EP1448735A2 - Feste strahlenhärtende bindemittel - Google Patents
Feste strahlenhärtende bindemittelInfo
- Publication number
- EP1448735A2 EP1448735A2 EP02792735A EP02792735A EP1448735A2 EP 1448735 A2 EP1448735 A2 EP 1448735A2 EP 02792735 A EP02792735 A EP 02792735A EP 02792735 A EP02792735 A EP 02792735A EP 1448735 A2 EP1448735 A2 EP 1448735A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- isocyanates
- groups
- compounds
- binders
- radiation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
Definitions
- the present invention relates to new powder coating binders consisting of (meth) acryloyl group-containing polyurethanes which are applied to a substrate
- oligo- and polyurethanes as powdered binders makes it possible to obtain particularly high-quality coatings.
- EP-A 410 242 describes the production of such binders in organic solvents
- DE-A 19 939 843 teaches solvent-free production using a high mass fraction of 10 to 95% of a crystalline component consisting of a mono- or diisocyanate and a Mono-hydroxyalkyl (meth) acrylate is built up, the synthesis without solvent being made possible by the viscosity-reducing effect of the melted, crystalline component.
- a urethane acrylate which is not stable in storage but can be milled at room temperature is described in DE-A 2 436 186.
- Powder handling must take place below room temperature, otherwise the powder particles will stick together.
- Ovens required for powder coatings can be expected to have higher temperatures than normal room temperatures of 20 to 25 ° C. In practice, a sufficiently high glass transition temperature is therefore required for powder coating. These two criteria are mutually dependent in reverse: a desired high glass transition temperature causes undesirably high viscosities and vice versa. In order to achieve the lowest possible melting temperature, an amorphous powder coating material must have the lowest possible viscosity and at the same time have the lowest possible glass transition temperature.
- Example 40 ° C according to Example 40 that Example 9 according to the invention is sprayable after 7.5 hours, while Example 35 according to DE-A 2 436 186 is not bonded after 2 hours.
- the object on which the invention is based was therefore to provide storage-stable, powdery urethane acrylates which are stable at room temperature and which have no tendency to cake and which can continue to be produced without solvents and are particularly low-viscosity compared to the prior art.
- powder coatings which are readily milled and stable in storage are obtained at room temperature and can also be produced in the melt without solvent if suitable polyols and polyisocyanates are selected and a suitable molecular weight is set. The latter is done by adjusting the operating conditions of the raw materials.
- the invention relates to new urethane acrylates curable by means of high-energy radiation as binders for powder coatings, which, without additives customary in the coating formulation, have a melt viscosity ⁇ at 100 ° C of less than 1000 Pa-s, characterized in that they have a glass transition temperature between 45 and 80 ° C, except a urethane acrylate, which results from the reaction of one
- the invention also relates to a process for the preparation of binders for powder coating materials which can be hardened by means of high-energy radiation and which do not contain
- Coatings customary additives have a melt viscosity ⁇ at 100 ° C of less than 1000 Pa-s, from (meth) acryloyl groups containing polyurethanes without the use of organic solvents, by reacting
- the ratio of the amount of substance A) (mol of NCO groups) to the sum of the amounts of substances with isocyanate-reactive building blocks from B) and C) is between 0.8 and 1.2 and the (meth) acryloyl groups either in B) or in C ) or are contained in both components, characterized in that the ratio of the equivalents of the groups reacting with isocyanates on monofunctional compounds C) to the equivalents of the groups reacting with isocyanates on compounds B) reacting polyfunctionally is less than 1.2 and the Compounds B) reacting polyfunctionally with isocyanates have an average functionality of less than 2.5 and the weight fraction of soft groups in the di- or higher functional isocyanates and in the di- or higher functional components reacting with isocyanates is less than 25% by weight.
- the invention furthermore relates to the use of the binders according to the invention for powder coatings for coating substrates made of wood, metal, plastic, mineral substances and / or substrates already coated therefrom or substrates thereof, which consist of any combinations of the materials mentioned.
