WO1997033929A1 - Verfahren zur herstellung eines witterungsbeständigen, dekorativen formteils - Google Patents
Verfahren zur herstellung eines witterungsbeständigen, dekorativen formteils Download PDFInfo
- Publication number
- WO1997033929A1 WO1997033929A1 PCT/AT1997/000049 AT9700049W WO9733929A1 WO 1997033929 A1 WO1997033929 A1 WO 1997033929A1 AT 9700049 W AT9700049 W AT 9700049W WO 9733929 A1 WO9733929 A1 WO 9733929A1
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- Prior art keywords
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- hydroxyl
- aminoplast
- isocyanate
- groups
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C5/00—Processes for producing special ornamental bodies
- B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
- B44C5/0469—Ornamental plaques, e.g. decorative panels, decorative veneers comprising a decorative sheet and a core formed by one or more resin impregnated sheets of paper
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/54—Polycondensates of aldehydes
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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
- C08G18/6705—Unsaturated polymers not provided for in the groups C08G18/671, C08G18/6795, C08G18/68 or C08G18/69
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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
- C08G18/68—Unsaturated polyesters
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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
Definitions
- the invention relates to a method for producing a decorative molded part comprising a core layer and weather-resistant decorative layer (s) surrounding it on one or both sides.
- aminoplast resins such as urea-formaldehyde resins or better melamine-formaldehyde resins as the outermost surfaces of coating systems have good scratch resistance.
- melamine resin surfaces can bring scratch resistance of up to approx. 10 Newtons (abbreviated N; according to DIN 53799, part 10).
- N approx. 10 Newtons
- the curing of aminoplast resins is a polycondensation in which water is split off.
- aminoplast resins have proven themselves well as impregnating resins for decorative papers, which, after lamination or compression with carrier materials such as laminated, chipboard or fiberboard, result in a good bond with the carrier material, so that apart from the poor weather resistance - satisfactory decorative parts and panels are created.
- acrylic resins and also polyester resins and polymers made from ester acrylates, urethane acrylates, ether acrylates and epoxy acrylates generally have much better weathering properties, but such systems are in turn not nearly as suitable for impregnating decorative papers as the aforementioned ones Aminoplast or phenoplast resins. In addition, they give only relatively soft, not very scratch-resistant coatings.
- the conventional coating consisting of a single resin layer cannot achieve satisfactory results for the production of molded parts and plates for outdoor use.
- the simplest method in this regard is the lamination of a finished, weather-resistant polyacrylate film as a top and protective layer on a carrier material which is already coated with an aminoplast or phenoplast-impregnated decorative paper.
- This combines the advantages of a decorative paper surface that adheres well to the carrier material and the good decorative paper properties known from amino and phenoplastic impregnations, with the advantages of weather-resistant synthetic resin layers, into which, if necessary - for example to protect the UV-sensitive phenolic nical impregnating resins - substances that absorb UV rays can also be incorporated.
- This coating system now consists of two layers of resins with different chemical constitution, so that a sharp, straight dividing line between the two layers, namely the carrier film and the decorative film, is clearly visible under the microscope in cross section.
- the chemical composition of the two layers is uniform throughout, namely on the one hand the aminoplast or phenoplast impregnating resin layer and on the other hand the cover layer based on the acrylic resin.
- this layer structure achieves a weather-resistant surface, it has the disadvantages that the layers can only be mutually bonded by physical adhesion. forces are connected. However, these adhesive forces only act on the respective layer.
- any mechanical damage to the outermost layer leads to infiltration starting from this point of injury, due to diffusion processes and thus also to large-scale weathering disturbances up to the detachment of the outermost laminate layer.
- the paint systems mentioned are much less scratch-resistant than aminoplast or phenoplast surfaces.
- the coating under the microscope shows a uniform layer which consists of two phases in which one polymer is more or less finely dispersed in the other polymer, but with clear, sharp phase boundaries on its particle surfaces are delimited from the matrix polymer in which it is embedded.
- Such mixtures do not add up the desired properties of the mixture components, so that the finished products essentially only the bad ones
- EP-A-166 153 it is therefore proposed to apply aminoplast-free, unsaturated (meth) acrylate layers as the outermost layer on phenolic or aminoplast-impregnated decorative paper layers.
