EP0152781B1 - Non-tacky carrier web impregnated with a curable aminoplast resin and coated with a heat-curable polyester resin for the modification of the surface of flat materials - Google Patents

Non-tacky carrier web impregnated with a curable aminoplast resin and coated with a heat-curable polyester resin for the modification of the surface of flat materials Download PDF

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Publication number
EP0152781B1
EP0152781B1 EP19850100603 EP85100603A EP0152781B1 EP 0152781 B1 EP0152781 B1 EP 0152781B1 EP 19850100603 EP19850100603 EP 19850100603 EP 85100603 A EP85100603 A EP 85100603A EP 0152781 B1 EP0152781 B1 EP 0152781B1
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EP
European Patent Office
Prior art keywords
carrier web
resin
weight
coated
curable
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.)
Expired
Application number
EP19850100603
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German (de)
French (fr)
Other versions
EP0152781A2 (en
EP0152781A3 (en
Inventor
Jürgen Dr. Fock
Werner Schäfer
Dietmar Dr. Schedlitzki
Manfred Scheiba
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Evonik Operations GmbH
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TH Goldschmidt AG
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Publication date
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Publication of EP0152781A2 publication Critical patent/EP0152781A2/en
Publication of EP0152781A3 publication Critical patent/EP0152781A3/en
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Publication of EP0152781B1 publication Critical patent/EP0152781B1/en
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/121—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyesters, polycarbonates, alkyds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material