- binders according to the invention for powder coatings for coating substrates made of wood, metal, plastic, mineral substances and / or substrates already coated therefrom or substrates thereof, which consist of any combinations of the materials mentioned.
- MDF boards preassembled high-quality goods that already contain temperature-sensitive assemblies but also the coating of furniture, coils, everyday objects, automobile bodies and their attachments.
- the urethane acrylates according to the invention can also be used in combination with one another or with other binders customary in powder coating chemistry. So e.g. with polyesters, polyacrylates, polyethers, polyamides, polycarbonates, which may also contain unsaturated groups.
- the term equivalents (eq.) As is customary in the language used in chemistry, relates to the relative number of reacting groups present in the reaction. According to the invention, these are those which react with isocyanates Groups such as alcohols or amines. In the case of alcohols, for example, when
- Functionality of Compounds Reacting Polyfunctionally with Isocyanates "describes the arithmetic mean weighted with the functionality of the molar proportions of compounds reacting with isocyanates with their functionality. For example, 1 mol of trimethylolpropane (functionality 3) and 2 mol ethylene glycol (functionality 2) are used this results in an average functionality of 1 mol / (1
- the proportion by weight of soft groups required for the description according to the invention relates to the chemical substructures in the at least difunctional structural components.
- These chemical substructures include
- the proportion by weight of soft groups of an individual at least bifunctional structural component is calculated e.g. for hexanediol to the weight fraction of the 6th
- the isocyanates A) can be aliphatic or aromatic: cyclohexyl isocyanate, butyl isocyanate, phenyl isocyanate, toluene isocyanate, 1,4-tetramethylene diisocyanate,
- HDI 1,6-hexamethylene diisocyanate
- 1,8-octamethylene diisocyanate 1,11-undecamethylene diisocyanate
- 1,12-dodecamethylene diisocyanate 2,2,4 or 2,4,4-trimethyl
- TMDI 1,6-hexamethylene diisocyanate
- IPDI 1,3- and 1,4-cyclohexane diisocyanate
- IPDI 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane
- LMCI -isocyanatomethylcyclohexane
- 1,4-phenylene diisocyanate 1,5-naphthylene diisocyanate
- l-isocyanato-2-isocyanatomethylcyclopentane (4,4'- and or 2,4'-
- H12-MDI Diisocyanatodicyclohexylmethane
- XDI xylylene diisocyanate
- TXDI 1,3- and / or 1,4-hexahydro-xylylene diisocyanate
- H6-XDI 1,3- and / or 1,4-hexahydro-xylylene diisocyanate
- H6-TDI 2,4- and / or 2,6-hexahydrotoluenediisocyanate
- TDI 2,6-toluenediisocyanate
- MDI 2,4'- and / or 2,4'-diphenylmethane diisocyanate
- IPDI, TDI, H12-MDI, H6-XDI and mixtures thereof are preferred.
- TDI, IPDI and H12-MDI are particularly preferred.
- Component B) can include polyols such as ethylene glycol, 1,2- and 1,3-propanediol, the isomeric butanediols, neopentyl glycol, 1,6-hexanediol, 2-methyl-propanediol-1, 3, 2,2,4-trimethylpentanediol-1 , 3, 2-n-butyl-2-ethyl-propanediol-1, 3, glycerol monoalkanoates (such as the glycerol monostearates), dimer fatty alcohols, diethylene glycol, triethylene glycol, tetraethylene glycol, 1, 4-dimethylolcyclohexane, dodecanediol, bisphenol -A, hydrogenated bisphenol A, 1,3-hexanediol, 1,3-octanediol, 1,3-decanediol, 3-methylpentanediol-1,5,
- TCD Tricyclodecanediol
- OH-functional esters with an average Mw ⁇ 2000, preferably Mw ⁇ 500, which are obtained by reacting the above-mentioned polyols with ⁇ -caprolactone, can also be used according to the invention.
- Unsaturated are also used
- Esters which, in addition to the alcohols mentioned, consist of unsaturated acids or alcohols such as: maleic acid (anhydride), fumaric acid, itaconic acid, citraconic acid (anhydride), aconitic acid, tetrahydrophthalic acid (anhydride), 3,6-endomethylene-1, 2,3,6 -tetrahydrophthalic acid (anhydride), butenediols.
- unsaturated acids or alcohols such as: maleic acid (anhydride), fumaric acid, itaconic acid, citraconic acid (anhydride), aconitic acid, tetrahydrophthalic acid (anhydride), 3,6-endomethylene-1, 2,3,6 -tetrahydrophthalic acid (anhydride), butenediols.
- Alcohols and amines (meth) acryloyl groups or reaction products essentially consisting of these are also suitable, which are obtained by condensation of n-valent alcohols or amines or amino alcohols with (meth) acrylic acid, mixtures of which are also alcohols, amines or amino alcohols can be used.
- These compounds or product mixtures include, for example, the reaction products of glycerol, Trimethylolpropane and / or pentaerythritol, of low molecular weight alkoxylation products of such alcohols, such as, for example, ethoxylated or propoxylated trimethylolpropane with (meth) acrylic acid.
- DMPS Dimethylolpropionic acid
- N-methyldiethanolamine N-ethyldiethanolamine, N (tert.) - butyldiethanolamine
- N-isopropyldiethanolamine Nn-propyldiethanolamine, N-hexyldiethanolamine
- N-phenyldiethanolamine N-benzyldiethanolamine
- N-benzyldiethanolamine N-benzyldiethanolamine
- N-stearyl-diethanolamine triethanolamine
- Tris (2-aminoethyl) amine N, N-bis (2-hydroxyethyl) ethylenediamine, 2- (2-dimethylaminoethylamino) ethanol, 2- (2-diethylaminoethylamino) ethanol, bis-2- (methylaminoethyl) methylamine, 1,4,7-triethyldiethylene triamine.
- mixtures of various urethane acrylates are also produced, which on the one hand contain DMPS and on the other hand contain a tertiary amine as described above.
- amines can also be used to produce urea acrylates; Ethanolamine, N-methylethanolamine, N- ethylethanolamine, 2-aminopropanol-1, tetramethylxylylenediamine, ethylenediamine, 1, 6-hexamethylenediamine, isophoronediamine (IPDA), (4,4'- and / or 2, 4 '-) diamino-dicyclohexylmethane, (4,4'- and or 2,4' -) diamino-3,3'-dimethyldicyclohexylmethane.
- IPDA isophoronediamine
- ethylene glycol, 1,2- and 1,3-propanediol Preference is given to ethylene glycol, 1,2- and 1,3-propanediol, the isomeric butanediols, neopentylglycol, 1,6-hexanediol, 2-ethylhexanediol-1,3, perhydrobisphenol, 4,8-bis (hydroxymethyl) tricyclo [5.2 .0 (2.6)] - dean (TCD alcohol).
- Ethylene glycol, 1,2-propanediol and 1,4-butanediol are particularly preferred.
- Suitable as component C) are aliphatic and aromatic alcohols such as methanol, ethanol, N-propanol, isopropanol, butanol, hexanol, fatty alcohols, phenols, etc., and in particular hydroxyalkyl (meth) acrylates with 2 to 12 carbon atoms in the alkyl chain, preferably 2 to 4 Carbon atoms in the hydroxyalkyl radical such as hydroxyethyl (meth) acrylate, 2- and 3-hydroxypropyl (meth) acrylate and 2-, 3- and 4-
- hydroxyalkyl (meth) acrylates with 2 to 12 carbon atoms in the alkyl chain, preferably 2 to 4 Carbon atoms in the hydroxyalkyl radical such as hydroxyethyl (meth) acrylate, 2- and 3-hydroxypropyl (meth) acrylate and 2-, 3- and 4-
- Hydroxybutyl (meth) acrylate furthermore OH functional vinyl ethers, such as e.g. Hydroxybutyl vinyl ether and mixtures thereof. Hydroxyethyl acrylate and the isomeric hydroxypropyl acrylates are preferred.
