限公司 一种新型植物基车用胶水
US10711155B2 (en) 2017-12-20 2020-07-14 Ppg Industries Ohio, Inc. Ultradurable coating composition
WO2021262953A1 (fr) * 2020-06-25 2021-12-30 Dow Global Technologies Llc Polyol et mousse fabriquée à partir de celui-ci

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EP1524283A2 (fr) * 2003-10-15 2005-04-20 Degussa AG Lacques de polyuréthane pulvérulentes contenant des compsosés de poly-addition ayant des groupes d'urethdione solides et un procédé pour leur préparation
WO2005085314A1 (fr) * 2004-03-06 2005-09-15 Degussa Ag Procede de production de compositions de polyurethanne solides hautement reactives contenant des groupes uretdione
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8758862B2 (en) 2012-06-26 2014-06-24 Prc Desoto International, Inc. Coating compositions with an isocyanate-functional prepolymer derived from a tricyclodecane polyol, methods for their use, and related coated substrates
EP2977395A1 (fr) * 2014-07-21 2016-01-27 Evonik Degussa GmbH Compositions de polyurethane hautement reactives a base de groupes uretdione contenant des sels carbonate
CN111527118A (zh) * 2017-12-28 2020-08-11 科思创德国股份有限公司 水性分散体
WO2023176641A1 (fr) * 2022-03-17 2023-09-21 三菱ケミカル株式会社 Composition de tricyclodécanediméthanol, composition durcissable aux uv, composition de polymère et procédé de production de composition de tricyclodécanediméthanol

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