Definitions

  • the invention relates to a non-tacky carrier web impregnated with curable aminoplast resin and coated with thermosetting polyester resin for the surface treatment of flat cellulose-based materials, in particular wood-based panels or laminate boards, and the flat materials coated with such carrier webs.
  • the process products are flexible, storable and tack-free. When cured, they form gap-resistant, hard, scratch and abrasion-resistant surface coatings with good weathering ability.
  • thermoplastics and those monomeric compounds in the curable coating resin which are suitable on the one hand for copolymerization with the curable polyester resin and on the other hand able to react with the thermoplastic is of essential importance.
  • the aim is to avoid the formation of interfaces between the thermoplastic and the polyester and to obtain a transparent, haze-free coating.
  • the present invention is therefore based on the object of finding thermosetting coating resin systems which are storable prior to curing and in particular are tack-free and form surfaces in the cured state which result in crack-resistant, glossy, hard and haze-free surfaces, in particular under the conditions of external weathering, and also with long-term surfaces Keep weathering.
  • Curable polyester resins based on neopentyl glycol and isophthalic acid, maleic acid or mixtures of isophthalic acid and maleic acid are known from the prior art.
  • carrier webs are impregnated with curable aminoplast resin and coated with curable polyester resins based on neopentyl glycol
  • the formation of interfaces between the layer of polyester resin and the surface of the carrier web impregnated with aminoplast resin is observed, which, due to the poor compatibility of the resins, cause clouding and other visual disturbances.
  • Due to the inadequate bond of the polyester resin based on neopentyl glycol and maleic acid the mechanical properties of the surface layer are also impaired after curing. does. Often one can observe splitting off of the hardened polyester resin layer from the hardened aminoplast resin in smaller or larger areas.
  • the main component of the coating resin system contains 49 to 80% by weight of the aforementioned curable polyester resin, made from neopentyl glycol and isophthalic acid and / or maleic acid.
  • the coating resin contains 1 to 15% by weight of one or more monomeric compounds which have at least one polymerizable double bond. These require the crosslinking of the polyester and it increase the flow of the coating resin during curing. Since the coating resin is applied to the impregnated carrier web in the form of a solution and the solvent is evaporated off, it is expedient to use compounds with a lower vapor pressure, such as diallyl phthalate or 1,4-divinylbenzene, as polymerizable monomers. Styrene is less suitable for the reasons mentioned above.
  • component c) of the coating resin system is of particular importance.
  • Component c) is contained in the system in an amount of 1 to 15% by weight and, like component b), consists of a monomer or a mixture of several monomers, each of which contains a polymerizable double bond.
  • the monomers of component c) in the monomer molecule additionally have a group reactive with aminoplast resins.
  • the reactive group is preferably an amide or alkoxymethylamide group which is in the vicinity of the polymerizable double bond.
  • suitable monomeric compounds are acrylamide, methylene-bis-acrylamide, N-alkoxy-methylacrylamide and the corresponding derivatives of methacrylic acid.
  • the monomers of component c) are incorporated into the framework of the polyester resin during curing and, on the other hand, react with their reactive group with the aminoplast resin. This results in a chemical bond between the polyester resin and the aminoplast resin in the course of curing without the weather resistance of the polyester resin itself, based on neopentyl glycol, being obviously impaired.
  • the compounds of component c) therefore have a different function than component d) of DE-PS-2 734 669, which is comparable to them.
  • the linear thermoplastic is bonded to the curable polyester by the reactive compounds.
  • Anchoring of the polyester resin with the aminoplast resin of the substrate can only be done very subordinate, since the reaction of the monomeric compound with both the polyester and the thermoplastic takes place first.
  • Component c) thus has another task in the coating resin system of the present invention.
  • the anchorage of the polyester resin based on neopentyl glycol with the aminoplast resin of the substrate could not have been foreseen. It was particularly surprising that the modified polyester resins based on neopentyl glycol would retain their resistance to weathering after curing. Modification of the polyester resins based on neopentyl glycol was not possible due to their incompatibility with thermoplastics.
  • the coating resin still contains 1 to 10% by weight of component d).
  • This is an aminoplast resin etherified with short-chain alcohols.
  • the short-chain alcohols used are in particular those with 1 to 4 carbon atoms.
  • the etherified aminoplast resin also reacts with the monomers of component c) and the aminoplast resin with which the carrier web is impregnated. This also improves the adhesion of the polyester resin coating to the impregnated carrier web.
  • the etherified aminoplast resins commercially available can be used as component d).
  • Component e) is contained in an amount of 0.1 to 8% by weight and is formed by an organic peroxide or by the mixture of monomeric organic peroxides. These serve to crosslink the polyester resin a) and the monomers b) and c).
  • the known diacyl peroxides, dialkyl peroxides, peresters or perketals, such as e.g. Dibenzoyl peroxide, dicumyl peroxide, tert-butyl perbenzoate. or 1,1-di- (tert-butylperoxy) -3.3.5-trimethylcyclohexane can be used.
  • the peroxides should have activation temperatures above 60 ° C.
  • the coating resins also contain 0.5 to 3% by weight of one or more organic acid (s) as component f). These acids accelerate the reaction of component c) with the etherified aminoplast resin d) and the aminoplast resin of the impregnated carrier web.
  • organic acid s
  • An example of a particularly suitable organic acid is p-toluenesulfonic acid.
  • the coating resin can also contain dyes, UV Stabilizers, pigments, metal powder, fillers, antistatic agents and / or release agents can be added. This addition takes place within the framework of the customary prior art.
  • the layer thickness of the curable coating resin is not to be equated with the layer thickness of the cured coating resin, since the curable coating resin is flowable under the curing conditions and can partially penetrate into the impregnated carrier web, the compression pressure maintained during curing having an influence on the layer thickness of the cured polyester coating resin . Since the layer thickness of the coating resin cured under heat and pressure is thus also determined by parameters which are determined by the processing of the product according to the invention, it is not possible to determine the preferred layer thickness of the coating resin before curing.
  • Such a coated carrier web is therefore preferred, in which the layer thickness of the coating resin after the intended use of the impregnated and coated carrier web and curing of the resins is at least 35 ⁇ m.
  • the amount of coating resin required for this before curing must therefore be determined by preliminary tests, in which the parameters of the further treatment are taken into account.
  • the desired layer thickness is achieved if the coating resin is applied to the impregnated carrier web in an amount of at least 100 g m 2 .
  • the impregnated and coated carrier web according to the invention is produced in a manner known per se by first impregnating the carrier webs with the aqueous solution of a curable aminoplast resin precondensate.