- This system of (oligomeric) prepolymers consisting of two delimited layers, is first radiation-hardened after the impregnation process and then pressed at a pressure of at least 15 bar and at temperatures of at least 80 ° C. The result is an essentially physical bond between the outermost radiation-crosslinked aminoplast-free acrylate layer and the underlying aminoplast layer, which is chemically and physically delimited from the acrylate layer.
- Electron beam curing polymerizes and optionally crosslinks the acrylate oligomer layer, while the aminoplast layer, which is separated by a sharp phase boundary, condenses into a thermosetting plastic after pressing.
- any pigmentation or decoration is already indicated in the amino-plast undercoat, while only an unpigmented and thus easily non-porous clearcoat is used as the acrylate topcoat.
- Such a system - as explained in more detail by the following sketch - shows weathering, in particular with slight irregularities in the topcoat layer, an undermining at the only physically connected boundary layer between the aminoplast base and the topcoat.
- the top coat layer can therefore easily stand out from the aminoplast substrate or have undesirable shades of gray.
- n R can also be: Layer 2
- the acrylate layer is pressed to different depths into the underlying amino or phenolic layer, so that a toothed phase boundary can be determined in the microscopic cross-sectional image (i.e. the two separate ones) Phases mesh with each other like gears). Satisfactory weather properties and also significantly improved scratch resistance of up to 7 N are achieved with the above-mentioned processes.
- the object of the invention is now to provide a method of the type mentioned at the outset, in which the technical advantages of the individual resin systems such as the aminoplasts or phenoplasts for decorative paper impregnation and those of the acrylates for the outermost protective layer are retained and, in contrast to those Conventional processes between aminoplast or phenol plastic and the acrylate or polyester form an intimate chemical bond in the form of a reaction product of the two.
- a process of the type mentioned is proposed, which is characterized in that in a 1st step onto the backing layer consisting of backing materials impregnated with isocyanate group-reactive aminoplast or phenoplast, a hydroxyl group-containing polyacrylate containing incorporated unsaturated comonomers in the polymer chain, with the exception of those with free or unblocked acrylic and / or methacrylic double bonds (abbreviated UPA) or an unsaturated hydroxyl-containing polyester (abbreviated UPE) with a di- and / or poly-isocyanate, with the boundary layer between aminoplast or phenoplast and hydroxyl group-containing polyacrylate or polyester, a clear mixing and mutual diffusion occurs and a stoichiometric excess of isocyanate component in the form of an NCO group overshoot relative to the existing NCO-reactive groups from the hydroxyl group-containing polyacrylate or polyester and possible NCO consumption by side reactions is used, so that a chemical compound from
- Step in the weatherproof decorative layers thus obtained Film shape is pressed onto the core layer to be coated at a temperature and pressure, as is usually set for the pressing of carrier materials with aminoplast or phenoplast-impregnated decorative films.
- This method ensures that, in contrast to the prior art, an intimate chemical bond is formed in the form of a reduction product between the aminoplast or phenoplast and the acrylate.
- Transition urethane acrylate-URETHANAMINOPLAST mixed phase URETHANAMINOPLAST-URETHANACRYLATE pure phase
- Zone 3 Transitional URETHANAMINOPLAST-aminoplast mixed phase URETHANAMINOPLAST-aminoplast mixed phase
- this method uses a new, third component as a chemical Connection component brought into play, namely substance 3, a urethane aminoplast or a urethane phenoplast, namely the reaction product mentioned from only partially reacted
- the process according to the invention thus gives a coating which adheres well to the boundary layer from the base material to the film, analogously to conventional aminoplast or phenoplast-impregnated decorative papers, which is chemically only a single coating Outer layer can be defined.
- Such products therefore differ fundamentally from the products of the prior art, in which only ever different the substances are physically combined with one another, while in the method according to the invention the coating materials are connected to one another by a real chemical reaction and only then are radically crosslinked, and in the finished product also other substances, such as the radical-induced crosslinked urethane aminoplasts or Urethane phenoplasts are present. Accordingly, such products show even when the surface is sanded to such an extent that the outermost zone has partially been completely removed, and the underlying urethane aminoplast-urethane or urethane phenolic, or even partially except for the purely lowest aminoplast or phenoplastic.
- Paper which can be impregnated with aminoplasts or phenoplasts is suitable as a carrier material.
- nonwovens based on natural or synthetic fibers or on the basis of mixtures thereof are also suitable.
- So-called decorative papers are particularly suitable.
- Laminated boards chipboard, fiberboard such as medium or high density fiberboard (HDF, MDF), woodfibre materials or profile bodies made of such materials.
- HDF medium or high density fiberboard
- MDF medium or high density fiberboard
- a phenolic resin for the impregnation of the carrier material which is preferably present in an aqueous dispersion and is only precondensed to such an extent that it is still mixed with isocyanate groups are reactive and are still flowable at temperatures above 80 ° C., preferably above 100 ° C.
- an aqueous melamine resin for impregnating the carrier material, which is only precondensed to such an extent that it is still capable of reacting with isocyanate groups and at temperatures above 80 ° C., preferably above 100 ° C., is still flowable.
- aminoplast resin preferably a melamine-formaldehyde resin
- UPA or UPE lacquer system pre-condense the aminoplast resin, preferably a melamine-formaldehyde resin, before applying the UPA or UPE lacquer system to a total residual water content of 5 to 25% by weight, preferably 10 to 15% by weight .
- Carrier material has been impregnated to such an extent that it has an NCO titer of at most 25, preferably at most 20, in particular at most 15 milliequivalents of NCO per square meter.
- NCO titer of the aminoplasts or phenoplasts can be determined by pouring a solution of the isocyanate to be used in the process over a sample of 1 dm 2 of the precondensed aminoplast - after shock drying as described below - and heating after heating Reaction temperature determined the isocyanate consumption based on this standard area by back titration with di-n-butylamine and then converted to 1 square meter.
- the total amount of isocyanate to be used according to the invention results from a) the stoichiometric requirement of the UPA or UPE system for (with isocyanate groups) reactive groups, preferably whose hydroxyl groups, expressed in mol% OH, plus b) the isocyanate loss to be calculated in and determined in a preliminary test (see below) by side reactions such as hydrolysis among the
- the proportion of isocyanate which is consumed under process conditions by processes other than the desired main reactions or is lost as a result is determined in a preliminary test, certainly. This proportion is then added to the calculated net excess when using the method according to the invention in order to determine the gross isocyanate requirement required.
- An aminoplast or phenoplast of the same type is produced and precondensed to the same extent as provided for the process according to the invention, with the only difference that the degree of condensation is shock-cooled and freeze-dried in vacuo immediately after the desired ("B state") degree of condensation has been reached.
- the aminoplast or phenoplast B impregnate sample is poured over with an excess of the UPA or UPE isocyanate coating system to be used for the process, brought to the process reaction temperature and then the remaining isocyanate excess is added, for example titrated back using the di-n-butylamine method.
- the NCO loss results from the difference between the NCO consumption on the shock-dried sample and an undried sample due to the residual water content of the aminoplast or phenoplast substrate, which is accessible to the isocyanate in the mixing and boundary phase and is reactive during the curing time.
- the total amount of isocyanate to be used according to the invention then results from a) the stoichiometric requirement of the UPA or UPE system, based on its number of NCO-reactive groups, b) increased by the amount mentioned above.
- unconverted isocyanate groups on the product can optionally be determined after drying by reaction with di-n-butylamine and back-titration of the unconverted amine against bromocresol green.
- the optimal excess of isocyanate can be obtained by reaction of the aminoplast as in the precondensed state, i.e. after predrying with a large excess of isocyanate and then titrating back the unused isocyanate by the di-n-butylamine method.
- Aliphatic and / or cycloaliphatic di- or polyisocyanates are preferably used as isocyanate components, ie the so-called "component B" of the coating system.
- hexamethylene diisocyanate isophorone diisocyanate and their intermolecular addition products such as Desmodur N or L from BAYER, but also so-called masked isocyanates such as "Desmodur AP stable" from BAYER, in particular those which remain stable for some time in aqueous systems at processing temperature but below the curing temperature.
- capped isocyanates preferably have a pot life at room temperature of at least 10 minutes, preferably of at least 1 hour, in particular of at least 3 hours.
- compounds can be used which can release or form isocyanate groups at or just below the curing temperature. This in turn produces reactive di- or polyfunctional isocyanates, preferably those selected from the group of aliphatic and / or cycloaliphatic isocyanates.
- customary urethanization catalysts can be added, preferably immediately before applying UPA or UPE lacquer, such as triethylenediamine (T ⁇ DA), dimethalaminoethyl morpholine (XDM) - so-called DABLOs - or dibutyltin dilaurate, etc. .
- T ⁇ DA triethylenediamine
- XDM dimethalaminoethyl morpholine
- DABLOs dibutyltin dilaurate
- the UPA to be used according to the invention are hydroxyl group-containing polyacrylates containing unsaturated comonomers, with the exception of those with free or unblocked acrylic and / or methacrylic double bonds. Branched and unbranched alkyl acrylates and / or come as monomers for the polyacrylate
- Methacrylates such as methyl acrylate (MA), ethyl acrylate (EA), n-propyl and / or isopropyl acrylate (n / iPA), n-, iso- and / or tert.
- the proportion of these ACDB comonomers is 0.1 to 20 mol%, preferably 2 to 10 mol%.
- ACDB comonomers preference is given to comonomers such as allyl acrylate (AA), vinyl acrylate (VA), mono- and / or di-allyl maleate (MAM, DAM), mono- and / or di-allyl fumarate (MAF, DAF), mono- and / or di-allyl tetrahydrophthalate (MATHPH, DATHPH), 2,2-dimethylpropane diol (1,3) diacrylate (DMPDDA), tert-butyl-ethylene glycol diacrylate (tBuEGDA) or mixtures thereof.
- AA allyl acrylate
- VA vinyl acrylate
- MAM mono- and / or di-allyl maleate
- MAF mono- and / or di-allyl fumarate
- MATHPH 2,2-dimethylpropane diol
- DMPDDA 2,2-dimethylpropane diol
- tBuEGDA tert-butyl-ethylene glycol diacrylate
- the proportions of acidic ACDB comonomers can be used to adjust the water dispersibility of the systems analogously or together with and in consideration of the acrylic acid and / or methacrylic acid proportions described in the systems, which may also be copolymerizable for this purpose, with preference being given to them Is allyl acrylate.
- the UPAs can also contain small amounts, preferably 0.1-20 mol% of di- or polyfunctional, crosslinking components such as mono- or diethylene glycol diacrylate (DEGDA) and / or butanediol diacrylate (BDDA) and / or trimethylolpropane di- or triacrylate (TMPDA, TMPTA ) and / or tripropylene glycol diacrylate (TPGDA), whereby in order to avoid undesirable excessive crosslinking when selecting and dosing, the possibly partially pre-crosslinking effect of ACDB comonomers such as DMPDDA or tBuEGDA must also be taken into account, the ACDB behavior of which is not the same as for the allyl compounds is based on their lower reactivity due to the hyperconjugation of the TT electrons in the allyl group, but on the steric hindrance due to the respective substituents.
- DEGDA mono- or diethylene glycol diacrylate
- BDDA butanediol
- comonomers such as styrene can also be used in the mixture. In this case, it is no longer pure UPA but, for example, styrene acrylates. In these cases, the proportion of such comonomers should not be more than 30 mol%, preferably not more than 10 mol%.
- the methacrylates in particular the MMA, in the acrylic components cause glassier topcoat films and thereby lead to a certain embrittlement, they are particularly preferred in rather minor amounts, in particular only in the range from 0 to 10 mol% used in the range of 1-5 mol%.
- the appropriate mechanical property of the coating can thus be adjusted or the embrittlement or stress crack formation avoided by appropriate combination of the monomers if deformation over narrow radii is necessary to produce the molded part produced according to the invention.
- Acrylic acid units are preferred.
- the proportion of these comonomers may also be at the upper limit, that is to say 5-20 mol%, preferably 5-10 mol%, based on the average total number of monomer units per UPA. Molecule can be chosen.
- TMPDAs When using comonomers to provide post-curable double bonds of the type of mono- or polyunsaturated compounds with double bonds of similar reactivity as To avoid undesirable premature crosslinking, TMPDAs tend to have low proportions, that is to say in the range from 0.1 to 5 mol%, preferably 1 to 3 mol%, based on the average total number of monomer units per UPA molecule.
- the UPE to be used according to the invention are also unsaturated polyesters, that is to say polycondensates from monomers such as fumaric acid (FS) and / or maleic acid (anhydride) (MSA) and / or tetrahydrophthalic acid (THP) which are usually used for the production of unsaturated polyesters, where optionally also phthalic acid (anhydride) (PSA) as acid components and ethylene glycol (EG) and / or diethylene glycol (DEG) and / or propylene glycol (PG) and / or dipropylene glycol (DPG) and / or butanediol (BD) and / or hexanediol (HD) are condensed.
- PSA phthalic acid
- EG ethylene glycol
- DEG diethylene glycol
- PG propylene glycol
- DPG dipropylene glycol
- BD butanediol
- HD hexanediol
- small amounts, preferably 1-10 mol%, in particular 2-6 mol%, of products which can be reacted radically or by radiation such as trimethylolpropane mono- or dialyl ether (TMPMAE or TMPDAE), and 0 to 15 mol%, preferably 2 up to 10 mol% of polyacrylates with one or more hydroxyl group (s) such as trimethylolpropane monoacrylate (TMPMA) and / or trimethylolpropane diacrylate (TMPDA) as the alcohol component and optionally also small amounts of crosslinking agents such as trimethylolpropane (TMP) and / or pentaerythritol ( PER) can be condensed.
- TMPMAE or TMPDAE trimethylolpropane mono- or dialyl ether
- TMPDAE trimethylolpropane diacrylate
- crosslinking agents such as trimethylolpropane (TMP) and / or pentaerythritol (
- hydroxyl group-containing polyacrylates can also be used in a mixture with the UPE lacquer system, the total hydroxyl group content of the UPE resins and their admixed crosslinking agents in the form of a) OH end groups together with b) the chain-centered OH groups for example from condensed TMP in comparison to the acid components used, so that UPE resins with OH end groups are formed in principle and also the content of reactive OH groups (including these
- End groups of the UPE system is 1 to 15 mol%, preferably 1 to 10 mol%, in particular 1 to 5 mol%.
- TMPDA condensable unsaturated compounds
- TMPMA and TMPDAE and TMPMAE are preferred for the UPE systems, and TMPDAE is particularly preferred.
- polyester acrylates are used.
- Both the UPA and the UPE are particularly preferred resins in which the copolymerization or the condensation of the comonomer, which is intended to provide the radiation-curable double bonds, is carried out in such a way that these monomers are used in the preparation of the UPA. or UPE resin are only added when oligomers of a certain chain length have already formed from the other comonomers, so that the ACDB comonomers are statistically uniformly distributed over the UPA or UPA molecule chains.
- UPA systems are preferred, in particular pure UPA systems.
- the two paint components are only combined using the so-called pot life before processing.
- they are only brought together with intimate mixing when applied to the substrate to be coated.
- coating resins as described above in a mixture with 1-50 mol%, preferably 1-30 mol%, based on the central monomer unit of the coating resin polymer, acrylic monomers such as, in particular, butyl acrylate, or 2-ethylhexyl acrylate, or methyl methacrylate or their
- Mixtures can be used as the total acrylic component 1 of the lacquer.
- the urethanization reaction that is the reaction between the isocyanate groups and the hydroxyl groups of the polyacrylate, is post-cured at temperatures above the light-off temperature.
- the temperature range is preferably between 100 and 180 ° C, in particular between 110 and 150 ° C.
- the post-reaction and drying temperature set is advantageously chosen so that on the one hand the formation of vapor bubbles is avoided and on the other hand the methylol groups from the aminoplast are converted as quickly and completely as possible with the isocyanate groups.
- the urethanized UPA or UPE system on the aminoplast or phenoplast-impregnated carrier material, hereinafter referred to as the primary film, is / are radically crosslinked.
- This crosslinking can also take place during the urethanizing lacquer hardening, in that the lacquer is hardened by blasting.
- UV rays can be used as the radiation source in a manner known per se so-called UV sensitizers such as IRGACURE, ESACURE or DAROCURE from CIBA-GEIGY are added to the varnish for UV curing.
- the curing reaction in the coating system can also be triggered by an electron beam.
- the decorative films obtained in this way are aminoplast / urethanaminoplast or phenoplast / urethanphenoplast impregnated carrier materials. They are easy to store and stack and can be used immediately
- Storage at room temperature is preferably not longer than 6 weeks, particularly preferably not longer than 14 days.
- the air humidity during storage should preferably not be above 60% rel.LF for a long time, especially not above 50% rel.LF.
- the coating system thus prefabricated as the only film is applied to the core layer to be coated, which can be, for example, a laminate, particle board or wood fiber board, in a manner known per se, that is to say at temperatures of at least 80 ° C. , preferably at temperatures between 110 and 200 ° C. and at pressures of at least 5 bar, preferably of at least 10 bar, in particular of at least 25 bar, and a pressing time which is preferably in the range of 30 seconds and 10 minutes .
- the minimum pressing time to be used should be observed using the following formula, depending on the selected pressing temperature:
- Example 1 The invention is illustrated by the following examples: Example 1 :
- the precondensed impregnate has an NCO titer (determined by the n-butylamine back titration method) of 14 milliequivalents NCO / m 2 .
- a 2-component acrylate varnish (UPA varnish) in the form of premixed component A (consisting of: UPA varnish resin + pigments + additives) in total is immediately applied to the belt coming out of the dryer in a next station of the impregnation / coating machine all in aqueous dispersion with a total solids content of 50% by weight (including 20 parts by weight of pigments in addition to 5 parts by weight of dispersing agents and additives)) plus component B, which is added to component 1 immediately before application (this is the isocyanate) System).
- UPA varnish 2-component acrylate varnish
- the amount applied after urethanization is 75 g / m 2 based on the content of the lacquer and solid.
- the coated impregnate is fed into a dryer.
- This has the following temperature profile: 5m unheated exhaust zone + 6m floating dryer with 125 ° C + 6m floating dryer with 140 ° C.
- a residual water content of 5% by weight is set and the coated decorative film produced is then stacked.
- a copolymer of 30 mol% 2HEA with 30 mol% EA + 15 mol% BA, 4 mol% HA, 5 mol% MMA and 5 mol% AS, and 1 mol% of DEGDA and 10 mol% AA is used as the coating resin.
- a proportion of 45 parts by weight of paint resin in addition to 5 parts by weight of 2EHA monomer a total of 25% by weight of acrylic component of the total solids content of lacquer component A.
- This paint component is now mixed with the isocyanate component directly on the paint application roller by means of a 2-component metering and a short turbo mixing section.
- the stacked film is subjected to electron beam curing at 200 kV in a separate process step.
- the film hardened by means of electron beams, is pressed in a short-cycle press onto a 10mm thick laminate made of phenolic resin-impregnated papers at a temperature of 150oC and a pressure of 30 bar for 5 minutes.
- a decorative plate with a scratch resistance on the decorative side of 5 Newtons is obtained.
- a procedure is carried out as in Example 1, except that a UPE lacquer is used instead of the UPA lacquer.
- the resin base of this UPE varnish is a mixture of 2 parts by weight of a UPE resin of the type "UPE-LV” in addition to one part by weight of a UPE resin of the type "UPE-M”.
- the entire UPE resin system thus had an average OH content of 4.5 mol%.
- IPDI isophorone diisocyanate
- M 222.28, that is i
- Irgacure 651 solid and 1% by weight of Irgacure 184 from CIBA-GEIGY are added to the coating preparation as UV sensitizers.
- the film is subjected to UV radiation with 6 pieces of 200 W lamps at a throughput speed of 6 m / min.
- the cured film was pressed in a short-cycle press onto a 10 mm thick laminate consisting of phenol resin-impregnated papers at a temperature of 140 ° C and a pressure of 10 bar for 7 minutes.
- a decorative plate with a scratch resistance on the decorative side of 2 Newtons is obtained.
- the composite materials produced by the coating method according to the invention are particularly suitable as facade panels for outdoor use.
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Abstract
Description
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Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97906925A EP0824560A1 (de) | 1996-03-12 | 1997-03-11 | Verfahren zur herstellung eines witterungsbeständigen, dekorativen formteils |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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ATA467/96 | 1996-03-12 | ||
AT46796A AT405151B (de) | 1996-03-12 | 1996-03-12 | Verfahren zur herstellung eines witterungsbeständigen, dekorativen formteils |
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Publication Number | Publication Date |
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WO1997033929A1 true WO1997033929A1 (de) | 1997-09-18 |
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PCT/AT1997/000049 WO1997033929A1 (de) | 1996-03-12 | 1997-03-11 | Verfahren zur herstellung eines witterungsbeständigen, dekorativen formteils |
Country Status (3)
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EP (1) | EP0824560A1 (de) |
AT (1) | AT405151B (de) |
WO (1) | WO1997033929A1 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001055236A1 (de) * | 2000-01-29 | 2001-08-02 | Cognis Deutschland Gmbh & Co. Kg | Verfahren zur herstellung radikalisch nachvernetzter polymere unter einsatz von reaktiven anhydriden |
WO2006074754A1 (de) * | 2005-01-13 | 2006-07-20 | Kunz-Holding Gmbh & Co.Kg | Bahnförmige beschichtungsfolie |
DE102006054890A1 (de) * | 2006-11-20 | 2008-05-21 | WKP Württembergische Kunststoffplatten-Werke GmbH & Co. KG | Beschichtungsmaterialien sowie Verfahren zum Herstellen solcher Beschichtungsmaterialien |
WO2017109118A1 (de) * | 2015-12-23 | 2017-06-29 | Fundermax Gmbh | Schichtpressstoffplatten und verfahren zu ihrer herstellung |
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US4109043A (en) * | 1977-02-11 | 1978-08-22 | Formica Corporation | Low pressure melamine resin laminates |
US4659780A (en) * | 1985-03-18 | 1987-04-21 | E. I. Du Pont De Nemours And Company | Acrylourethane reaction product |
WO1992020724A1 (en) * | 1991-05-17 | 1992-11-26 | Ppg Industries, Inc. | Thermally curable coating composition |
EP0548690A1 (de) * | 1991-12-20 | 1993-06-30 | BASF Corporation | Beschichtungsverfahren für einen Einkomponenten-Klarlack unter Verwendung von blockiertem Isocyanat |
WO1994010211A1 (en) * | 1992-10-30 | 1994-05-11 | Ppg Industries, Inc. | Aminoplast-curable film-forming compositions providing films having resistance to acid etching |
Family Cites Families (3)
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JPS595965B2 (ja) * | 1973-11-30 | 1984-02-08 | 株式会社日立製作所 | デイジタル記録におけるクロツク信号抽出回路 |
DE3418282A1 (de) * | 1984-05-17 | 1985-11-21 | Hoechst Ag, 6230 Frankfurt | Dekorative platte mit verbesserten oberflaecheneigenschaften |
DE3925451C1 (en) * | 1989-08-01 | 1990-09-06 | Th. Goldschmidt Ag, 4300 Essen, De | Decorative film of melamine-formaldehyde resin-coated paper - with outer coating of acrylate copolymer grafted with hardenable styrene-- or methacrylate-copolymer |
-
1996
- 1996-03-12 AT AT46796A patent/AT405151B/de not_active IP Right Cessation
-
1997
- 1997-03-11 EP EP97906925A patent/EP0824560A1/de not_active Withdrawn
- 1997-03-11 WO PCT/AT1997/000049 patent/WO1997033929A1/de not_active Application Discontinuation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4109043A (en) * | 1977-02-11 | 1978-08-22 | Formica Corporation | Low pressure melamine resin laminates |
US4659780A (en) * | 1985-03-18 | 1987-04-21 | E. I. Du Pont De Nemours And Company | Acrylourethane reaction product |
WO1992020724A1 (en) * | 1991-05-17 | 1992-11-26 | Ppg Industries, Inc. | Thermally curable coating composition |
EP0548690A1 (de) * | 1991-12-20 | 1993-06-30 | BASF Corporation | Beschichtungsverfahren für einen Einkomponenten-Klarlack unter Verwendung von blockiertem Isocyanat |
WO1994010211A1 (en) * | 1992-10-30 | 1994-05-11 | Ppg Industries, Inc. | Aminoplast-curable film-forming compositions providing films having resistance to acid etching |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001055236A1 (de) * | 2000-01-29 | 2001-08-02 | Cognis Deutschland Gmbh & Co. Kg | Verfahren zur herstellung radikalisch nachvernetzter polymere unter einsatz von reaktiven anhydriden |
WO2006074754A1 (de) * | 2005-01-13 | 2006-07-20 | Kunz-Holding Gmbh & Co.Kg | Bahnförmige beschichtungsfolie |
DE102006054890A1 (de) * | 2006-11-20 | 2008-05-21 | WKP Württembergische Kunststoffplatten-Werke GmbH & Co. KG | Beschichtungsmaterialien sowie Verfahren zum Herstellen solcher Beschichtungsmaterialien |
WO2017109118A1 (de) * | 2015-12-23 | 2017-06-29 | Fundermax Gmbh | Schichtpressstoffplatten und verfahren zu ihrer herstellung |
US10850486B2 (en) | 2015-12-23 | 2020-12-01 | Fundermax Gmbh | High pressure laminate panel and method for the production thereof |
Also Published As
Publication number | Publication date |
---|---|
ATA46796A (de) | 1998-10-15 |
AT405151B (de) | 1999-06-25 |
EP0824560A1 (de) | 1998-02-25 |
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