- B) and C) separately in succession separately at the same time or as a mixture.
- the mixture is preferably metered in.
- the addition reaction leading to urethane can be carried out in a manner known per se by means of suitable catalysts such as, for example, tin octoate, Dibutyltin dilaurate or tertiary amines such as dimethylbenzylamine can be accelerated.
- suitable catalysts such as, for example, tin octoate, Dibutyltin dilaurate or tertiary amines such as dimethylbenzylamine can be accelerated.
- the urethane acrylate obtained as the reaction product is usually obtained by adding suitable inhibitors or antioxidants such as, for example, phenols and / or hydroquinones and / or stable N-oxyl radicals and / or phenothiazine or other radical scavengers in amounts of 0.0005 to 0.3% by weight. based on the resin melt, protected from premature and undesired polymerization.
- auxiliaries can be added before, simultaneously and / or after the reaction leading to the polyure
- reaction kneader In addition to a discontinuous procedure, it is also possible to carry out the reactions in a tubular reactor, static mixer or reaction extruder or reaction kneader.
- the shorter reaction times are advantageous, although higher temperatures (80-200 ° C.) can also be used.
- the powder coatings according to the invention have glass transition temperatures of 45 to
- melt viscosities should ideally be minimized. However, this depends in particular on the type of structural components and here also on the molecular weight set, which is largely determined by the ratio of the equivalents of the groups reacting with isocyanates to monofunctional compounds to the equivalents of the groups reacting with isocyanates to compounds with polyfunctional reactions. This ratio is less than 1.2, preferably less than 1.1, particularly preferably less than or equal to 1.
- the average functionality of the compounds which react polyfunctionally with isocyanates is less than 2.5.
- the viscosity can be kept at a low value by varying the monol to polyol ratio (see Examples 36-38).
- the proportion of soft groups in the at least difunctional structural components according to the definition given above may not be higher than 25% by weight, since otherwise it is no longer possible to generate sufficiently high glass transition temperatures.
- the products are then not grindable and non-blocking (see Example 39).
- the (meth) acrylate group-containing polyurethanes / ureas obtained by the process according to the invention are valuable binders for powder coatings. They can be processed without further additives as thermally crosslinkable powder clearcoats (in which case the binder would be identical to the coating agent) or , preferably, with the auxiliaries and additives customary in coating technology, such as, for example, pigments, such as, for example Titanium dioxide, leveling agents such as e.g. Polybutyl acrylate or silicones, deaerating agents such as e.g. Benzoin, tribo-additives such as aliphatic amines and / or other additives and e.g.
- the resulting solid is then ground in a manner known per se and sieved to remove coarse grain fractions, preferably at least those with a grain size above 0.1 mm.
- the powdery coating compositions produced according to the invention can be prepared using conventional powder application methods, such as e.g. electrostatic powder spraying, triboelectric application or whirl sintering, to which substrates to be coated are applied.
- the coatings are then first melted by the action of heat (e.g. using LR emitters), a clear film is formed, if none
- the necessary temperature is above 50 ° C, preferably above 70 ° C, particularly preferably above 90 ° C.
- the coatings can be cured either by heating to 130 to 220 ° C., preferably 150 to 190 ° C., and / or by the action of high-energy radiation such as UV or electron radiation.
- high-energy radiation such as UV or electron radiation.
- electron radiation is generated by means of thermal emission and accelerated via a potential difference.
- the high-energy electrons then hit a titanium foil and are directed onto the binders to be hardened.
- the general principles of electron beam curing are described in "Chemistry & Technology of UV & EB Formulations for Coatings, Inks &Paints", Vol. 1, PKT Oldring (Ed.), SITA Technology, London, England, pp. 101-157, Described in detail in 1991. No photoinitiator is required in electron beam curing.
- photoinitiators are homogeneously incorporated into the coating compositions.
- the compounds normally used are suitable as photoinitiators if they do not negatively influence the powder properties such as flowability and storage stability. Examples of these are 1-hydroxycyclohexylphenyl ketone, benzidimethyl ketal or - in the case of pigmented systems - 2-methyl-1 - (4- (methythio) phenyl-2-mo ⁇ holino-propanone-1 or trimethyl-benzoyl-diphenyl-phosphine oxide.
- the photoinitiators which are used in amounts between 0.1 and 10% by weight, preferably 0.1 to 5% by weight, based on the weight of the paint binder, can be used as a single substance or, because of the frequently advantageous synergistic effects, can also be used in combination.
- thermal curing this can also be done with the addition of thermally decomposing radical formers.
- thermally decomposing radical formers are suitable, as is known to those skilled in the art, e.g. B. peroxy compounds such as tert-butyl perbenzoate, ammonium peroxodisulfate, potassium peroxodisulfate, or azo compounds such as 2,2'-azobis [N- (2-propenyl) - 2-methylpropionamide], l - [(cyano-l-methylethyl) azo] formamide , 2,2'-azobis (N-butyl-2-methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide), 2,2'-azobis ⁇ 2-methyl-N- [2 - (l-Hydroxybutyl)] propionamide ⁇ , 2,2'-azobis ⁇ 2-methyl-N- [2- (1-hydroxybutyl)] propionamide, 2,2'-azobis ⁇ 2-
- Solid form initiators with a melting point below 130 ° C. and a half-life in the minute range at a decomposition temperature above 100 ° C. are particularly suitable.
- the binders for powder coatings according to the invention are suitable for coating substrates made of wood, metal, plastic, mineral substances and / or substrates already coated therefrom or substrates thereof, which consist of any combination of the materials mentioned.
- applications in the industrial painting of MDF boards preassembled high-value goods that already contain temperature-sensitive assemblies such as electronic assemblies, but also the painting of furniture, coils, everyday objects, automobile bodies and their attachments.
- the urethane acrylates according to the invention can also be used in combination with one another or with other binders customary in powder coating chemistry; such as. with polyesters, polyacrylates, polyethers, polyamides, polycarbonates, which may also contain unsaturated groups. Suitable unsaturated groups are acrylate, methacrylate, fumarate, maleate,
- Example 3 Vinyl and / or vinyl ether groups. Acrylate and methacrylate groups are preferred. The quantitative ratios are determined in such a way that the double bond density of the resulting mixture does not fall below 1.0 mol of double bonds per kilogram, since sufficient hardening is then no longer possible. If Example 3 according to the invention is considered with a double bond density of 2.26 mol of double bonds / kg, it follows that for a mixture with a resin which does not contain double bonds, at least 44% of the urethane acrylate from Example 3 must be present.
- the binders according to the invention can also be used as adhesives and sealants.
- UN steel hardening it is a prerequisite that at least one of the two substrates to be bonded or sealed to one another must be transparent to UV radiation, ie generally transparent. A sufficient permeability for electrons must be ensured for electron radiation.
- Suitable substrates consist of wood, metal, plastic, mine ralischen substances and / or already coated substrates or mixture of these substrates.
- the binders according to the invention are also suitable as hardening compounds in molding, injection and die casting processes.
- An object to be coated is introduced into a mold, a distance of at most 1 cm, preferably less than 0.3 cm, remaining between the object surface and the mold.
- the binder according to the invention is then pressed into the mold via an extruder and then cured thermally and / or by means of radiation.
- the melt is transferred to an aluminum pan and allowed to cool.
- the glass temperature of the amorphous, glass-hard, brittle product is 53.0 ° C.
- the complex melt viscosity at 100 ° C is 400 Pa-s.
- the ratio according to the invention of the equivalents (monoalcohol to dialcohol) is 0.6.
- the soft group content is 7.8%, the average functionality with
- ®Desmodur I [1-isocyanato-3-isocyanatoethyl-3,5,5-trimethylcyclohexane (IPDI)] (Bayer AG, Leverkusen, DE) are placed in a flat ground pot and 1.90 at 90 ° C. g 2,5-di-tert-butylhydroquinone, 4.00 g 2,6-di-tert-butyl-4-methylphenol, 2.00 g ®Desmorapid Z (dibutyltin dilaurate) (Bayer AG, Leverkusen, DE) and 4.00 g of p-methoxyphenol dissolved.
- IPDI 1-isocyanato-3-isocyanatoethyl-3,5,5-trimethylcyclohexane
- a mixture of 1179.24 g of hydroxypropyl acrylate and 383.46 g of 1,2-ethanediol is then metered in over the course of 3 hours, while the temperature is kept at 90.degree.
- the viscosity of the resin melt increases, the temperature rises to 116 ° C.
- an NCO content of 0.05% by weight is reached.
- the melt is transferred to an aluminum pan and allowed to cool.
- the glass temperature of the amorphous, glass-hard, brittle product is 49.2 ° C.
- the complex melt viscosity at 100 ° C is 400 Pa-s.
- the invention The ratio of equivalents (mono alcohol to dial alcohol) is 0.73.
- the soft group content is 8.1%, the average functionality of the compounds which react polyfunctionally with isocyanates is 2.
- Example 4 The following examples were carried out analogously to Example 4. The amounts of stabilizer are not listed separately in Table 1, since the amounts used do not differ from Example 4.
- Example 4 The following examples were carried out analogously to Example 4. The amounts of stabilizer are not listed separately in Table 3, since the amounts used do not differ from Example 4.
- the following non-inventive storage-stable (Tg> 45 ° C.) but not low-viscosity (viscosity> 1000 Pas marked in bold) comparative examples have in common the average polyol functionality> 2.5 not according to the invention.
- ®Desmodur T80 (Bayer AG, Leverkusen, DE); IPDI: ®Desmodur I (Bayer AG, Leverkusen, DE); W: ®Desmodur W (Bayer AG, Leverkusen, DE); HEA: hydroxyethyl acrylate.
- Example 39 The following example was produced analogously to example 4.
- the amounts of stabilizer are not listed separately in Table 4, since the amounts used do not differ from Example 4.
- the following non-inventive, non-storage-stable (Tg ⁇ 45 ° C.) comparative example 39 has the non-inventive soft group fraction> 25%.
- the material is finely ground in a mortar and piles of powder (approx. 0.1 g powder) are piled up in an aluminum bowl. 30 ml of air per second are pumped through a glass pipette with a diameter of 1 mm at the extended end using a hose attached to the other side and a pump. The air flow can now be easily directed onto the powder heap at a distance of 0.5 - 1 cm. If the piled-up powder is blown away in fine-grained form, the short test for sprayability is passed. Table 5 summarizes the results of the measurements on Examples 9 and 35.
- Example 3 The product from Example 3 was hexed with a Hexler from Apline type CA 80 a -2. 98.25% by weight of the scrubbed urethane acrylate from Example 3, 1.0% by weight of the leveling agent ®Worlee Add 101 (Worlee-Chemie GmbH, Lauenburg, DE) and 0.75% by weight are placed in a premix vessel .-% Photoinitiator ®Irgacure 2959 (Ciba Specialty Chemicals Inc., Basel, CH) weighed out and premixed in a Premixer ® Prism Pilot 3 (premixer setting: 30 s 2500 RPM).
- the chips obtained were ground on a Neumann & Esser type: ICM 4 mill (classifier 20 m / s, rotor 80 m / s) and sieved with a 120 ⁇ m sieve and immediately with an ITW Gema spray gun (50-60 mV, pressure variable , Dosage variable) sprayed onto a wooden plate pretreated with an intermediate sanding based on ®Roskydal 500 A (Bayer AG, Leverkusen, DE). In a forced air oven, 15 minutes. the film was melted at 110 ° C.
- the hot wooden plate was irradiated with UV light using a device IST S131 P-7FO (CK normal 2, belt speed 10 m / min).
- the film is hard immediately and, after cooling to room temperature and 60 min. Storage assessed.
- the layer thickness obtained was greater than 60 ⁇ m.
- the solvent resistance is determined using an in
- Cotton swab impregnated with butyl acetate which is moved over the film in 100 double strokes with a pressure of approx. 1 kg.
- the film is resistant to solvents and scratches.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Sealing Material Composition (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10156322 | 2001-11-19 | ||
DE10156322A DE10156322A1 (de) | 2001-11-19 | 2001-11-19 | Feste strahlenhärtende Bindemittel |
PCT/EP2002/012374 WO2003044111A2 (de) | 2001-11-19 | 2002-11-06 | Feste strahlenhärtende bindemittel |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1448735A2 true EP1448735A2 (de) | 2004-08-25 |
Family
ID=7705987
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02792735A Withdrawn EP1448735A2 (de) | 2001-11-19 | 2002-11-06 | Feste strahlenhärtende bindemittel |
Country Status (6)
Country | Link |
---|---|
US (1) | US6809126B2 (de) |
EP (1) | EP1448735A2 (de) |
JP (1) | JP4511181B2 (de) |
AU (1) | AU2002358484A1 (de) |
DE (1) | DE10156322A1 (de) |
WO (1) | WO2003044111A2 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012065966A1 (en) | 2010-11-19 | 2012-05-24 | Bayer Materialscience Ag | Multilayer decorative film |
WO2014044694A1 (de) | 2012-09-19 | 2014-03-27 | Bayer Materialscience Ag | Verfahren zur herstellung eines mit einem uv-gehärteten lack versehenen formteil aus kunststoff sowie selbiges formteil |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
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DE10331672A1 (de) * | 2003-07-03 | 2005-01-20 | Bayer Materialscience Ag | Verfahren zur lösemittelfreien Herstellung ethylenisch ungesättigter Polyurethane |
DE10347087A1 (de) * | 2003-10-10 | 2005-05-04 | Bayer Materialscience Ag | Strahlenhärtende Carbonsäureester enthaltende Bindemittel |
DE10356041A1 (de) * | 2003-12-01 | 2005-06-23 | Bayer Materialscience Ag | Feste,strahlenhärtende Bindemittel mit Reaktivverdünnern |
DE10357713A1 (de) * | 2003-12-09 | 2005-07-14 | Bayer Materialscience Ag | Beschichtungsmittel |
US20050187341A1 (en) * | 2004-02-19 | 2005-08-25 | Carmen Flosbach | Process for the production of polyurethane di(meth)acrylates |
WO2006081346A2 (en) * | 2005-01-26 | 2006-08-03 | Chemcraft International, Inc. | Methods of reducing surface checking on wood compositions |
US20060173122A1 (en) * | 2005-02-01 | 2006-08-03 | Carmen Flosbach | Non-aqueous, liquid coating compositions curable by free-radical polymerization of olefinic double bonds |
EP1980579A3 (de) | 2007-04-12 | 2009-05-27 | Bayer MaterialScience LLC | Urethanacrylate für UV-Pulverbeschichtungen |
AU2008289848B2 (en) * | 2007-08-23 | 2013-04-04 | Sumitomo Electric Industries, Ltd. | Powder coating composition for PC strand coating, coating method, and coating film |
JP5578060B2 (ja) * | 2010-01-15 | 2014-08-27 | 東洋インキScホールディングス株式会社 | 活性エネルギー線硬化型接着剤 |
JP2014043594A (ja) * | 2013-12-13 | 2014-03-13 | Fujikura Kasei Co Ltd | 活性エネルギー線硬化型塗料組成物 |
CN110016143B (zh) * | 2019-03-28 | 2021-08-27 | 深圳职业技术学院 | 一种多官能度混杂固化树脂及其制备方法 |
JP7255373B2 (ja) * | 2019-06-10 | 2023-04-11 | 三菱ケミカル株式会社 | 活性エネルギー線硬化性剥離型粘着剤組成物および剥離型粘着シート |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5419895B2 (de) * | 1973-07-27 | 1979-07-18 | ||
DE3924679A1 (de) * | 1989-07-26 | 1991-01-31 | Bayer Ag | Verwendung von (meth)acryloylgruppen aufweisenden polyurethanen als bindemittel fuer pulverlacke |
DE4228514A1 (de) * | 1992-08-27 | 1994-03-03 | Hoechst Ag | Bindemittel für Pulverlacke |
GB2290793B (en) * | 1994-06-20 | 1998-05-06 | Cray Valley Ltd | Powder coating compositions |
DE4432644A1 (de) * | 1994-09-14 | 1996-03-21 | Hoechst Ag | Ungesättigte Polyesterurethanacrylate als Bindemittel für Pulverlacke |
US5922473A (en) * | 1996-12-26 | 1999-07-13 | Morton International, Inc. | Dual thermal and ultraviolet curable powder coatings |
DE19939843A1 (de) | 1999-08-23 | 2001-03-01 | Bayer Ag | Neue Bindemittel für Pulverlacke enthaltend (Meth)Acryloylgruppen aufweisende Oligo- und Polyurethane |
DE19947523A1 (de) * | 1999-10-02 | 2001-04-05 | Basf Coatings Ag | Feststoff, enthaltend über Urethangruppen an die Grundstruktur gebundene Gruppen, die mit aktinischer Strahlung aktivierbare Bindungen enthalten, und ihre Verwendung |
DE19947522A1 (de) * | 1999-10-02 | 2001-04-05 | Basf Ag | Polymerisierbare olefinisch ungesättigte Doppelbindungen enthaltende feste aliphatische Polyurethane auf der Basis linearer Diisocyanate und ihre Verwendung |
DE10058617A1 (de) * | 2000-11-25 | 2002-05-29 | Degussa | UV-Härtbare Pulverlackzusammensetzungen |
-
2001
- 2001-11-19 DE DE10156322A patent/DE10156322A1/de not_active Withdrawn
-
2002
- 2002-11-06 WO PCT/EP2002/012374 patent/WO2003044111A2/de not_active Application Discontinuation
- 2002-11-06 AU AU2002358484A patent/AU2002358484A1/en not_active Abandoned
- 2002-11-06 JP JP2003545740A patent/JP4511181B2/ja not_active Expired - Fee Related
- 2002-11-06 EP EP02792735A patent/EP1448735A2/de not_active Withdrawn
- 2002-11-15 US US10/295,082 patent/US6809126B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
See references of WO03044111A2 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012065966A1 (en) | 2010-11-19 | 2012-05-24 | Bayer Materialscience Ag | Multilayer decorative film |
US9108357B2 (en) | 2010-11-19 | 2015-08-18 | Bayer Intellectual Property Gmbh | Multilayer decorative film |
WO2014044694A1 (de) | 2012-09-19 | 2014-03-27 | Bayer Materialscience Ag | Verfahren zur herstellung eines mit einem uv-gehärteten lack versehenen formteil aus kunststoff sowie selbiges formteil |
US10173355B2 (en) | 2012-09-19 | 2019-01-08 | Covestro Deutschland Ag | Method for producing a molded part made of plastic and provided with a UV-cured paint, and said molded part |
Also Published As
Publication number | Publication date |
---|---|
JP4511181B2 (ja) | 2010-07-28 |
US6809126B2 (en) | 2004-10-26 |
WO2003044111A2 (de) | 2003-05-30 |
WO2003044111A3 (de) | 2003-12-11 |
DE10156322A1 (de) | 2003-06-05 |
US20030134125A1 (en) | 2003-07-17 |
AU2002358484A8 (en) | 2003-06-10 |
AU2002358484A1 (en) | 2003-06-10 |
JP2005509721A (ja) | 2005-04-14 |
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