  • the cellulose fibers of the carrier web are to be completely covered.
  • 50 to 100% of the paper weight of aminoplast resin, calculated as solid resin, is therefore introduced into the carrier web.
  • the carrier webs obtained in this way are dried while avoiding complete curing of the aminoplast resin.
  • the impregnated carrier webs can be coated in a manner known per se by the polyester resin being dissolved in a solvent such as e.g.
  • the processing of the resin-coated, tack-free carrier web according to the invention is carried out in a manner known per se, for example in single or multi-day surface presses and in molding or profile presses in continuously operating press systems, such as double steel belt systems.
  • the required pressure is 0.3 to 2.0 N / mm 2 , preferably 0.5 to 1.6 N / mm 2.
  • the temperature, measured on the surface of the resin-coated carrier web, should be 130 to 180 ° C.
  • the processing time required depends on the material to be tempered, the processing temperature and the special features of the respective processing method. The guidelines are between 0.5 and 10 minutes. Considerable deviations are possible in individual cases with regard to pressure, temperature and processing time. The optimal processing conditions must therefore be determined in preliminary tests.
  • the structure or gloss level of the surface formed corresponds to the press plate used.
  • a plain-dark brown decorative paper with a weight per unit area of 80 g / m 2 is impregnated with a 50% by weight aqueous solution of a commercially available melamine resin precondensate and dried at 140 ° C. for 1 minute.
  • the impregnated paper web still contains 5% by weight of volatile constituents, predominantly water. Its weight is 140 g / m 2 .
  • the polyester resin solution prepared according to A) is poured onto the paper web thus impregnated using a casting knife. After evaporation of the solvent, the coated and impregnated paper web has a weight of 250 g / m 2 . The proportion of volatile constituents is 7% by weight.
  • Both sides of the coated film are non-tacky.
  • the film is flexible and has good mechanical strength; it can be stored at 20 ° C for at least three months without significant changes.
  • the polyester resin-coated carrier web produced according to B) is used to temper a plywood panel.
  • a heated, hydraulic steel plate press using a siliconized release paper is used for this.
  • a paper web impregnated with a commercially available melamine resin precondensate with a paper weight of 80 g / m 2 and a film weight of 200 g / m 2 as well as a paper web impregnated with a commercially available phenolic resin precondensate with a paper weight of 80 serve as a barrier between the resin-coated carrier web and the plywood board g / m 2 and a film weight of 180 g / m 2 .
  • the pressing takes place at a temperature of 140 ° C and with a pressure of 1.5 N / mm 2 for 10 minutes.
  • the coated plywood surface is completely closed; no signs of graying are found.
  • stress group 1 B is met; no change occurs in the water vapor test according to DIN 53 799.
  • the abrasion test carried out in accordance with DIN 53 799 shows an abrasion of 0.66 mg / rev at 300 to 400 revolutions; The end of the test is reached after 375 revolutions in accordance with DIN 53 799.
  • the hardness determined by an Erichsen tester using a plastic roller, is approximately 180 to 220 p.
  • a film produced according to Examples 1 A) and 1 B) is used to coat a chip mixture bonded with a melamine resin condensate, the proportion of urea resin reinforced with melamine being 25% by weight.
  • a heated stainless steel mold is used for this purpose, with the coating and the molding of a molded part from a chip cake taking place simultaneously.
  • a paper web impregnated with a commercially available melamine resin precondensate with a paper weight of 80 g / m 2 and a film weight of 180 g / m 2 as well as a paper web impregnated with a commercial phenolic resin precondensate with a paper weight serve as a barrier between the synthetic resin-coated film and the particle board of 80 g / m 2 and a film weight of 180 g / M 2 .
  • the pressing takes place at a temperature of 150 ° C and with a pressure of 1.3 N / mm 2 for 3.5 minutes.
  • a sample of the chip mold which is tempered in accordance with 2A) is stored in water in the V-100 cooking test according to DIN 68 763 (flat pressed panels for the building trade) at 100 ° C. for 2 hours. After taking the sample treated in this way from the water bath, no bubbles, no turbidity and no detachment of the cured polyester resin from the substrate are observed.
  • a short weathering test is carried out in accordance with DIN 53 387, in which a sample of the tempered chip mold is exposed at a black panel temperature of 45 ° C. in the cycle for 17 minutes of irradiation / 3 minutes of irradiation and irrigation.
  • the first signs of an attack in the form of a loss of gloss and individual spots can only be detected after an exposure period of 9000 hours.
  • a film is produced according to Example 1 A) and 1 B) with the exception that the use of acrylamide; Methoxymethyl methacrylamide and the butyl etherified melamine resin is dispensed with.
  • the film obtained is processed according to Example 2.
  • a sample of the tempered chip mold is stored in water in the V-100 cooking test according to DIN 68 763 at 100 ° C for 2 hours. After taking the sample treated in this way from the water bath, detachments of the cured polyester resin from the substrate as well as irregular bubbles and a slight graying are observed.
  • a short weathering test is carried out in accordance with DIN 53 387, in which a sample of the tempered chip mold is exposed at a black panel temperature of 45 ° C. in the cycle for 17 minutes of irradiation / 3 minutes of irradiation and irrigation.
  • the first signs of an attack in the form of a significant loss of gloss and bubbles in the polyester resin can be seen after an exposure period of 5000 hours.
  • Example 1A The procedure for preparing the impregnating resin solution is as in Example 1A), with the exception that an additional 45 g of a polyvinyl formal, each containing about 10% acetate and free hydroxyl groups, are added. After the solution has been stored for a short time, there is a separation into two phases, one essentially containing the polyester component and diallyl phthalate prepolymer and the other essentially containing polyvinyl formal. Further processing by pouring the contained mixture into a homogeneous film is not possible due to the incompatibility of the components.
  • a film is produced according to Example 1 A) and 1 B) with the exception that instead of Unsaturated polyester used there 110 g of a polyester based on 2.7 moles of maleic anhydride, 2.5 moles of i-phthalic acid and 5 moles of propylene glycol are used (as is the case in Example 1 a) of DE-PS-2 734 669 was).
  • the film obtained is processed according to Example 2.
  • a short weathering test is carried out in accordance with DIN 53 387, in which a sample of the tempered chip mold is exposed at a black panel temperature of 45 ° C. in the cycle for 17 minutes of irradiation / 3 minutes of irradiation and irrigation.
  • the first signs of an attack in the form of a significant loss of gloss can be seen after an exposure period of 5500 hours.
  • a film is produced according to Examples 1 A) and 1 B), but less polyester resin solution is poured on, so that the weight per unit area of the coated and impregnated paper web is only 190 g / m 2 .
  • the volatile constituents are 6.5% by weight.
  • the film obtained is processed according to Example 2.
  • a short weathering test is carried out in accordance with DIN 53 387, in which a sample of the tempered chip mold is exposed at a black panel temperature of 45 ° C. in the cycle for 17 minutes of irradiation / 3 minutes of irradiation and irrigation.
  • the first signs of an attack in the form of single spots can be seen after an exposure period of 6000 hours.

Description

Die Erfindung betrifft eine mit härtbarem Aminoplastharz imprägnierte und mit wärmehärtbarem Polyesterharz beschichtete, klebfreie Trägerbahn für die Oberflächenvergütung von flächigen Werkstoffen auf Cellulosebasis, insbesondere von Holzwerkstoff- oder Schichtstoffplatten sowie die mit derartigen Trägerbahnen vergüteten flächigen Werkstoffe.The invention relates to a non-tacky carrier web impregnated with curable aminoplast resin and coated with thermosetting polyester resin for the surface treatment of flat cellulose-based materials, in particular wood-based panels or laminate boards, and the flat materials coated with such carrier webs.

Aus der DE-PS-2 734 669 sind mit härbaren Aminoplastharzen und mit härtbarem Polyesterharz beschichtete Trägerbahnen bekannt. Sie sind dadurch gekennzeichnet, dass das Polyesterbeschichtungsharz ein modifiziertes Polyesterharz ist, das aus

  • a) 60 bis 80 Gew.-% eines härtbaren Polyester,
  • b) 1 bis 15 Gew.-% eines Vernetzungsmittels für den Polyester,
  • c) 5 bis 40 Gew.-% eines vorwiegend linearen, hochmolekularen, reaktionsfähige Gruppen aufweisenden Thermoplasten,
  • d) 1 bis 15 Gew.-% eines mindestens eine polymerisierbare Doppelbindung aufweisenden Monomeren mit mindestens einer bei Härtungsbedingungen mit der reaktionsfähigen Gruppe des Thermoplasten reagierenden Gruppe, besteht, sowie
  • e) Härtungskatalysatoren und gegebenenfalls Farbstoffe, Pigmente und/oder Füllstoffe enthält, und wobei, falls die Trägerbahn keine Aminoplastharzimprägnierung aufweist, der Quotient aus Harzgewicht der beharzten Trägerbahn und Papiergewicht der Trägerbahn 0,75 bis 2,0 beträgt.
Carrier webs coated with curable aminoplast resins and with curable polyester resin are known from DE-PS-2 734 669. They are characterized in that the polyester coating resin is a modified polyester resin made from
  • a) 60 to 80% by weight of a curable polyester,
  • b) 1 to 15% by weight of a crosslinking agent for the polyester,
  • c) 5 to 40% by weight of a predominantly linear, high-molecular, reactive group-containing thermoplastic,
  • d) 1 to 15% by weight of a monomer having at least one polymerizable double bond with at least one group which reacts with the reactive group of the thermoplastic under curing conditions, and
  • e) curing catalysts and optionally dyes, pigments and / or fillers, and wherein, if the carrier web has no aminoplast resin impregnation, the quotient of resin weight of the resinous carrier web and paper weight of the carrier web is 0.75 to 2.0.

Die Verfahrensprodukte sind flexibel, lagerfähig und klebfrei. Sie bilden im ausgehärteten Zustand spaltfeste, harte, kratz- und abriebfeste Oberflächenbeschichtungen mit guter Bewitterungsfähigkeit.The process products are flexible, storable and tack-free. When cured, they form gap-resistant, hard, scratch and abrasion-resistant surface coatings with good weathering ability.

Von wesentlicher Bedeutung ist dabei der Gehalt des härtbaren Beschichtungsharzes an Thermoplasten und solchen monomeren Verbindungen, welche einerseits zur Copolymerisation mit dem härtbaren Polyesterharz geeignet und andererseits mit dem Thermoplasten zu reagieren in der Lage sind. Durch diese chemische Anbindung des Thermoplasten an das Polyesterharz wird angestrebt, die Bildung von Grenzflächen zwischen dem Thermoplasten und dem Polyester zu vermeiden und eine transparente, trübungsfreie Beschichtung zu erhalten.The content of thermoplastics and those monomeric compounds in the curable coating resin which are suitable on the one hand for copolymerization with the curable polyester resin and on the other hand able to react with the thermoplastic is of essential importance. Through this chemical bonding of the thermoplastic to the polyester resin, the aim is to avoid the formation of interfaces between the thermoplastic and the polyester and to obtain a transparent, haze-free coating.

Diese Produkte des Standes der Technik haben sich bewährt und werden insbesondere zur Beschichtung von Holzwerkstoffplatten oder Schichtstoffen verwendet, die einer Aussenbewitterung ausgesetzt sind. Es hat sich jedoch gezeigt, dass bei einer längeren Aussenbewitterung und damit verbundenem häufigen Temperaturwechsel gelegentlich Vergrauungen und Eintrübungen der Oberfläche zu beobachten sind, welche das optische Bild der vergüteten Platten beeinträchtigen und, insbesondere wenn es im Laufe der Zeit zu einer Ausbildung von Mikrorissen kommt, auch tiefer gehende Beschädigungen der Oberflächenschicht eintreten können.These products of the prior art have proven themselves and are used in particular for coating wood-based panels or laminates which are exposed to external weathering. However, it has been shown that with prolonged outdoor weathering and the associated frequent changes in temperature, graying and clouding of the surface can occasionally be observed, which impair the optical image of the coated panels and, in particular if microcracks develop over time, deeper damage to the surface layer can also occur.

Der vorliegenden Erfindung liegt deshalb die Aufgabe zugrunde, wärmehärtbare Beschichtungsharzsysteme aufzufinden, welche vor der Aushärtung lagerfähig und insbesondere klebfrei sind und im ausgehärteten Zustand Oberflächen ausbilden, die insbesondere unter den Bedingungen der Aussenbewitterung rissfeste, glänzende, harte und trübungsfreie Oberflächen ergeben und diese auch bei langzeitiger Bewitterung behalten.The present invention is therefore based on the object of finding thermosetting coating resin systems which are storable prior to curing and in particular are tack-free and form surfaces in the cured state which result in crack-resistant, glossy, hard and haze-free surfaces, in particular under the conditions of external weathering, and also with long-term surfaces Keep weathering.

Diese Aufgabe wird erfindungsgemäss dadurch gelöst, dass das Beschichtungsharz aus

  • a) 49 bis 80 Gew.-% eines härtbaren Polyesterharzes, hergestellt aus Neopentylglykol und Isophthalsäure und/oder Maleinsäure,
  • b) 1 bis 15 Gew.-% eines oder mehrerer Monomerer mit mindestens einer polymerisierbaren Doppelbindung,
  • c) 1 bis 15 Gew.-% eines oder mehrerer Monomerer mit jeweils einer polymerisierbaren Doppelbindung und einer mit Aminoplastharzen reaktiven Gruppe,
  • d) 1 bis 10 Gew.-% eines oder mehrerer veretherter Aminoplastharze(s),
  • e) 0,1 bis-8 Gew.-% eines oder mehrerer organischer Peroxide(s),
  • f) 0,05 bis 3 Gew.-% einer oder mehrerer organischer Säure(n), besteht.
According to the invention, this object is achieved in that the coating resin is made of
  • a) 49 to 80% by weight of a curable polyester resin, made from neopentyl glycol and isophthalic acid and / or maleic acid,
  • b) 1 to 15% by weight of one or more monomers with at least one polymerizable double bond,
  • c) 1 to 15% by weight of one or more monomers each having a polymerizable double bond and a group reactive with aminoplast resins,
  • d) 1 to 10% by weight of one or more etherified aminoplast resins (s),
  • e) 0.1 to 8% by weight of one or more organic peroxides,
  • f) 0.05 to 3% by weight of one or more organic acid (s).

Härtbare Polyesterharze auf der Basis von Neopentylglykol und Isophthalsäure, Maleinsäure oder Isophthalsäure- und Maleinsäuregemischen sind aus dem Stand der Technik bekannt. Imprägniert man jedoch Trägerbahnen mit härtbarem Aminoplastharz und beschichtet diese mit härtbaren Polyesterharzen auf Basis Neopentylglykol, beobachtet man die Ausbildung von Grenzflächen zwischen der Schicht des Polyesterharzes und der Oberfläche der mit Aminoplastharz imprägnierten Trägerbahn, die aufgrund mangelnder Verträglichkeit der Harze Trübungen und andere optische Störungen verursachen. Durch den mangelhaften Verbund des Polyesterharzes auf Basis Neopentylglykol und der Maleinsäure sind auch die mechanischen Eigenschaften der Oberflächenschicht nach der Aushärtung beeinträch-. tigt. Häufig kann man in kleineren oder grösseren Bereichen Abspaltungen der ausgehärteten Polyesterharzschicht von dem ausgehärteten Aminoplastharz beobachten.Curable polyester resins based on neopentyl glycol and isophthalic acid, maleic acid or mixtures of isophthalic acid and maleic acid are known from the prior art. However, if carrier webs are impregnated with curable aminoplast resin and coated with curable polyester resins based on neopentyl glycol, the formation of interfaces between the layer of polyester resin and the surface of the carrier web impregnated with aminoplast resin is observed, which, due to the poor compatibility of the resins, cause clouding and other visual disturbances. Due to the inadequate bond of the polyester resin based on neopentyl glycol and maleic acid, the mechanical properties of the surface layer are also impaired after curing. does. Often one can observe splitting off of the hardened polyester resin layer from the hardened aminoplast resin in smaller or larger areas.

Bei Verwendung des erfindungsgemässen Beschichtungsharzsystems zum Überziehen der mit härtbarem Aminoplastharz imprägnierten Trägerbahn zeigen sich diese Fehlerquellen nicht. Dies ist eine Folge der speziellen Zusammensetzung des Beschichtungsharzsystems. Das Beschichtungsharzsystem enthält als Hauptkomponente 49 bis 80 Gew.-% des vorgenannten härtbaren Polyesterharzes, hergestellt aus Neopentylglykol und Isophthalsäure und/oder Maleinsäure.When using the coating resin system according to the invention for covering the carrier web impregnated with curable aminoplast resin, these sources of error do not appear. This is a result of the special composition of the coating resin system. The main component of the coating resin system contains 49 to 80% by weight of the aforementioned curable polyester resin, made from neopentyl glycol and isophthalic acid and / or maleic acid.

Als Komponente b) enthält das Beschichtungsharz 1 bis 15 Gew.-% einer oder mehrerer monomerer Verbindungen, welche mindestens eine polymerisierbare Doppelbindung aufweisen. Diese bedingen die Vernetzung des Polyesters und erhöhen den Fluss des Beschichtungsharzes während der Aushärtung. Da das Beschichtungsharz in Form einer Lösung auf die imprägnierte Trägerbahn aufgetragen und das Lösungsmittel abgedunstet wird, verwendet man zweckmässig als polymerisierbare Monomere Verbindungen mit geringerem Dampfdruck, wie z.B. Diallylphthalat oder 1,4-Divinylbenzol. Styrol ist aus den vorgenannten Gründen weniger geeignet.As component b), the coating resin contains 1 to 15% by weight of one or more monomeric compounds which have at least one polymerizable double bond. These require the crosslinking of the polyester and it increase the flow of the coating resin during curing. Since the coating resin is applied to the impregnated carrier web in the form of a solution and the solvent is evaporated off, it is expedient to use compounds with a lower vapor pressure, such as diallyl phthalate or 1,4-divinylbenzene, as polymerizable monomers. Styrene is less suitable for the reasons mentioned above.

Von besonderer Bedeutung ist der Gehalt der Komponente c) des Beschichtungsharzsystems. Die Komponente c) ist in dem System zu 1 bis 15 Gew.-% enthalten und besteht wie die Komponente b) aus einem Monomeren oder einem Gemisch mehrerer Monomerer, die jeweils eine polymerisierbare Doppelbindung enthalten. Im Gegensatz zur Komponente b) weisen die Monomeren der Komponente c) im Monomermolekül zusätzlich eine mit Aminoplastharzen reaktive Gruppe auf. Vorzugsweise ist die reaktive Gruppe eine Amid- oder Alkoxymethylamidgruppe, welche in Nachbarschaft zur polymerisierbaren Doppelbindung steht. Beispiele geeigneter monomerer Verbindungen sind Acrylamid, Methylen-bis-acrylamid, N-Alkoxy-methylacrylamid sowie die entsprechenden Derivate der Methacrylsäure. Diese Verbindungen entsprechen den folgenden FormelnThe content of component c) of the coating resin system is of particular importance. Component c) is contained in the system in an amount of 1 to 15% by weight and, like component b), consists of a monomer or a mixture of several monomers, each of which contains a polymerizable double bond. In contrast to component b), the monomers of component c) in the monomer molecule additionally have a group reactive with aminoplast resins. The reactive group is preferably an amide or alkoxymethylamide group which is in the vicinity of the polymerizable double bond. Examples of suitable monomeric compounds are acrylamide, methylene-bis-acrylamide, N-alkoxy-methylacrylamide and the corresponding derivatives of methacrylic acid. These connections correspond to the following formulas

Figure imgb0001
Verwendet man Gemische von Monomeren der Komponente c), so kann ein Teil der Monomeren als funktionelle Gruppe eine Hydroxyl- oder Epoxygruppe tragen. Beispiele solcher Verbindungen sind Hydroxyalkylacrylate oder Glycidylacrylat sowie die entsprechenden Derivate der Methacrylsäure. Diese Verbindungen entsprechen folgenden Formeln
Figure imgb0001
 If mixtures of monomers of component c) are used, some of the monomers can carry a hydroxyl or epoxy group as a functional group. Examples of such compounds are hydroxyalkyl acrylates or glycidyl acrylate and the corresponding derivatives of methacrylic acid. These connections correspond to the following formulas

Figure imgb0002
Figure imgb0003
Figure imgb0004
Die Monomeren der Komponente c) werden aufgrund ihrer polymerisierbaren Doppelbindung bei der Aushärtung in das Gerüst des Polyesterharzes eingebunden und reagieren andererseits mit ihrer reaktiven Gruppe mit dem Aminoplastharz. Hierdurch kommt es zu einem chemischen Verbund des Polyesterharzes mit dem Aminoplastharz im Verlauf der Aushärtung, ohne dass offensichtlich die Bewitterungsfestigkeit des Polyesterharzes selbst auf Basis Neopentylglykol beeinträchtigt wird. Die Verbindungen der Komponente c) haben somit eine andere Funktion als die mit ihnen vergleichbare Komponente d) der DE-PS-2 734 669. Bei dieser Patentschrift wird durch die reaktiven Verbindungen der lineare Thermoplast mit dem härtbaren Polyester verbunden. Eine Verankerung des Polyesterharzes mit dem Aminoplastharz des Untergrundes kann nur ganz untergeordnet erfolgen, da zunächst die Reaktion der monomeren Verbindung sowohl mit dem Polyester als auch mit dem Thermoplasten abläuft. Die Komponente c) hat im Beschichtungsharzsystem vorliegender Erfindung somit eine andere Aufgabe. Die Verankerung des Polyesterharzes auf Basis Neopentylglykol mit dem Aminoplastharz des Untergrundes war nicht vorherzusehen. Dabei war es besonders überraschend, dass die so modifizierten Polyesterharze auf Basis Neopentylglykol ihre Bewitterungsfestigkeit nach der Aushärtung behalten würden. Eine Modifizierung der Polyesterharze auf Basis Neopentylglykol war aufgrund ihrer Unverträglichkeit mit Thermoplasten nicht möglich.
Figure imgb0002
Figure imgb0003
Figure imgb0004
 Due to their polymerizable double bond, the monomers of component c) are incorporated into the framework of the polyester resin during curing and, on the other hand, react with their reactive group with the aminoplast resin. This results in a chemical bond between the polyester resin and the aminoplast resin in the course of curing without the weather resistance of the polyester resin itself, based on neopentyl glycol, being obviously impaired. The compounds of component c) therefore have a different function than component d) of DE-PS-2 734 669, which is comparable to them. In this patent specification, the linear thermoplastic is bonded to the curable polyester by the reactive compounds. Anchoring of the polyester resin with the aminoplast resin of the substrate can only be done very subordinate, since the reaction of the monomeric compound with both the polyester and the thermoplastic takes place first. Component c) thus has another task in the coating resin system of the present invention. The anchorage of the polyester resin based on neopentyl glycol with the aminoplast resin of the substrate could not have been foreseen. It was particularly surprising that the modified polyester resins based on neopentyl glycol would retain their resistance to weathering after curing. Modification of the polyester resins based on neopentyl glycol was not possible due to their incompatibility with thermoplastics.

Das Beschichtungsharz enthält noch 1 bis 10 Gew.-% der Komponente d). Hierbei handelt es sich um ein mit kurzkettigen Alkoholen verethertes Aminoplastharz. Als kurzkettige Alkohole dienen dabei insbesondere solche mit 1 bis 4 Kohlenstoffatomen. Das veretherte Aminoplastharz reagiert ebenfalls mit den Monomeren der Komponente c) und dem Aminoplastharz, mit dem die Trägerbahn imprägniert ist. Auch hierdurch wird die Haftung der Polyesterharzbeschichtung auf der imprägnierten Trägerbahn verbessert. Dabei können als Komponente d) die im Handel befindlichen veretherten Aminoplastharze eingesetzt werden.The coating resin still contains 1 to 10% by weight of component d). This is an aminoplast resin etherified with short-chain alcohols. The short-chain alcohols used are in particular those with 1 to 4 carbon atoms. The etherified aminoplast resin also reacts with the monomers of component c) and the aminoplast resin with which the carrier web is impregnated. This also improves the adhesion of the polyester resin coating to the impregnated carrier web. The etherified aminoplast resins commercially available can be used as component d).

Die Komponente e) ist in einer Menge von 0,1 bis 8 Gew.-% enthalten und wird durch ein organisches Peroxid bzw. durch die Mischung monomerer organischer Peroxide gebildet. Diese dienen zur Vernetzung des Polyesterharzes a) und der Monomeren b) und c). Dabei können die an sich hierfür bekannten Diacylperoxide, Dialkylperoxide, Perester oder Perketale, wie z.B. Dibenzoylperoxid, Dicumylperoxid, tert.-Butylperbenzoat. oder 1.1-Di-(tert.-butylperoxy)-3.3.5-trimethylcyclohexan, verwendet werden. Die Peroxide sollen Aktivierungstemperaturen oberhalb 60 °C aufweisen.Component e) is contained in an amount of 0.1 to 8% by weight and is formed by an organic peroxide or by the mixture of monomeric organic peroxides. These serve to crosslink the polyester resin a) and the monomers b) and c). The known diacyl peroxides, dialkyl peroxides, peresters or perketals, such as e.g. Dibenzoyl peroxide, dicumyl peroxide, tert-butyl perbenzoate. or 1,1-di- (tert-butylperoxy) -3.3.5-trimethylcyclohexane can be used. The peroxides should have activation temperatures above 60 ° C.

Die Beschichtungsharze enthalten ferner 0,5 bis 3 Gew.-% einer oder mehrerer organischer Säure(n) als Komponente f). Diese Säuren beschleunigen die Reaktion der Komponente c) mit dem veretherten Aminoplastharz d) und dem Aminoplastharz der imprägnierten Trägerbahn. Beispiel einer besonders geeigneten organischen Säure ist p-Toluolsulfonsäure.The coating resins also contain 0.5 to 3% by weight of one or more organic acid (s) as component f). These acids accelerate the reaction of component c) with the etherified aminoplast resin d) and the aminoplast resin of the impregnated carrier web. An example of a particularly suitable organic acid is p-toluenesulfonic acid.

Dem Beschichtungsharz können zusätzlich zu den Komponenten a) bis f) noch Farbstoffe, UV-Stabilisatoren, Pigmente, Metallpulver, Füllstoffe, Antistatika und/oder Trennmittel zugesetzt werden. Dieser Zusatz erfolgt im Rahmen des üblichen Standes der Technik.In addition to components a) to f), the coating resin can also contain dyes, UV Stabilizers, pigments, metal powder, fillers, antistatic agents and / or release agents can be added. This addition takes place within the framework of the customary prior art.

Um eine Langzeitbewitterungsfähigkeit sicherzustellen, ist es notwendig, dass eine Mindestmenge an Beschichtungsharz auf der Trägerbahn vorhanden ist. Die Schichtdicke des härtbaren Beschichtungsharzes ist jedoch nicht mit der Schichtdicke des ausgehärteten Beschichtungsharzes gleichzusetzen, da das härtbare Beschichtungsharz unter den Aushärtungsbedingungen fliessfähig ist und zum Teil in die imprägnierte Trägerbahn eindringen kann, wobei der bei der Aushärtung aufrechterhaltene Pressdruck Einfluss auf die Schichtdicke des ausgehärteten Polyesterbeschichtungsharzes hat. Da die Schichtdicke des unter Wärme und Druck ausgehärteten Beschichtungsharzes somit auch von Parametern bestimmt wird, die durch die Verarbeitung des erfindungsgemässen Produktes bestimmt werden, ist es nicht möglich, die bevorzugte Schichtdicke des Beschichtungsharzes vor der Aushärtung festzulegen. Es ist deshalb eine solche beschichtete Trägerbahn bevorzugt, bei der die Schichtdicke des Beschichtungsharzes nach der bestimmungsgemässen Verwendung der imprägnierten und beschichteten Trägerbahn und Aushärtung der Harze mindestens 35 µm beträgt. