CA2103520C - Binders for powder coatings - Google Patents
Binders for powder coatings Download PDFInfo
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- CA2103520C CA2103520C CA 2103520 CA2103520A CA2103520C CA 2103520 C CA2103520 C CA 2103520C CA 2103520 CA2103520 CA 2103520 CA 2103520 A CA2103520 A CA 2103520A CA 2103520 C CA2103520 C CA 2103520C
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Classifications
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- 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
- C08G2150/00—Compositions for coatings
- C08G2150/20—Compositions for powder coatings
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/934—Powdered coating composition
-
- 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.]
Abstract
Binders for powder coatings comprising A) a solid unsat-urated polyester and B) a polyurethane comprising (meth)-acryloyl groups. These polyester-containing mixtures are distinguished by an improved blocking stability as compared with polyurethane alone.
Description
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~2/K 054 Binders for powder coatings EP-A-0,410,242 discloses polyurethanes containing (meth)-acryloyl groups, which are prepared by reacting A) 40-80 parts by weight of an organic polyisocyanate with B) 15-50 parts by weight of a monohydric alcohol containing (meth)acryloyl groups, and C) 2-20 parts by weight of a further structural com-ponent comprising at least one compound which is free from (meth)acryloyl groups and contains groups which are reactive towards isocyanate groups.
These polyurethanes are used as binders in powder coat-ings; however, these coatings in many cases are of insufficient blocking stability, and it has now been found that the blocking stability of these polyurethanes can be improved by blending them with solid unsaturated polyesters. In addition, these polyesters are less expensive than the said polyurethanes, so that replacing part of the polyurethanes by the polyesters in this way brings about an overall cost saving for the powder coatings.
The invention therefore relates to binders for powder coatings comprising A) a solid unsaturated polyester and B) a polyurethane containing (meth)acryloyl groups.
Preferred polyesters are those containing hydroxyl groups and/or carboxyl groups, which have hydroxyl numbers of from 5 to 120, in particular from 10 to 100, mg of KOH/g, a viscosity of less than 100,000, in particular less than 40,000, mPa's and melting points of from 50 to 130°C, preferably from 65 to 120°C. Their acid values are between 2 and 60, in particular between 2 and 40, mg of 2103~2(~
KOI-I/g.
The unsaturated solid polyesters are prepared by the condensation as known per se of unsaturated dicarboxylic acids or their anhydrides, and if desired further satur- , ated dicarboxylic acids, with polyhydric alcohols. The content of unsaturated groups (C=C content) in the polyester should be 2 to 20, preferably 2 to 15 and in particular 2 to 10, %.
Particularly suitable unsaturated dicarboxylic acids are malefic acid and fumaric acid, and their anhydrides.
The saturated dicarboxylic acids may be aliphatic, cycloaliphatic, aromatic and/or heterocyclic in nature and may be substituted, for example by halogen atoms, and/or show unsaturation. Examples of these are:
succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, terephthalic acid, iso-phthalic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, dimethylolpropionic acid, hexahydrophthalic acid, di- and tetrachlorophthalic acid, endomethylenetetrahydrophthalic acid and its hexachloro derivative, glutaric acid, dimeric and trimeric fatty acids, such as oleic acid, if desired as a mixture with monomeric fatty acids; dimethyl terephthalate, bis-glycol terephthalate, and also cyclic monocarboxylic acids, such as benzoic acid, p-tert-butylbenzoic acid or hexahydro-benzoic acid.
Examples of suitable polyhydric alcohols are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, di-(3-hydroxy-ethylbutanediol, 1,6-hexanediol, 1,8-octanediol, neo-pentyl glycol, cyclohexanediol, 1,4-bis(hydroxymethyl)-cyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane, 2,2-bis[4-(~i-hydroxyethoxy)phenyl]propane, 2-methyl-1,3-propanediol, glycerol, trimethylolpropane, 21~D~~~r~
1,2,6-hexanetriol, 1,2,4-butanetriol, tris(~3-hydroxy-ethyl) isocyanurate, trimethylolethane, pentaerythritol, quinitol, mannitol and sorbitol, formose and hydroxy alkylation products thereof, methyl glycoside, and also diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, tri-propylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols and xylylene glycol. Mono-esters and polyesters of lactones, for example e-capro-lactone, or hydroxycarboxylic acids such as hydroxy-pivalic acid, w-hydroxydecanoic acid and w-hydroxycaproic acid can be employed, as can polyesters of the above-mentioned polycarboxylic acids and/or their derivatives and polyphenols, such as hydroquinone, bisphenol A, 4,4'-dihydroxybiphenyl or bis(4-hydroxyphenyl) sulfone, polyesters modified with fatty acids (oil alkyds) and naturally occurring saturated or unsaturated polyesters, their degradation products or transesterification pro-ducts with polyols such as castor oil, tall oil, soya oil and linseed oil, and polyesters of carbonic acid which are obtainable from hydroquinone, diphenylolpropane, p-xylylene glycol, ethylene glycol, butanediol or 1,6-hexanediol and other polyols by conventional conden-sation reactions, for example with phosgene or diethyl or diphenyl carbonate, or from cyclic carbonates such as glycol carbonate or vinylidene carbonate, by polymer-ization in a known manner.
Examples of preferred polyesters also include the reaction products of dicarboxylic acids and glycidyl com-pounds, as described, for example, in DE-A-2,410,513.
Examples of glycidyl compounds which can be used in this respect are esters of 2,3-epoxy-1-propanol with monobasic acids containing 4 to 18 carbon atoms, such as glycidyl palmitate, glycidyl laurate and glycidyl stearate or Cardura E10; alkylene oxides having 4 to 18 carbon atoms, such as butylene oxide, and glycidyl ethers such as octylene glycidyl ether. Dicarboxylic acids which can be used here are all polycarboxylie acids as listed above.
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Preferred components also include monomeric esters, for example dicarboxylic acid bis(hydroxy alcohol) esters, monocarboxylic acid esters with triols and higher polyols .and oligoesters which can be prepared by condensation reactions from raw materials conventional in the chemistry of coatings.
The solid unsaturated polyesters can be obtained in a manner known per se by condensation in an inert-gas atmosphere at temperatures from 100-260°C, preferably 130-220°C, in the melt or by an azeotropic procedure, as described for example in Methoden der Organischen Chemie [Methods of Organic Chemistry] (Houben-Weyl), Vol. 14/2, 1-5, 21-23, 40-44, George Thieme Verlag, Stuttgart, 1963 or in C.R. Martens, Alkyd Resins, 51-59, Reinhold Plastics Appl. Series, Reinhold Publishing Comp., New York, 1961.
The second constituent of the binders according to the invention comprises urethanes containing (meth)acryloyl groups, for example, as described in EP-A-410 242. These polyurethanes are obtained by reacting A) 35-80 parts by weight of a polyisocyanate component comprising at least one organic polyisocyanate with B) 15-70 parts by weight of an alcohol component con-taining (meth)acryloyl groups, and comprising at least one mono- or polyhydric alcohol containing (meth)acryloyl groups, and if desired C) 0-30 parts by weight of a further structural com ponent comprising at least one compound which is free from (meth)acryloyl groups and has groups which are reactive towards isocyanate groups.
These polyurethanes have a melting point in the temper ature range from 40 to 180°C and have a content of olefinic double bonds in the form of (meth)acryloyl groups (calculated as -C=C-, molecular weight = 24) of 2 to 13% by weight.
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_ These polyurethanes are prepared by reacting the above-mentioned starting components A) - C), which components are preferably chosen in terms of their nature and amount such that the resulting polyurethanes are practically 5 free from isocyanate groups and have a number-average molecular weight of 400 to 10,000. The ratio of equiv-alents of all the groups which are reactive toward isocyanate groups to the isocyanate groups is accordingly from 0.9-1.1 to 1.1-0.9.
Component A) comprises at least one organic polyiso-cyanate. Suitable polyisocyanates are any of the organic polyisocyanates which are known from polyurethane chemi-stry, having isocyanate groups which are attached to aliphatic, cycloaliphatic and/or aromatic structures, which preferably have a molecular weight of 150 to 1000, preferably 168 to 300. Suitable examples are 1-iso-cyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), tetramethylxylylene diisocyanate (TMXDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate, 4,4'-diisocyanato-dicyclohexylmethane,4,4'-diisocyanatodiphenylmethane and its technical-grade mixtures with 2,4-diisocyanatodi-phenylmethane and if appropriate the higher homologs of these diisocyanates, 2,4-diisocyanatotoluene and its technical grade mixtures with 2,&-diisocyanatotoluene, and copolymers of a,a'-dimethyl-meta-isopropenylbenzyl isocyanate (TMI).
Also suitable are biuret-, isocyanurate-, urethane- or urea-modified polyisocyanates based on these simple polyisocyanates. These derivatives generally have a molecular weight of up to about 1000. The preparation of such derivatives is described in, for example, US-A-3,124,605, US-A-3,183,112, US-A-3,919,218 or US-A-4,324,879.
It is preferred to use as component A) 2,4-diisocyanato-toluene or its technical-grade mixtures with up to 35% by ~~.0a:~2U
weight, based on the mixture, of 2,6-diisocyanatotoluene, IPDI, TMXDI and/or polyisocyanates obtained by trimerization of IPDI, TMXDI or HDI and containing isocyanurate groups.
Component B) comprises at least one mono- or polyhydric alcohol containing (meth)acryloyl groups. Such alcohols include in particular hydroxyalkyl esters of acrylic acid or methacrylic acid having preferably 2-4 carbon atoms in the hydroxyalkyl radical, such as hydroxyethyl (meth)-acrylate, 2- and 3-hydroxypropyl (meth)acrylate, 2-, S-and 4-hydroxybutyl (meth)acrylate. It is, however, also possible to employ small quantities of reaction products of these hydroxyalkyl acrylates with caprolactone.
However, as an alternative it is also possible to use reaction products of acrylic acid with diepoxides or polyepoxides, for example the diglycidyl ethers of bisphenol A or F, of hexanediol, butanediol or neopentyl glycol and of cyclohexane dimethanol. These products then also possess the properties of component C and can have a chain-lengthening action. Also suitable are trimethyl propane diacrylate and pentaerythritol triacrylate.
Component C) is a compound which has at least two groups which are reactive towards isocyanate groups, in particular at least two, preferably 2-4 and particularly preferably 2-3, alcoholic hydroxyl groups or else, poss-ibly, amine groups. Compounds which are particularly suitable as component C) or as part of component C) have a molecular weight of 62-1000. Examples are ethylene glycol, 1,2- and 1,3-propanediol, neopentyl glycol, glycerol, trimethylolpropane, trishydroxyethyl iso-cyanurate and pentaerythritol or diethanolamine. Also suitable, although less preferred, as component C) or as part of component C) are the higher molecular weight compounds known per se from polyurethane chemistry which have groups, in particular hydroxyl groups, which are reactive toward isocyanate groups, for example the known 21g3~~(~
polyhydroxypolyethers or polyhydroxypolyesters with a molecular weight above 200. Mention is here made of polycaprolactone or polycarbonatediols or trials. It is also possible, however, to include polyamines, which leads to the formation of urea groups and raises the glass transition temperature of these polyurethanes.
Examples of suitable polyamines are ethylenediamine, propylenediamine, 2-methylpentamethylenediamine, hexa-methylenediamine, trimethylhexamethylenediamine, neo-pentyldiamine, octamethylenediamine, triacetonediamine, dioxadecanediamine and higher homologs, cycloaliphatic diamines such as 1,2-, 1,3- or 1,4-cyclohexanediamine, 4,4'-methylenebiscyclohexylamine, 4,4'-isopropylenebiscyclohexylamine, isophoronediamine, tricyclododecenyldiamine, methanediamine, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 3-aminomethyl-1-(3-aminopropyl-1-methyl)-4-methylcyclohexane, m-xylylenediamine,N-methylethylenediamine,hydroxyethyl-amine, hydroxypropylamine, N-aminoethylpiperazine, 2-aminoethylpiperazine, N,N'-dimethylethylenediamine, N,N-dimethylpropylenediamine, aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetra-ethylenepentamine,pentaethylenehexamine,iminobispropyl-amine, methyliminobispropylamine, bis(hexamethylene)-triamine, and tetrapropylenepentamine. , Further suitable amines include those containing hydroxyl groups in addition to secondary or primary amino groups, for example hydroxyethyldiethylenetriamine or bishydroxy-ethyldiethylenetriamine. Also suitable are monoethanol-amine, diethanolamine, aminoethylethanolamine, N-(2-hydroxypropyl)ethylenediamine, mono- or di-(n- or iso)propanolamine, ethylene glycol bispropylamine, neo-pentanolamine, methylethanolamine, 2-(2-aminoethoxy)-ethanol, 3-aminopropyltrialkoxysilane (alkoxy = methoxy, ethoxy or tridecyloxy), 2-amino-2-hydroxymethyl-1,3-propanediol and the like.
2~.03a2U
_$_ Examples of preferred polyurethanes containing (meth)acryloyl groups are the reaction products of trimerized isophorone diisocyanate, containing isocyanate groups, with hydroxylethyl acrylate, or the branched reaction products obtained by reacting isophorone diisocyanate, tetramethylxylylene diisocyanate or diisocyanatotoluene or mixtures thereof with trimethylolpropane, pentaerythritol or trimethylolpropane modified with caprolactone, and subsequently reacting with hydroxyethyl acrylate.
The preparation of the polyurethanes by reacting the said starting components can be carried out in inert solvents, for example acetone, ethyl acetate, butyl acetate or toluene, with preferred reaction temperatures being 20 to 150°C, in particular 20 to 140°C. A preferred procedure comprises initially, in a first reaction step, carrying out the reaction of component A) with component B), followed by the reaction of the resulting reaction product with component C) until the isocyanate content has fallen to below 0.1% by weight. The resulting polyurethane solution in the solvent is then added to water to precipitate the polyurethane, which is then filtered off.
The addition reaction leading to the polyurethane can be accelerated in a known manner using suitable catalysts, such as tin octanoate, dibutyltin dilaurate or tertiary amines such as dimethylbenzylamine. On the other hand, the polyurethane or urethane acrylate obtained as reaction product can be protected, by adding suitable inhibitors and antioxidants such as phenols and/or hydroquinones in amounts of in each case 0.001 to 0.3% by weight, based on polyurethane, against premature and unwanted polymerization. These auxiliaries can be added before, at the same time as and/or after the reaction leading to the polyurethane.
At the end of the reaction the solvent used is removed ?~~~r~2~J
again. This can be effected by, for example, heating the reaction solution under vacuum at 60-100°C. The polyurethanes should not contain more than 1-2% residual solvent.
Solvent-free polyurethanes are also obtained by preparing the products in aprotic water-miscible solvents such as ketones (acetone), THF, DMF or dimethyldiglycol and subsequently precipitating these solutions in an excess of water. After filtering off and drying the solid resin l0 which precipitates, these products contain no residual solvent, which leads to a significant improvement in storage stability.
For application in UV-curable powder coatings these polyurethanes containing (meth)acryloyl groups are mixed with the solid unsaturated polyesters. The mixing ratios can be varied within a wide range depending on the desired coating objective; it is possible and preferred ".
for the proportion of one of the two components to be 10 to 95% by weight, the proportion of the other component then making up the shortfall to 100% by weight.
The mixtures of the two components obtained in this manner result in valuable binders for powder coatings.
They can be processed as heat-crosslinkable powder clear coats without additional additives (in which case the binder would be identical with the coating agent) or else, preferably, together with the auxiliaries and additives conventional in coatings technology, for example pigments, such as titanium dioxide, levelling agents, such as polybutyl acrylate or silicones, and/or other additives. These mixtures are homogenized in extruders or kneaders at temperatures from about 80 to 140°C, preferably 100-120°C. The resulting solid is then milled in a manner known per se and screened to remove coarse fractions, preferably at least those having a particle size greater than 0.1 mm.
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The powdered coating compositions prepared in this way can be applied by conventional powder application methods, for example electrostatic powder spraying or fluidi2ed-bed sintering, to the shaped components to be coated. In the case of wood as the substrate it is also possible, for example prior to electrostatic spraying, to apply a conductivity assistant. In general these binders are suitable both for cold and hot coating; in the case of substrates of large surface area, such as wooden or metal panels or paper webs, vertical coating is also possible without the powder caking together. In this method it is possible in some circumstances to forego electrostatic spraying. The coating compositions according to the invention can be used for coating substrates such as wood, glass, metal, paper or plastic.
The curing of the coatings can be carried out either by heating to temperatures from 130-220°C, preferably 150-190°C, or by the action of high-energy radiation such as UV or electron beams. In the case of crosslinking by W-irradiation it is necessary to add photoinitiators to the coating compositions prior to homogenization.
Suitable photoinitiators are the compounds conventionally employed as described, for example, in the monograph by J. Kosar, Light-Sensitive Systems, J. Wiley & Sons, New York - London, or as described in, for example, UV & EB
Curing Formulations for Printing Inks, Coatings & Paints, ISBN 0 947798 02 1 or in DE-A 38 15 622.
When the aim is to obtain very smooth coatings or to powder-coat thermally sensitive material, it is also possible, and highly advantageous, to follow a procedure wherein, in a first step, the surface of the applied powder is melted using an IR-radiator until the material f lows and then, in a second step, these powder coating melts can be cured using W light or using electron beams.
Particularly suitable photoinitiators are those compounds 2103~~~
which exist in free form and can be powdered. Examples of these are 1-hydroxycyclohexyl phenyl ketone, benzil dimethyl ketal or - in pigmented systems - 2-methyl 1-[4-(methylthio)phenyl]-2-morpholino-1-propanol or trimethylbenzoyldiphenylphosphine oxide.
Also highly suitable are benzoin ethers such as benzoin isopropyl ether, benzil ketals such as benzil dimethyl ketal, and hydroxyalkylphenols such as 2-hydroxy-2-methyl-1-phenylpropan-1-one.
The said photoinitiators which, depending on the intended use of the compositions according to the invention, are employed in amounts of between 0.1 and 10% by weight, ..
preferably 0.1 to 5% by weight, based on the weight of the binder, were used as the individual substance or else, on account of frequent advantageous synergistic effects, can be used in combination with one another.
If curing is carried out using electron beams, the energy applied is between 50 and 500 keV.
Example 1 (unsaturated polyester) 850 parts of ethylene glycol and 1180 parts of tere-phthalic acid and 2 parts of dibutyltin oxide are heated in a water separator to 190-200°C. After all of the terephthalic acid has dissolved, the mixture is cooled to 160°C, and 570 parts of malefic anhydride are 0.3 part of hydroquinone are added. The mixture is then again heated slowly to 195-200°C and stirred at this temperature until an acid number < 25 mg of KOH/g is reached. The product is cooled to give a clear, solid, unsaturated polyester which has an acid number of 24 mg of KOH/g and a hydroxyl number of 36 mg of KOH/g. The melting point of the product is 88-92°C.
Example 2 (acrylate) 1470 parts of an isophoronediisocyanate containing isocyanurate groups (NCO content: 17.1%) are dissolved in ~~~3~2 540 parts of acetone, and 1.1 parts of dibutyltin dilaur ate and 5.3 parts of hydroquinone monomethyl ether are added. After heating to 50°C 696 parts of hydroxyethyl acrylate are added dropwise, and the mixture is then stirred to an NCO content < 0.3%.
The clear solution is diluted with a further 540 parts of acetone and is then added dropwise with vigorous stirring to 18 1 of water; stirring is continued for 30 min, and the precipitate is filtered off with suction and dried at room temperature.
A white powder is obtained having a double bond content of 6.2%, a glass transition temperature of 55°C and a melting point of 85-9o°C.
Example 3 (acrylate) corresponds to Example 1 from EP 0, 410, 242, using acetone instead of ethyl acetate. The procedure was otherwise as in Example 1.
The product has a double bond content of 4.8% and a glass transition temperature of 30°C.
Powder coating preparation and application:
Example 1 558 parts of the unsaturated polyester from Example 1 and 372 parts of the acrylate from Example 2 are mixed with 40 parts Irgacure~ 651 (commercial photoinitiator from Ciba-Geigy) and with 30 parts of Additol0 XL 496 (commer-cial levelling agent from Hoechst AG), extruded and milled to give a powder having an average particle size of 50 ~,m.
After application to cleaned iron panels, the coating films are heated for 10 min at 140°C and then irradiated with a W-radiator (80 W/min, 10 cm distance, 10 m/min).
A hard, solvent- and scratch-resistant coating is obtained.
2~~3~2(~
Example 2 438 parts of the unsaturated polyester from Example 1, 292 parts of the acrylate from Example 2 and 200 parts of titanium dioxide are mixed with 40 parts Darocuree 64263 (commercial photoinitiator from Merck) and with 30 parts of Additol~ XL 496 (commercial levelling agent from Hoechst AG), extruded and milled to give a powder having an average particle size of 50 hem.
After application to cleaned steel panels, the coating films are heated for 10 min at 140°C and then irradiated with a UV-radiator (80 W/cm2, 10 cm distance, 10 m/min).
A hard, solvent- and scratch-resistant coating is obtained.
~2/K 054 Binders for powder coatings EP-A-0,410,242 discloses polyurethanes containing (meth)-acryloyl groups, which are prepared by reacting A) 40-80 parts by weight of an organic polyisocyanate with B) 15-50 parts by weight of a monohydric alcohol containing (meth)acryloyl groups, and C) 2-20 parts by weight of a further structural com-ponent comprising at least one compound which is free from (meth)acryloyl groups and contains groups which are reactive towards isocyanate groups.
These polyurethanes are used as binders in powder coat-ings; however, these coatings in many cases are of insufficient blocking stability, and it has now been found that the blocking stability of these polyurethanes can be improved by blending them with solid unsaturated polyesters. In addition, these polyesters are less expensive than the said polyurethanes, so that replacing part of the polyurethanes by the polyesters in this way brings about an overall cost saving for the powder coatings.
The invention therefore relates to binders for powder coatings comprising A) a solid unsaturated polyester and B) a polyurethane containing (meth)acryloyl groups.
Preferred polyesters are those containing hydroxyl groups and/or carboxyl groups, which have hydroxyl numbers of from 5 to 120, in particular from 10 to 100, mg of KOH/g, a viscosity of less than 100,000, in particular less than 40,000, mPa's and melting points of from 50 to 130°C, preferably from 65 to 120°C. Their acid values are between 2 and 60, in particular between 2 and 40, mg of 2103~2(~
KOI-I/g.
The unsaturated solid polyesters are prepared by the condensation as known per se of unsaturated dicarboxylic acids or their anhydrides, and if desired further satur- , ated dicarboxylic acids, with polyhydric alcohols. The content of unsaturated groups (C=C content) in the polyester should be 2 to 20, preferably 2 to 15 and in particular 2 to 10, %.
Particularly suitable unsaturated dicarboxylic acids are malefic acid and fumaric acid, and their anhydrides.
The saturated dicarboxylic acids may be aliphatic, cycloaliphatic, aromatic and/or heterocyclic in nature and may be substituted, for example by halogen atoms, and/or show unsaturation. Examples of these are:
succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, terephthalic acid, iso-phthalic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, dimethylolpropionic acid, hexahydrophthalic acid, di- and tetrachlorophthalic acid, endomethylenetetrahydrophthalic acid and its hexachloro derivative, glutaric acid, dimeric and trimeric fatty acids, such as oleic acid, if desired as a mixture with monomeric fatty acids; dimethyl terephthalate, bis-glycol terephthalate, and also cyclic monocarboxylic acids, such as benzoic acid, p-tert-butylbenzoic acid or hexahydro-benzoic acid.
Examples of suitable polyhydric alcohols are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, di-(3-hydroxy-ethylbutanediol, 1,6-hexanediol, 1,8-octanediol, neo-pentyl glycol, cyclohexanediol, 1,4-bis(hydroxymethyl)-cyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane, 2,2-bis[4-(~i-hydroxyethoxy)phenyl]propane, 2-methyl-1,3-propanediol, glycerol, trimethylolpropane, 21~D~~~r~
1,2,6-hexanetriol, 1,2,4-butanetriol, tris(~3-hydroxy-ethyl) isocyanurate, trimethylolethane, pentaerythritol, quinitol, mannitol and sorbitol, formose and hydroxy alkylation products thereof, methyl glycoside, and also diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, tri-propylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols and xylylene glycol. Mono-esters and polyesters of lactones, for example e-capro-lactone, or hydroxycarboxylic acids such as hydroxy-pivalic acid, w-hydroxydecanoic acid and w-hydroxycaproic acid can be employed, as can polyesters of the above-mentioned polycarboxylic acids and/or their derivatives and polyphenols, such as hydroquinone, bisphenol A, 4,4'-dihydroxybiphenyl or bis(4-hydroxyphenyl) sulfone, polyesters modified with fatty acids (oil alkyds) and naturally occurring saturated or unsaturated polyesters, their degradation products or transesterification pro-ducts with polyols such as castor oil, tall oil, soya oil and linseed oil, and polyesters of carbonic acid which are obtainable from hydroquinone, diphenylolpropane, p-xylylene glycol, ethylene glycol, butanediol or 1,6-hexanediol and other polyols by conventional conden-sation reactions, for example with phosgene or diethyl or diphenyl carbonate, or from cyclic carbonates such as glycol carbonate or vinylidene carbonate, by polymer-ization in a known manner.
Examples of preferred polyesters also include the reaction products of dicarboxylic acids and glycidyl com-pounds, as described, for example, in DE-A-2,410,513.
Examples of glycidyl compounds which can be used in this respect are esters of 2,3-epoxy-1-propanol with monobasic acids containing 4 to 18 carbon atoms, such as glycidyl palmitate, glycidyl laurate and glycidyl stearate or Cardura E10; alkylene oxides having 4 to 18 carbon atoms, such as butylene oxide, and glycidyl ethers such as octylene glycidyl ether. Dicarboxylic acids which can be used here are all polycarboxylie acids as listed above.
2~~3~~~J
Preferred components also include monomeric esters, for example dicarboxylic acid bis(hydroxy alcohol) esters, monocarboxylic acid esters with triols and higher polyols .and oligoesters which can be prepared by condensation reactions from raw materials conventional in the chemistry of coatings.
The solid unsaturated polyesters can be obtained in a manner known per se by condensation in an inert-gas atmosphere at temperatures from 100-260°C, preferably 130-220°C, in the melt or by an azeotropic procedure, as described for example in Methoden der Organischen Chemie [Methods of Organic Chemistry] (Houben-Weyl), Vol. 14/2, 1-5, 21-23, 40-44, George Thieme Verlag, Stuttgart, 1963 or in C.R. Martens, Alkyd Resins, 51-59, Reinhold Plastics Appl. Series, Reinhold Publishing Comp., New York, 1961.
The second constituent of the binders according to the invention comprises urethanes containing (meth)acryloyl groups, for example, as described in EP-A-410 242. These polyurethanes are obtained by reacting A) 35-80 parts by weight of a polyisocyanate component comprising at least one organic polyisocyanate with B) 15-70 parts by weight of an alcohol component con-taining (meth)acryloyl groups, and comprising at least one mono- or polyhydric alcohol containing (meth)acryloyl groups, and if desired C) 0-30 parts by weight of a further structural com ponent comprising at least one compound which is free from (meth)acryloyl groups and has groups which are reactive towards isocyanate groups.
These polyurethanes have a melting point in the temper ature range from 40 to 180°C and have a content of olefinic double bonds in the form of (meth)acryloyl groups (calculated as -C=C-, molecular weight = 24) of 2 to 13% by weight.
2I03~2~
_ These polyurethanes are prepared by reacting the above-mentioned starting components A) - C), which components are preferably chosen in terms of their nature and amount such that the resulting polyurethanes are practically 5 free from isocyanate groups and have a number-average molecular weight of 400 to 10,000. The ratio of equiv-alents of all the groups which are reactive toward isocyanate groups to the isocyanate groups is accordingly from 0.9-1.1 to 1.1-0.9.
Component A) comprises at least one organic polyiso-cyanate. Suitable polyisocyanates are any of the organic polyisocyanates which are known from polyurethane chemi-stry, having isocyanate groups which are attached to aliphatic, cycloaliphatic and/or aromatic structures, which preferably have a molecular weight of 150 to 1000, preferably 168 to 300. Suitable examples are 1-iso-cyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), tetramethylxylylene diisocyanate (TMXDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate, 4,4'-diisocyanato-dicyclohexylmethane,4,4'-diisocyanatodiphenylmethane and its technical-grade mixtures with 2,4-diisocyanatodi-phenylmethane and if appropriate the higher homologs of these diisocyanates, 2,4-diisocyanatotoluene and its technical grade mixtures with 2,&-diisocyanatotoluene, and copolymers of a,a'-dimethyl-meta-isopropenylbenzyl isocyanate (TMI).
Also suitable are biuret-, isocyanurate-, urethane- or urea-modified polyisocyanates based on these simple polyisocyanates. These derivatives generally have a molecular weight of up to about 1000. The preparation of such derivatives is described in, for example, US-A-3,124,605, US-A-3,183,112, US-A-3,919,218 or US-A-4,324,879.
It is preferred to use as component A) 2,4-diisocyanato-toluene or its technical-grade mixtures with up to 35% by ~~.0a:~2U
weight, based on the mixture, of 2,6-diisocyanatotoluene, IPDI, TMXDI and/or polyisocyanates obtained by trimerization of IPDI, TMXDI or HDI and containing isocyanurate groups.
Component B) comprises at least one mono- or polyhydric alcohol containing (meth)acryloyl groups. Such alcohols include in particular hydroxyalkyl esters of acrylic acid or methacrylic acid having preferably 2-4 carbon atoms in the hydroxyalkyl radical, such as hydroxyethyl (meth)-acrylate, 2- and 3-hydroxypropyl (meth)acrylate, 2-, S-and 4-hydroxybutyl (meth)acrylate. It is, however, also possible to employ small quantities of reaction products of these hydroxyalkyl acrylates with caprolactone.
However, as an alternative it is also possible to use reaction products of acrylic acid with diepoxides or polyepoxides, for example the diglycidyl ethers of bisphenol A or F, of hexanediol, butanediol or neopentyl glycol and of cyclohexane dimethanol. These products then also possess the properties of component C and can have a chain-lengthening action. Also suitable are trimethyl propane diacrylate and pentaerythritol triacrylate.
Component C) is a compound which has at least two groups which are reactive towards isocyanate groups, in particular at least two, preferably 2-4 and particularly preferably 2-3, alcoholic hydroxyl groups or else, poss-ibly, amine groups. Compounds which are particularly suitable as component C) or as part of component C) have a molecular weight of 62-1000. Examples are ethylene glycol, 1,2- and 1,3-propanediol, neopentyl glycol, glycerol, trimethylolpropane, trishydroxyethyl iso-cyanurate and pentaerythritol or diethanolamine. Also suitable, although less preferred, as component C) or as part of component C) are the higher molecular weight compounds known per se from polyurethane chemistry which have groups, in particular hydroxyl groups, which are reactive toward isocyanate groups, for example the known 21g3~~(~
polyhydroxypolyethers or polyhydroxypolyesters with a molecular weight above 200. Mention is here made of polycaprolactone or polycarbonatediols or trials. It is also possible, however, to include polyamines, which leads to the formation of urea groups and raises the glass transition temperature of these polyurethanes.
Examples of suitable polyamines are ethylenediamine, propylenediamine, 2-methylpentamethylenediamine, hexa-methylenediamine, trimethylhexamethylenediamine, neo-pentyldiamine, octamethylenediamine, triacetonediamine, dioxadecanediamine and higher homologs, cycloaliphatic diamines such as 1,2-, 1,3- or 1,4-cyclohexanediamine, 4,4'-methylenebiscyclohexylamine, 4,4'-isopropylenebiscyclohexylamine, isophoronediamine, tricyclododecenyldiamine, methanediamine, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 3-aminomethyl-1-(3-aminopropyl-1-methyl)-4-methylcyclohexane, m-xylylenediamine,N-methylethylenediamine,hydroxyethyl-amine, hydroxypropylamine, N-aminoethylpiperazine, 2-aminoethylpiperazine, N,N'-dimethylethylenediamine, N,N-dimethylpropylenediamine, aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetra-ethylenepentamine,pentaethylenehexamine,iminobispropyl-amine, methyliminobispropylamine, bis(hexamethylene)-triamine, and tetrapropylenepentamine. , Further suitable amines include those containing hydroxyl groups in addition to secondary or primary amino groups, for example hydroxyethyldiethylenetriamine or bishydroxy-ethyldiethylenetriamine. Also suitable are monoethanol-amine, diethanolamine, aminoethylethanolamine, N-(2-hydroxypropyl)ethylenediamine, mono- or di-(n- or iso)propanolamine, ethylene glycol bispropylamine, neo-pentanolamine, methylethanolamine, 2-(2-aminoethoxy)-ethanol, 3-aminopropyltrialkoxysilane (alkoxy = methoxy, ethoxy or tridecyloxy), 2-amino-2-hydroxymethyl-1,3-propanediol and the like.
2~.03a2U
_$_ Examples of preferred polyurethanes containing (meth)acryloyl groups are the reaction products of trimerized isophorone diisocyanate, containing isocyanate groups, with hydroxylethyl acrylate, or the branched reaction products obtained by reacting isophorone diisocyanate, tetramethylxylylene diisocyanate or diisocyanatotoluene or mixtures thereof with trimethylolpropane, pentaerythritol or trimethylolpropane modified with caprolactone, and subsequently reacting with hydroxyethyl acrylate.
The preparation of the polyurethanes by reacting the said starting components can be carried out in inert solvents, for example acetone, ethyl acetate, butyl acetate or toluene, with preferred reaction temperatures being 20 to 150°C, in particular 20 to 140°C. A preferred procedure comprises initially, in a first reaction step, carrying out the reaction of component A) with component B), followed by the reaction of the resulting reaction product with component C) until the isocyanate content has fallen to below 0.1% by weight. The resulting polyurethane solution in the solvent is then added to water to precipitate the polyurethane, which is then filtered off.
The addition reaction leading to the polyurethane can be accelerated in a known manner using suitable catalysts, such as tin octanoate, dibutyltin dilaurate or tertiary amines such as dimethylbenzylamine. On the other hand, the polyurethane or urethane acrylate obtained as reaction product can be protected, by adding suitable inhibitors and antioxidants such as phenols and/or hydroquinones in amounts of in each case 0.001 to 0.3% by weight, based on polyurethane, against premature and unwanted polymerization. These auxiliaries can be added before, at the same time as and/or after the reaction leading to the polyurethane.
At the end of the reaction the solvent used is removed ?~~~r~2~J
again. This can be effected by, for example, heating the reaction solution under vacuum at 60-100°C. The polyurethanes should not contain more than 1-2% residual solvent.
Solvent-free polyurethanes are also obtained by preparing the products in aprotic water-miscible solvents such as ketones (acetone), THF, DMF or dimethyldiglycol and subsequently precipitating these solutions in an excess of water. After filtering off and drying the solid resin l0 which precipitates, these products contain no residual solvent, which leads to a significant improvement in storage stability.
For application in UV-curable powder coatings these polyurethanes containing (meth)acryloyl groups are mixed with the solid unsaturated polyesters. The mixing ratios can be varied within a wide range depending on the desired coating objective; it is possible and preferred ".
for the proportion of one of the two components to be 10 to 95% by weight, the proportion of the other component then making up the shortfall to 100% by weight.
The mixtures of the two components obtained in this manner result in valuable binders for powder coatings.
They can be processed as heat-crosslinkable powder clear coats without additional additives (in which case the binder would be identical with the coating agent) or else, preferably, together with the auxiliaries and additives conventional in coatings technology, for example pigments, such as titanium dioxide, levelling agents, such as polybutyl acrylate or silicones, and/or other additives. These mixtures are homogenized in extruders or kneaders at temperatures from about 80 to 140°C, preferably 100-120°C. The resulting solid is then milled in a manner known per se and screened to remove coarse fractions, preferably at least those having a particle size greater than 0.1 mm.
2~.03~2!~
The powdered coating compositions prepared in this way can be applied by conventional powder application methods, for example electrostatic powder spraying or fluidi2ed-bed sintering, to the shaped components to be coated. In the case of wood as the substrate it is also possible, for example prior to electrostatic spraying, to apply a conductivity assistant. In general these binders are suitable both for cold and hot coating; in the case of substrates of large surface area, such as wooden or metal panels or paper webs, vertical coating is also possible without the powder caking together. In this method it is possible in some circumstances to forego electrostatic spraying. The coating compositions according to the invention can be used for coating substrates such as wood, glass, metal, paper or plastic.
The curing of the coatings can be carried out either by heating to temperatures from 130-220°C, preferably 150-190°C, or by the action of high-energy radiation such as UV or electron beams. In the case of crosslinking by W-irradiation it is necessary to add photoinitiators to the coating compositions prior to homogenization.
Suitable photoinitiators are the compounds conventionally employed as described, for example, in the monograph by J. Kosar, Light-Sensitive Systems, J. Wiley & Sons, New York - London, or as described in, for example, UV & EB
Curing Formulations for Printing Inks, Coatings & Paints, ISBN 0 947798 02 1 or in DE-A 38 15 622.
When the aim is to obtain very smooth coatings or to powder-coat thermally sensitive material, it is also possible, and highly advantageous, to follow a procedure wherein, in a first step, the surface of the applied powder is melted using an IR-radiator until the material f lows and then, in a second step, these powder coating melts can be cured using W light or using electron beams.
Particularly suitable photoinitiators are those compounds 2103~~~
which exist in free form and can be powdered. Examples of these are 1-hydroxycyclohexyl phenyl ketone, benzil dimethyl ketal or - in pigmented systems - 2-methyl 1-[4-(methylthio)phenyl]-2-morpholino-1-propanol or trimethylbenzoyldiphenylphosphine oxide.
Also highly suitable are benzoin ethers such as benzoin isopropyl ether, benzil ketals such as benzil dimethyl ketal, and hydroxyalkylphenols such as 2-hydroxy-2-methyl-1-phenylpropan-1-one.
The said photoinitiators which, depending on the intended use of the compositions according to the invention, are employed in amounts of between 0.1 and 10% by weight, ..
preferably 0.1 to 5% by weight, based on the weight of the binder, were used as the individual substance or else, on account of frequent advantageous synergistic effects, can be used in combination with one another.
If curing is carried out using electron beams, the energy applied is between 50 and 500 keV.
Example 1 (unsaturated polyester) 850 parts of ethylene glycol and 1180 parts of tere-phthalic acid and 2 parts of dibutyltin oxide are heated in a water separator to 190-200°C. After all of the terephthalic acid has dissolved, the mixture is cooled to 160°C, and 570 parts of malefic anhydride are 0.3 part of hydroquinone are added. The mixture is then again heated slowly to 195-200°C and stirred at this temperature until an acid number < 25 mg of KOH/g is reached. The product is cooled to give a clear, solid, unsaturated polyester which has an acid number of 24 mg of KOH/g and a hydroxyl number of 36 mg of KOH/g. The melting point of the product is 88-92°C.
Example 2 (acrylate) 1470 parts of an isophoronediisocyanate containing isocyanurate groups (NCO content: 17.1%) are dissolved in ~~~3~2 540 parts of acetone, and 1.1 parts of dibutyltin dilaur ate and 5.3 parts of hydroquinone monomethyl ether are added. After heating to 50°C 696 parts of hydroxyethyl acrylate are added dropwise, and the mixture is then stirred to an NCO content < 0.3%.
The clear solution is diluted with a further 540 parts of acetone and is then added dropwise with vigorous stirring to 18 1 of water; stirring is continued for 30 min, and the precipitate is filtered off with suction and dried at room temperature.
A white powder is obtained having a double bond content of 6.2%, a glass transition temperature of 55°C and a melting point of 85-9o°C.
Example 3 (acrylate) corresponds to Example 1 from EP 0, 410, 242, using acetone instead of ethyl acetate. The procedure was otherwise as in Example 1.
The product has a double bond content of 4.8% and a glass transition temperature of 30°C.
Powder coating preparation and application:
Example 1 558 parts of the unsaturated polyester from Example 1 and 372 parts of the acrylate from Example 2 are mixed with 40 parts Irgacure~ 651 (commercial photoinitiator from Ciba-Geigy) and with 30 parts of Additol0 XL 496 (commer-cial levelling agent from Hoechst AG), extruded and milled to give a powder having an average particle size of 50 ~,m.
After application to cleaned iron panels, the coating films are heated for 10 min at 140°C and then irradiated with a W-radiator (80 W/min, 10 cm distance, 10 m/min).
A hard, solvent- and scratch-resistant coating is obtained.
2~~3~2(~
Example 2 438 parts of the unsaturated polyester from Example 1, 292 parts of the acrylate from Example 2 and 200 parts of titanium dioxide are mixed with 40 parts Darocuree 64263 (commercial photoinitiator from Merck) and with 30 parts of Additol~ XL 496 (commercial levelling agent from Hoechst AG), extruded and milled to give a powder having an average particle size of 50 hem.
After application to cleaned steel panels, the coating films are heated for 10 min at 140°C and then irradiated with a UV-radiator (80 W/cm2, 10 cm distance, 10 m/min).
A hard, solvent- and scratch-resistant coating is obtained.
Claims (9)
1. A binder for powder coatings, comprising A) a solid unsaturated polyester and B) a polyurethane comprising (meth)acryloyl groups.
2. The binder as claimed in claim 1, comprising 10 to 95% by weight of component A) and 90 to 5% by weight of component B).
3. The binder as claimed in claim 1 or 2, wherein component A) is obtained by condensation of unsaturated dicarboxylic acids or their anhydrides, if desired together with saturated dicarboxylic acids, with polyhydric alcohols.
4. The binder as claimed in any one of claims 1 to 3, wherein component A) has a hydroxyl number of from 5 to 120, an acid number of from 2 to 60, a viscosity of less than 100,000 mPa.s and a melting point of from 50 to 130°C.
5. The binder as claimed in any one of claims 1 to 4, wherein component B) is obtained by reacting A) 35-80 parts by weight of a polyisocyanate component comprising at least one organic polyisocyanate with B) 15-70 parts by weight of an alcohol component containing (meth)acryloyl groups, and comprising at least one mono- or polyhydric alcohol containing (meth)acryloyl groups, and if desired C) 0-30 parts by weight of at least one compound which is free from (meth)acryloyl groups and has groups which are reactive towards isocyanate groups selected from alcoholic hydroxyl groups and amine groups.
6. The binder as claimed in any one of claims 1 to 4, wherein component B) is obtained by reacting a trimerized isophorone diisocyanate containing isocyanurate groups with hydroxyethyl (meth)acrylate.
7. The binder as claimed in any one of claims 1 to 5, wherein component B) is obtained by reacting isophorone diisocyanate, tetramethylxylylene diisocyanate or diisocyanatotoluene or mixtures thereof with trimethylolpropane, pentaerythritol or trimethylolpropane modified with caprolactone, and subsequently reacting with hydroxyethyl acrylate.
8. A use of a binder as claimed in any one of claims 1 to 7 in powder coatings which are cured thermally or by irradiation with UV light or electron beams.
9. A use of a binder as claimed in any one of claims 1 to 7 in powder coatings for wood, glass, plastics, metal and paper.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4228514A DE4228514A1 (en) | 1992-08-27 | 1992-08-27 | Binder for powder coatings |
| DEP4228514.3 | 1992-08-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2103520A1 CA2103520A1 (en) | 1994-02-28 |
| CA2103520C true CA2103520C (en) | 2003-04-01 |
Family
ID=6466569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2103520 Expired - Fee Related CA2103520C (en) | 1992-08-27 | 1993-08-06 | Binders for powder coatings |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US5620751A (en) |
| EP (1) | EP0585742B1 (en) |
| JP (1) | JP3778578B2 (en) |
| KR (1) | KR100297307B1 (en) |
| AT (1) | ATE146512T1 (en) |
| BR (1) | BR9303493A (en) |
| CA (1) | CA2103520C (en) |
| DE (2) | DE4228514A1 (en) |
| DK (1) | DK0585742T3 (en) |
| ES (1) | ES2097407T3 (en) |
| GR (1) | GR3022134T3 (en) |
| MX (1) | MX9305172A (en) |
| MY (1) | MY110209A (en) |
| TW (1) | TW245737B (en) |
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| IT1397259B1 (en) * | 2009-12-04 | 2013-01-04 | Max Canti | PROTECTION AND DECORATION ON CERAMIC BISCUIT OR GLASS IN ENERGY SAVING; LAMINATION OF OTHER RAW SURFACES OF DIFFERENT MATERIALS SUCH AS WOODEN OR LAPID CONGLOMERATED WITH CONTEMPORARY EQUIPMENT OF OPAQUE OR POLISHED, OR EMBOSSED FINISHES. PROCESS, MACHINE, ELEMENTS OBTAINED. |
| US9051397B2 (en) | 2010-10-05 | 2015-06-09 | Basf Se | Oxime ester |
| EP2625166B1 (en) | 2010-10-05 | 2014-09-24 | Basf Se | Oxime ester derivatives of benzocarbazole compounds and their use as photoinitiators in photopolymerizable compositions |
| RU2610090C9 (en) | 2011-04-05 | 2018-04-26 | Басф Се | Photo-latent titanium-oxo-chelate catalysts |
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| CN105051087A (en) | 2012-12-18 | 2015-11-11 | 巴斯夫欧洲公司 | Cationically cross-linkable/polymerizable organic resin composition comprising an iodonium borate and having an acceptable smell |
| CN104870456A (en) | 2012-12-19 | 2015-08-26 | 巴斯夫欧洲公司 | Derivatives of bisacylphosphinic acid, their preparation and use as photoinitiators |
| US8721396B1 (en) * | 2013-03-12 | 2014-05-13 | BTD Wood Powder Coating, Inc. | Method for preparing and buffing a powder coated wood substrate |
| US10234761B2 (en) | 2013-07-08 | 2019-03-19 | Basf Se | Oxime ester photoinitiators |
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| JP6449445B2 (en) | 2014-09-04 | 2019-01-09 | アイ ジー エム マルタ リミテッド | Polycyclic photoinitiator |
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| BR112020013015A2 (en) | 2018-01-26 | 2020-11-24 | Allnex Netherlands B.V. | powder coating composition, process for preparing a powder coating composition, powder coating method, coated articles, use of a catalyst system c, polymer crosslinkable, polymer, and, use of a polymer |
| WO2022236519A1 (en) | 2021-05-10 | 2022-11-17 | Allnex Resins (Shanghai) Co., Ltd. | Powder coating compostion blend |
| CN117730112A (en) | 2021-07-05 | 2024-03-19 | 湛新荷兰有限公司 | Powder coating and crystalline donor and/or acceptor |
| BR112023024895A2 (en) | 2021-07-05 | 2024-02-15 | Allnex Netherlands B V | POWDER COATING COMPOSITION, RETARDANT OF (SEMI) CRYSTALLINE CATALYST T OR PRECURSOR P, METHOD FOR POWDER COATING A SUBSTRATE, AND, ITEMS COATED WITH A POWDER |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3448172A (en) * | 1966-12-08 | 1969-06-03 | Wyandotte Chemicals Corp | Flexibilized polyester resin compositions containing polyurethanes modified with vinyl monomers and process therefor |
| US3660144A (en) * | 1970-12-21 | 1972-05-02 | Ford Motor Co | Unsaturated acrylic rubber and vinyl monomer paint |
| JPS5419895B2 (en) * | 1973-07-27 | 1979-07-18 | ||
| JPS5929308B2 (en) * | 1975-05-22 | 1984-07-19 | 日本ペイント （株） | Method for curing photocurable coating composition |
| JPS5281394A (en) * | 1975-12-29 | 1977-07-07 | Showa Highpolymer Co Ltd | Curable resin compositions |
| JPS5667322A (en) * | 1979-11-05 | 1981-06-06 | Showa Highpolymer Co Ltd | Curable resin composition |
| JPH0745556B2 (en) * | 1987-06-08 | 1995-05-17 | 昭和高分子株式会社 | Curable resin composition |
| DE3924679A1 (en) * | 1989-07-26 | 1991-01-31 | Bayer Ag | USE OF POLYURETHANES CONTAINING (METH) ACRYLOYL GROUPS AS BINDERS FOR POWDER COATINGS |
-
1992
- 1992-08-27 DE DE4228514A patent/DE4228514A1/en not_active Withdrawn
-
1993
- 1993-07-20 TW TW82105771A patent/TW245737B/zh not_active IP Right Cessation
- 1993-08-06 CA CA 2103520 patent/CA2103520C/en not_active Expired - Fee Related
- 1993-08-19 ES ES93113257T patent/ES2097407T3/en not_active Expired - Lifetime
- 1993-08-19 DE DE59304798T patent/DE59304798D1/en not_active Expired - Lifetime
- 1993-08-19 EP EP19930113257 patent/EP0585742B1/en not_active Expired - Lifetime
- 1993-08-19 DK DK93113257T patent/DK0585742T3/en active
- 1993-08-19 AT AT93113257T patent/ATE146512T1/en not_active IP Right Cessation
- 1993-08-23 KR KR1019930016326A patent/KR100297307B1/en not_active IP Right Cessation
- 1993-08-25 JP JP21048293A patent/JP3778578B2/en not_active Expired - Lifetime
- 1993-08-25 MY MYPI93001715A patent/MY110209A/en unknown
- 1993-08-26 BR BR9303493A patent/BR9303493A/en not_active IP Right Cessation
- 1993-08-26 MX MX9305172A patent/MX9305172A/en not_active IP Right Cessation
-
1996
- 1996-03-14 US US08/615,433 patent/US5620751A/en not_active Expired - Lifetime
- 1996-12-20 GR GR960403572T patent/GR3022134T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DK0585742T3 (en) | 1997-01-13 |
| JPH06184467A (en) | 1994-07-05 |
| ES2097407T3 (en) | 1997-04-01 |
| KR100297307B1 (en) | 2001-11-22 |
| TW245737B (en) | 1995-04-21 |
| EP0585742A1 (en) | 1994-03-09 |
| MY110209A (en) | 1998-02-28 |
| US5620751A (en) | 1997-04-15 |
| GR3022134T3 (en) | 1997-03-31 |
| CA2103520A1 (en) | 1994-02-28 |
| EP0585742B1 (en) | 1996-12-18 |
| MX9305172A (en) | 1994-05-31 |
| DE59304798D1 (en) | 1997-01-30 |
| BR9303493A (en) | 1994-03-15 |
| KR940004020A (en) | 1994-03-14 |
| JP3778578B2 (en) | 2006-05-24 |
| DE4228514A1 (en) | 1994-03-03 |
| ATE146512T1 (en) | 1997-01-15 |
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| EEER | Examination request | ||
| MKLA | Lapsed |