WO2009047102A1 - Compositions de revêtement - Google Patents

Compositions de revêtement Download PDF

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Publication number
WO2009047102A1
WO2009047102A1 PCT/EP2008/062499 EP2008062499W WO2009047102A1 WO 2009047102 A1 WO2009047102 A1 WO 2009047102A1 EP 2008062499 W EP2008062499 W EP 2008062499W WO 2009047102 A1 WO2009047102 A1 WO 2009047102A1
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WIPO (PCT)
Prior art keywords
resins
ketone
aldehyde
diisocyanate
formaldehyde
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PCT/EP2008/062499
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German (de)
English (en)
Inventor
Patrick GLÖCKNER
Andreas Wenning
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Evonik Degussa Gmbh
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Publication of WO2009047102A1 publication Critical patent/WO2009047102A1/fr

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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
    • C08G6/00—Condensation polymers of aldehydes or ketones only
    • C08G6/02—Condensation polymers of aldehydes or ketones only of aldehydes with ketones
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/02—Condensation polymers of aldehydes or ketones only

Definitions

  • the invention relates to coating compositions comprising at least one binder, a formaldehyde-free, carbonyl-hydrogenated ketone-aldehyde resin based on formaldehyde with low viscosity, very low color number and very high heat and light resistance, a colorant and optionally auxiliaries and additives, their preparation and their use
  • the coating compositions are used for coating various substrates, e.g. Metals, plastics, paper, paper laminates, cardboard, cardboard, inorganic materials such. As ceramics, stone, concrete, plaster and / or glass, textiles, fibers, fabric materials, leather and synthetic materials, such as. As artificial leather, wood, films made of plastics and composites such. As aluminum-laminated films, wherein the coating is largely free of formaldehyde.
  • ketones or mixtures of ketones and aldehydes can be converted to resinous products in the presence of basic catalysts or acids.
  • resins from mixtures of cyclohexanone and methylcyclohexanone (Ullmann, Vol. 12, p. 551).
  • the reaction of ketones and aldehydes usually leads to hard resins, which are often used in the paint industry.
  • Technically important ketone-aldehyde resins are nowadays mostly produced using formaldehyde.
  • Ketone-formaldehyde resins have been known for a long time. Process for the preparation are for. As described in DE 33 24 287, US 2,540,885, US 2,540,886, DE 11 55 909, DD 12 433, DE 13 00 256 and DE 12 56 898.
  • ketones and formaldehyde are normally reacted with each other in the presence of bases.
  • Ketone-aldehyde resins are used in coating materials z. B. used as film-forming additional components to improve certain properties such as drying rate, gloss, hardness or scratch resistance. Because of their relatively low molecular weight, conventional ketone-aldehyde resins have a low melt and solution viscosity and therefore serve in coating materials and the like. a. as film-forming functional fillers.
  • the carbonyl groups of the ketone-aldehyde resins are subject to z. B. irradiation with e.g. Sunlight classic degradation reactions such as. From the Norrish type I or Il [Laue, Piagens, name and keyword responses, Teubner arrangementsbücher, Stuttgart, 1995].
  • Formaldehyde can cause health problems. However, an exact classification is not yet made.
  • IARC International Agency for Research on Cancer
  • WHO World Health Organization
  • Ketone-aldehyde resins have always been used to increase the content of non-volatile constituents in coating materials. Under the pressure of new guidelines such. For example, Council Directive 1999/13 / EC on the limitation of emissions of volatile organic compounds, these characteristics need to be further improved.
  • the object of the present invention was to find coating compositions for the coating of different substrates that are free from free formaldehyde.
  • the coating compositions should have a high drying rate, water resistance and scratch resistance and a low solution viscosity at high solids content.
  • the films should have a good adhesion to the substrate, a low gloss, high color stability and a high heat and light resistance.
  • the invention relates to coating compositions containing free formaldehyde below 100 ppm, essentially containing
  • R aromatic with 6-14 carbon atoms, (cyclo-) aliphatic with 1-12
  • the carbonyl-hydrogenated ketone-aldehyde resins A) essential to the invention are used in amounts of from 5 to 75% by weight, preferably from 5 to 50% by weight.
  • component A) are suitable carbonyl-hydrogenated ketone-aldehyde resins based on formaldehyde, having a content of free formaldehyde of less than 3 ppm, which contain substantially the structural elements of formula I.
  • R aromatic with 6-14 carbon atoms, (cyclo-) aliphatic with 1-12
  • the content of free formaldehyde is below 3 ppm, preferably below 2.5 ppm, particularly preferably below 2.0 ppm,
  • the carbonyl number is between 0 and 100 mg KOH / g, preferably between 0 and 50 mg KOH / g, more preferably between 0 and 25 mg KOH / g,
  • the hydroxyl number is between 50 and 450 mg KOH / g, preferably between 150 and 400 mg KOH / g, more preferably between 200 and 375 mg KOH / g,
  • the Gardner color number (50% in ethyl acetate) is less than 1.5, preferably less than 1.0, more preferably less than 0.75,
  • Gardner color number (50% in ethyl acetate) after thermal loading of the resin (24 h, 150 ° C.) is below 2.0, preferably below 1.5, particularly preferably below 1.0,
  • the polydispersity (Mw / Mn) of the resins is between 1, 35 and 1, 6, more preferably between 1, 4 and 1, 58,
  • the solution viscosity, 40% in phenoxyethanol is between 5,000 and 12,000 mPa.s, more preferably between 6,000 and 10,000 mPa.s,
  • the melting point / range is between 50 and 150 ° C, preferably between 75 and 140 ° C, more preferably between 100 and 130 ° C, and
  • Formaldehyde-free means that the carbonyl-hydrogenated ketone-aldehyde resins essential to the invention have a content of free formaldehyde below 3 ppm, preferably below 2.5 ppm, particularly preferably below 2.0 ppm. It has been found that a low color number and a high thermal stability is the result of a low carbonyl number (I ⁇ 2 of 1c).
  • the carbonyl number of the carbonyl-hydrogenated ketone-aldehyde resins A) essential to the invention is between 0 and 100 mg KOH / g, preferably between 0 and 50 mg KOH / g, more preferably between 0 and 25 mg KOH / g, so that the Gardner color number (50%) in ethyl acetate) of the invention essential carbonyl-hydrogenated ketone aldehyde resins below 1, 5, preferably below 1, 0, more preferably below 0.75 and the Gardner color number (50% in ethyl acetate) after thermal stress (24 h, 150 ° C) 2.0, preferably less than 1, 5, more preferably less than 1, 0.
  • the solution viscosity of the carbonyl-hydrogenated ketone-aldehyde resins essential to the invention is 40% in phenoxyethanol, between 5000 and 12000 rnPa-s, more preferably between 6000 and 1000o mPa-S.
  • the carbonyl-hydrogenated ketone-aldehyde resins A) essential to the invention have low polydispersities (Mw / Mn) between 1.35 and 1.6, more preferably between 1.4 and 1.58.
  • the highest possible melting range of the invention essential carbonyl-hydrogenated ketone-aldehyde A) is desirable so that z.
  • a high melting point / range can firstly be obtained via a high molecular weight (sum of k + I + m in formula I). However, the higher the molecular weight, the higher the solution viscosity. That's why it was desired to raise the melting point / range without increasing the molecular weight. This could be achieved, in which k always predominates in formula I and is preferably chosen as high as possible.
  • the value of k is from 2 to 15, preferably from 3 to 12, particularly preferably from 4 to 12.
  • the carbonyl-hydrogenated ketone-aldehyde resins A) essential to the invention have melting points of between 50 and 150.degree. C., preferably between 75 and 140.degree. C., more preferably between 100 and 130 ° C.
  • a high k according to formula I also has a positive effect on the solubility of the invention essential carbonyl-hydrogenated ketone-aldehyde A) in polar solvents such.
  • polar solvents such as alcohols, which is especially important in coating materials, since often alcohols such. Ethanol can be used.
  • the solubility properties can be adjusted by the ratio of k, I and m.
  • the ratio of k, I and m must be chosen so that other properties such. B. the water resistance can not be adversely affected.
  • the values for k, I and m as well as the sum of the values can be integers, e.g. B. 2, but also intermediate values, such. B. 2.4 assume.
  • ketones and aldehydes Suitable ketones for the preparation of the carbonyl-hydrogenated ketone-aldehyde resins A) based on formaldehyde are all ketones, in particular all ⁇ -methyl ketones which have no possibility of reacting in the ⁇ '-position to the carbonyl group or have only a low reactivity in the ⁇ '-position, such as As acetophenone, derivatives of acetophenone such.
  • ketones As hydroxyacetophenone, al kylsu bstitu ized acetophenone derivatives having 1 to 8 carbon atoms on the phenyl ring, methoxyacetophenone, 3,3-dimethylbutanone, methyl isobutyl ketone but also propiophenone alone or in mixtures.
  • These ketones are contained in the resins of the invention from 70 to 100 mol%, based on the ketone component.
  • Carbonyl-hydrogenated ketone-aldehyde resins A) based on the ketones acetophenone, 3,3-dimethylbutanone and methyl isobutyl ketone are preferred, alone or in a mixture.
  • CH-acidic ketones can be used in a subordinate scale in mixture with the abovementioned ketones up to 30 mol%, preferably up to 15 mol%, based on the ketone component, such as. Acetone, methyl ethyl ketone, heptanone-2, pentanone-3, cyclopentanone, cyclododecanone, mixtures of 2,2,4- and 2,4,4-trimethylcyclopentanone, cycloheptanone and cyclooctanone, cyclohexanone and all alkyl-substituted cyclohexanones having one or more alkyl radicals, having a total of 1 to 8 carbon atoms, individually or in mixture.
  • the ketone component such as. Acetone, methyl ethyl ketone, heptanone-2, pentanone-3, cyclopentanone, cyclododecanone, mixtures of 2,2,4- and 2,4,4-tri
  • alkyl-substituted cyclohexanones there may be mentioned 4-tert.-amylcyclohexanone, 2-sec.-butylcyclohexanone, 2-tert.-butylcyclohexanone, 4-tert.-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone.
  • aldehyde In addition to formaldehyde are suitable as additional aldehyde components of the carbonyl-hydrogenated ketone-aldehyde resins A) based on formaldehyde in principle, unbranched or branched aldehydes, such as. As acetaldehyde, n-butyraldehyde and / or iso-butyraldehyde, valeric aldehyde and dodecanal. In general, all the aldehydes mentioned in the literature as suitable for ketone resin syntheses can be used become. Preferably, however, formaldehyde is used alone.
  • the further aldehydes can be used in proportions between 0 and 75 mol%, preferably 0 and 50 mol%, particularly preferably between 0 and 25 mol%, based on the aldehyde component.
  • Aromatic aldehydes such as. As benzaldehyde, may be included in a mixture with formaldehyde up to 10 mol% also.
  • the required formaldehyde is usually used as about 20 to 40 wt .-% aqueous or alcoholic (eg, methanol or butanol) solution.
  • Other forms of formaldehyde are formaldehyde donating compounds such. Para- formaldehyde and / or trioxane.
  • ketone-aldehyde resins acetophenone, 3,3-dimethylbutanone and also methyl isobutyl ketone and optionally CH-acidic ketones selected from cyclohexanone, methyl ethyl ketone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone and 3,3,5-trimethylcyclohexanone alone or in mixture and formaldehyde. It is also possible to use mixtures of different ketone-aldehyde resins A).
  • the molar ratio between the ketone and the aldehyde component is between 1: 0.25 to 1 to 15, preferably between 1: 0.9 to 1: 5 and more preferably between 1: 0.95 to 1: 4.
  • the respective ketone or a mixture of different ketones is reacted with formaldehyde or a mixture of formaldehyde and additional aldehydes in the presence of at least one basic catalyst.
  • formaldehyde as an aqueous solution and ketones whose water solubility is limited
  • water-soluble organic solvents can be used advantageously.
  • at least one phase transfer catalyst can additionally be used, whereby z. B. is possible to reduce the amount of alkali compound.
  • the aqueous phase is separated from the resin phase.
  • the crude product is washed with acidic water until a melt sample of the resin appears clear. Then, the resin is dried by distillation.
  • the reaction to produce the base resins from ketone and aldehyde is carried out in a basic medium.
  • suitable basic catalysts such as alkali compounds are used.
  • Very particularly preferred are hydroxides of the cations NH 4 , NR 4 , Li, Na.
  • the reaction for producing the base resins of ketone and aldehyde can be carried out by using an auxiliary solvent.
  • auxiliary solvent As suitable, alcohols such. As methanol or ethanol proved. It is also possible to use water-soluble ketones as auxiliary solvents, which then react with the resin.
  • the basic catalyst used For purification of the base resins I. the basic catalyst used must be removed. This can be done easily by washing with water using acids for neutralization. In general, for neutralization all acids such. As all organic and / or inorganic acids suitable. Preferred are organic acids having 1 to 6 carbon atoms, more preferably organic acids having 1 to 4 carbon atoms.
  • phase transfer catalysts may optionally be additionally used.
  • phase transfer catalyst 0.01 to 15% by weight, based on the ketone, of a phase transfer catalyst of the general formula (II)
  • X a nitrogen or phosphorus atom
  • Ri, R2, R3, R 4 may be the same or different and are an alkyl radical having 1 to 22 carbon atoms in the carbon chain and / or a phenyl and / or benzyl and
  • Y the anion of an organic acid or a hydroxide ion.
  • alkyl radicals (Ri -4 ) having 1 to 22 C atoms, in particular those having 1 to 12 C atoms, in the carbon chain and / or phenyl and / or benzyl radicals and / or mixtures of both are preferred.
  • anions such strong (on) organic acids such. , Cl “, Br” J ", and also hydroxides, methoxide or acetates.
  • quaternary ammonium salts are cetyldimethylbenzylammonium, tributylbenzyl, trimethylbenzylammonium, Trimethylbenzylammoniumjodid, ammonium chloride Triethylbenzyl- or Thethylbenzylammoniumjodid, tetramethylammonium chloride, tetraethylammonium, tetrabutylammonium.
  • benzyltributylammonium, cetyldimethylbenzylammonium is and / or thethylbenzylammonium chloride used.
  • alkyl radicals having 1 to 22 C atoms and / or phenyl radicals and / or benzyl radicals are preferred for R 1-4 .
  • anions such strong (on) organic acids such. B. Cl “ , Br “ , J " but also hydroxides, methoxides or acetates in question.
  • phase transfer catalyst is used in amounts of from 0.01 to 15, preferably from 0.1 to 10.0, and in particular in amounts of from 0.1 to 5.0% by weight, based on the ketone used, in the polycondensation mixture used.
  • the carbonyl group-containing base resin I. is first prepared.
  • 10 mol of ketone in a 50 to 90% strength methanolic solution, 0 to 5% by mass of a phase transfer catalyst and 1 to 5 mol of an aqueous formaldehyde solution are introduced and homogenized with stirring.
  • the stirrer is stopped after further 0.5 to 5 h stirring at reflux temperature.
  • aqueous formaldehyde solution may be added.
  • the aqueous phase is separated from the resin phase.
  • the crude product is washed with water using an organic acid until a melt sample of the resin appears clear. Then, the resin is dried by distillation.
  • the resins of ketone and aldehyde are hydrogenated in the presence of a catalyst with hydrogen.
  • the carbonyl groups of the ketone-aldehyde resin are converted into a secondary hydroxy group.
  • a part of the hydroxy groups can be split off, so that methylene groups result.
  • the reaction conditions are chosen so that the proportion of unreduced carbonyl groups is low. For illustrative purposes, the following simplified scheme is used:
  • catalysts in principle all compounds can be used which catalyze the hydrogenation of carbonyl groups and the hydrogenation of free formaldehyde to methanol with hydrogen. It is possible to use homogeneous or heterogeneous catalysts; heterogeneous catalysts are particularly preferred.
  • metal catalysts selected from nickel, copper, copper-chromium, palladium, platinum, ruthenium and rhodium alone or in mixture have been suitable proven, particularly preferred are nickel, copper-chromium and ruthenium catalysts.
  • the catalysts may additionally contain doping metals or other modifiers.
  • Typical dopants are z. B. Mo, Fe, Ag, Cr, Ni, V, Ga, In, Bi, Ti, Zr and Mn and the rare earths.
  • Typical modifiers are for.
  • those with which the acid-base properties of the catalysts can be influenced such.
  • the catalysts may be in the form of powders or moldings, such as. As extrudates or pressed powders are used. Full contacts, Raney type catalysts or supported catalysts can be used. Preference is given to Raney type and supported catalysts.
  • Suitable carrier materials are, for.
  • the active metal can be applied in a manner known to those skilled in the carrier material, such as. B. by impregnation, spraying or precipitation.
  • known in the art preparation steps are necessary, such.
  • other auxiliaries such.
  • the catalytic hydrogenation may be carried out in the melt, in solution of a suitable solvent or the hydrogenation product itself as a "solvent.”
  • the optional solvent may, if desired, be separated after completion of the reaction after the solvent used, additional purification steps may be necessary to completely or partially remove minor or less volatile by-products, such as methanol and water Suitable solvents are those in which both the starting material and the product are present in the product dissolve sufficiently and behave inert under the selected hydrogenation. These are z.
  • alcohols preferably n- and i-butanol, cyclic ethers, preferably tetrahydrofuran and dioxane, alkyl ethers, aromatics, such as.
  • B. XyIoI and esters such as. For example, ethyl and butyl acetate.
  • concentration of the resin in the solvent can be varied between 1 and 99%, preferably between 10 and 50%.
  • the total pressure in the reactor is between 50 and 350 bar, preferably 100 to 300 bar.
  • the optimum hydrogenation temperature depends on the hydrogenation catalyst used. Thus, for rhodium catalysts already temperatures of 40 to 75 ° C, preferably from 40 to 60 ° C is sufficient, whereas with Cu or Cu / Cr catalysts higher temperatures are necessary, which are typically between 100 and 140 ° C.
  • the hydrogenation to the resins according to the invention can be carried out in discontinuous or continuous mode. It is also possible to use a semi-continuous procedure in which resin and / or solvent is fed in continuously in a batch reactor, and / or continuously one or more reaction products and / or solvents are removed.
  • the catalyst loading is 0.05 to 4 t of resin per cubic meter of catalyst per hour, preferably 0.1 to 2 t of resin per cubic meter of catalyst per hour.
  • process step II. Of the produced carbonyl-containing resin from process step I. is carried out in continuous fixed bed reactors. Particularly suitable for the preparation of the resins according to the invention are shaft furnaces and tube bundles, which are preferably operated in trickle bed mode. In this case, hydrogen and the resin to be hydrogenated, optionally dissolved in a solvent, are added to the catalyst bed at the top of the reactor. Alternatively, the hydrogen can also be passed in countercurrent from bottom to top. The optionally contained solvent can - if desired - then be separated.
  • the ketone-aldehyde resins (component A) can also be reacted with di- and / or polyisocyanates.
  • the urethanized products thus obtained have improved drying speed and water resistance.
  • Suitable isocyanates are aromatic, aliphatic and / or cycloaliphatic di- and / or polyisocyanates.
  • diisocyanates are cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, phenylene diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, tolylene diisocyanate, bis (isocyanatophenyl) methane, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, such as hexamethylene diisocyanate (HDI) or 1,5-diisocyanato-2-methylpentane (MPDI).
  • HDI hexamethylene diisocyanate
  • MPDI 1,5-diiso
  • polyisocyanates as component B) are the compounds prepared by dimerization, trimerization, allophanatization, biuretization and / or urethanization of simple diisocyanates having more than two isocyanate groups per molecule, for example the reaction products of these simple diisocyanates, such.
  • IPDI, TMDI, HDI and / or H 12 MDI with polyhydric alcohols (eg, glycerol, trimethylolpropane, pentaerythritol) or polyhydric polyamines.
  • isocyanurates obtainable by trimerization of the simple diisocyanates such as IPDI, HDI and H 12 MDI. Very particular preference is given to isocyanurates of IPDI and to reaction products of IPDI, TMDI, HDI and / or H 12 MDI with trimethylolpropane and / or pentaerythritol.
  • the binders B) essential to the invention are used in amounts of from 20 to 90% by weight, preferably from 30 to 75% by weight.
  • binders from the group of polyurethanes, polyacrylates, polyethers, saturated and / or unsaturated polyesters and copolyesters, alkyd resins, polyamides, casein, polyureas, derivatives of cellulose such as.
  • cellulose nitrate, cellulose ethers and / or Celluloseacetobutyrate polyvinyl alcohols and derivatives, polyvinyl acetates, polyvinylpyrolidones, (cyclo) rubbers, natural resins, hydrocarbon resins such.
  • aminoplasts e.g., melamine, benzoguanamine resins
  • polyolefins acrylated polyesters, acrylated polyethers, acrylated epoxy resins, urethane acrylates, epoxy resins, resole
  • chlorinated rubber chlorinated polyester
  • PVDF chlorinated polyester
  • the binders may be foreign and / or self-crosslinking, air-drying (physically drying) and / or oxidatively curing.
  • polyurethanes Preference is given to polyurethanes, polyacrylates, polyethers, saturated and / or unsaturated polyesters and copolyesters, alkyd resins, polyureas, derivatives of cellulose such as cellulose nitrate, cellulose ethers and / or cellulose acetobutyrates, polyvinyl alcohols and derivatives, polyvinyl acetates, polyvinylpyrolidones, natural resins, hydrocarbon resins such as coumarone, indene , Cyclopentadiene resins, terpene resins, maleate resins, phenolic resins, phenol-aldehyde resins, urea-aldehyde resins, ketone-aldehyde resins, ketone resins, aminoplasts such as melamine, benzoguanamine resins, resoles, rosin resins, resinates, used alone or in mixtures
  • the binders may be soluble in organic solvents but also in reactive diluents and / or soluble in water, mixed or dispersible.
  • Component C) is used in amounts of from 0 to 50% by weight, preferably from 10 to 40% by weight.
  • all colorants and / or fillers which are used in the paint industry are suitable. They are selected according to Colohstica aspects and requirements such as color tone, color intensity, brightness, saturation, transparency, hiding power, light fastness, bleeding, compatibility, etc., as well as mechanical aspects and requirements such. Hardness, elasticity, etc ..
  • isoindoline As isoindoline, azo, quinacridone, perylene, dioxazine, phthalocyanine pigments used.
  • metallic effect pigments such as aluminum, copper, copper / zinc and zinc pigments, fire-colored bronzes, iron oxide-aluminum pigments, interference or pearlescent effect pigments such.
  • metal oxide mica pigments, bismuth oxychloride, basic lead carbonate, fish silver or micronized titanium dioxide, platelet-shaped graphite, platelet-shaped iron oxide, multilayer effect pigments from PVD films or produced by the CVD process (Chemical Vapor Deposition) and liquid crystal (polymer) Pigments are used.
  • dyes are used.
  • the component D) essential to the invention is used in amounts of from 5 to 75% by weight, preferably from 5 to 45% by weight.
  • auxiliaries and additives (additives) that are used in the paint industry are suitable.
  • auxiliaries and additives such as, for example, inhibitors, organic solvents, water, surface-active substances, Oxygen and / or radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers and initiators, additives for influencing rheological properties such.
  • auxiliaries and additives such as, for example, inhibitors, organic solvents, water, surface-active substances, Oxygen and / or radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers and initiators, additives for influencing rheological properties such.
  • thixotropic and / or thickening agents leveling agents, anti-skinning agents, defoamers and deaerators, antistatic agents, lubricants, wetting and dispersing agents, crosslinking agents such.
  • melamine-formaldehyde resins blocked and / or unblocked (poly) isocyanates, (poly) amines and / or (poly) carboxylic acids, preservatives such.
  • fungicides and / or biocides thermoplastic additives, plasticizers, matting agents, fire retardants, internal release agents and / or blowing agents.
  • Suitable solvents D are those which are used in the paint industry.
  • z As alcohols, acetates, ketones, ethers, glycol ethers, aliphatic, aromatic, alone or in mixture.
  • reactive diluents which are commonly used in radiation-curing coating materials, such as, for example, B. mono-, or higher functional acrylate monomers, which may also be alkoxylated, and / or vinyl ethers.
  • the preparation of the coating compositions is carried out by intensive mixing of the components at temperatures of 20 to 80 ° C ("Textbook of Lacktechnologie", Th. Brock, M. Groteklaes, P. Mischke, ed. V. Zorll, Vincentz Verlag, Hannover, 1998, Page 229 ff.).
  • Non-liquid components may be first dissolved in suitable solvents or water prior to mixing, then the remaining components are added with stirring.
  • dispersion takes place using suitable aggregates such as, for example, dissolvers, three-rolls, bead mills, ball mills or the like
  • suitable aggregates such as, for example, dissolvers, three-rolls, bead mills, ball mills or the like
  • the formaldehyde content of the coating compositions is below 100 ppm, preferably below 50 ppm and more preferably below 10 ppm.
  • the claimed coating compositions are used for coating various substrates, e.g. Metals, plastics, paper, paper laminates, cardboard, cardboard, inorganic materials such. As ceramics, stone, concrete, gypsum, glass, textiles, fibers, Gewebematehalien, leather, synthetic materials, such as. As artificial leather, wood, films made of plastics, or composites such. B. aluminum-laminated films.
  • the coating compositions are used both indoors and outdoors such. B. as BautenschutzmaschineAlacke, road marking paints, automotive coatings (OEM, Refinish), coil coatings, can coatings, textile finishing, wood coatings, plastic coatings, and for decorative applications, etc. Also for use in adhesives, such. As for the bonding of textiles, leather, paper, plastics, metals and similar materials, such compositions are suitable.
  • the coating materials of the invention can be applied by any known method, e.g. Rolling, brushing, dipping, flooding, spraying, pouring, rolling, spraying, printing, wiping, washing, tumbling, centrifuging.
  • the coating compositions according to the invention are distinguished by a particularly high rate of drying, scratch and water resistance.
  • the films have a high gloss and a low gloss, high color stability and a very high heat and light resistance.
  • the dried, cured or crosslinked films have good adhesion properties on underlying coatings; Also, the intercoat adhesion to overlying layers is positively affected.
  • the claimed coating compositions have a good flow on the substrates used and are free of surface defects, such as craters and wetting disorders.
  • the viscosities of the coating material compositions are adjusted.
  • the claimed coating compositions have a non-volatile content of from 10% to 100% by weight, preferably from 25% to 100%.
  • the invention also relates to the articles coated with the coating material compositions.
  • the formaldehyde content is determined by the lutidine method by HPLC (Official
  • HPLC system with two isocratic pumps, thermostatically controlled reactor, variable UVA / IS detector and evaluation unit, eg. B. Hewlett-Packard HP 1100 with
  • Sample preparation Dissolve 250 mg in 3 ml THF and make up to 25 ml with water
  • the OH number of component A) essential to the invention is determined on the basis of DIN 53240-2 "Determination of the Hydroxyl Number.” Care must be taken to ensure that an acetylation time of 3 hours is exactly maintained.
  • the Gardner color number of component A) essential to the invention is determined in 50% strength solution of the resin in ethyl acetate on the basis of DIN ISO 4630. Also in this way the color number after thermal stress of the invention essential Component A) determined. For this purpose, 5 g of the resin A) are first stored for 24 h at 150 ° C in an air atmosphere. The Gardner color number is then determined in 50% strength solution of the thermally loaded resin in ethyl acetate on the basis of DIN ISO 4630.
  • the solution viscosity is determined according to DIN EN ISO 3219.
  • the solid resin is dissolved in a suitable solvent such as phenoxyethanol, for example with a solids content of 40%.
  • the viscosity is measured at 23 ° C by means of a plate / cone rotation viscometer (1/4 Os).
  • the molecular weight distribution of the component A) essential to the invention is measured by means of gel permeation chromatography in tetrahydrofuran against polystyrene as standard.
  • the polydispersity (Mw / Mn) is calculated from the ratio of weight average (Mw) to number average (Mn).
  • the determination of the melting point / melting range of the component A) essential to the invention is carried out with a capillary melting point measuring device (Büchi B-545) on the basis of DIN 53181.
  • the molecular weight (Mn) is 1000 g / mol
  • the OH number is 300 mg KOH / g
  • the carbonyl number is 10 mg KOH / g.
  • the coating compositions were applied, freed from solvent and subjected to a Xenon 1200 test or stored at 100 ° C. for 24 hours.
  • the CIE-Lab color differences before and after loading between the comparative films without the invention essential component A) and the film with the invention essential component A) were according to DIN 6174 / DIN 5033 with the meter x-rite 8200 spectrophotometer (measurement parameters: without gloss / aperture 12.7mm / illuminant D65 / 10 °).
  • Tropentest Storage of the applied films at 40 ° C and 95% humidity Storage: DIN EN ISO 2812-2 (storage of the test panels at 40 0 C in demineralised water)
  • the coating materials are applied to the substrates to be examined.
  • the fingernail test (see scratch resistance) is carried out for 5 min, 1 h and 24 h.
  • the index finger is pulled over the coating and the degree of damage to the coating is assessed visually.
  • nonvolatile fraction is calculated according to the following equation:
  • the formaldehyde content is determined by the lutidine method by HPLC (Official
  • HPLC system with two isocratic pumps, thermostatically controlled reactor, variable UVA / IS detector and evaluation unit, eg. B. Hewlett-Packard HP 1100 with
  • Sample preparation Dissolve 250 mg in 3 ml THF and make up to 25 ml with water
  • the resin is clear and brittle and has a melting point of 67 ° C.
  • the Gardner color number is 3.8 (50% in ethyl acetate). It is Z. B. in acetates such. Butyl and ethyl acetate, soluble in aromatics such as toluene and xylene. It is insoluble in ethanol.
  • the formaldehyde content is 255 ppm.
  • Example B Adjustment of Example 3 of DE 33 34 631 A1
  • Example 3 of DE 33 34 631 A1 the resin obtained from Example A was continuously hydrogenated at 300 bar and 180 ° C. in a trickle bed reactor.
  • the reactor was filled with 100 ml of Harshaw Ni-5124 contact (available from Engelhard Corp.). Every hour, 50 ml of a 30% strength solution of the resin in i-butanol were added, the pressure in the reactor being kept constant at 300 bar by adjusting the consumed hydrogen.
  • the resin is clear and brittle and has a melting point of 72 ° C.
  • the Gardner color number is 0.8 (50% in ethyl acetate). It is Z. B. in acetates such. Butyl and ethyl acetate, soluble in aromatics such as toluene and xylene. It is insoluble in ethanol.
  • the formaldehyde content is 35 ppm.
  • Example I The resin of Example I was dissolved with 30% heating in i-butanol.
  • the hydrogenation takes place in a continuously operated fixed bed reactor which is filled with 400 ml of a commercially available, silicon-supported copper-chromium contact. At 300 bar and 130 ° C 500 ml_ of the reaction mixture is driven hourly from top to bottom through the reactor (trickle). The pressure is kept constant by the addition of hydrogen.
  • Example I The resin of Example I was dissolved in 30% i-butanol with heating.
  • the hydrogenation takes place in a continuously operated fixed bed reactor which is filled with 400 ml of a commercially available, Raney-type nickel catalyst. At 300 bar and 130 ° C., 400 ml of the reaction mixture are passed through the reactor from top to bottom every hour (trickle-flow method). The pressure is kept constant by the addition of hydrogen.
  • the resins are soluble in common paint solvents.
  • the resins are now soluble in polar solvents such as alcohols.
  • the resins are soluble in dichloromethane, ethyl acetate, butyl acetate, isopropanol, acetone and diethyl ether.
  • the resins of Examples 1-4 are soluble in ethanol in any proportion.
  • the resin of Comparative Example B) is not perfectly soluble in ethanol at concentrations below 10% solids.
  • the resins 1 to 4 essential to the invention have a lower content of free formaldehyde compared to the noninventive resin of Example B. Corresponding to the lower carbonyl number, the color number and the color number after thermal stress are lower. Although these resins have up to 35% higher melting points than the noninventive resin of Example B, the viscosity is comparable to the resin of Example B. This may be explained by the higher polydispersity of the noninventive resin, if desired.
  • Application Example 1 Plastic paint
  • the coatings were applied to polystyrene substrates with a layer thickness of about 30 microns.
  • the course of the blank is unsatisfactory. One recognizes a pronounced intrinsic structure (orange peel). Partially pinholes are visible.
  • the use of the comparative resin B in the formulation V2 leads to better results. The best course and the best wetting reach the coatings according to inventive examples A1 and A2
  • the drying rate is poor (V1).
  • the use of the comparative resin B in the formulation V2 leads to better results; However, a good adhesion is reached only after 24 h, which may be due to the low melting point of the resin of V2 is due.
  • the paints according to inventive examples A1 and A2 have very good values already after 5 minutes. It is thus shown that the resins according to the invention improve the drying rate.
  • the coatings were applied to polystyrene substrates with a layer thickness of about 30 microns. After 24 h, the panels were stored under standard climate, tropical climate and under water for 24 h, then the cross-cut was carried out and the adhesion checked.
  • the CIE-Lab color differences before and after exposure between the comparative films without the invention essential component A) and the film with the invention essential component A) were according to DIN 6174 / DIN 5033 with the meter x-rite 8200 spectrophotometer (measurement parameters: without gloss / aperture 12.7mm / illuminant D65 / 10 0 ).
  • the lacquers were applied to polystyrene substrates with a layer thickness of about 30 ⁇ m. After storage in normal atmosphere for 24 h, the measurement was carried out.
  • the paints were applied to pine wood with a layer thickness of approx. 50 ⁇ m. In the paint of the blank V3, the paint penetrated strongly into the substrate (no sagging). The best topcoat and the best wetting reach the coatings with the addition of a hydrogenated ketone-aldehyde resin
  • the lacquers were applied to pine wood with a layer thickness of about 50 ⁇ m. After storage under normal conditions for 24 h, the

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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)
  • Paints Or Removers (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

La présente invention concerne des compositions de revêtement composées d'au moins un liant, d'une résine cétone/aldéhyde, hydrogénée par un carbonyle, sans formaldéhyde, à base de formaldéhyde faiblement visqueux, présentant un indice de couleur très faible et une très grande résistance à la chaleur et à la lumière et contenant un agent colorant et le cas échéant des auxiliaires et des additifs. L'invention concerne également leur utilisation et leur application.
PCT/EP2008/062499 2007-10-05 2008-09-19 Compositions de revêtement WO2009047102A1 (fr)

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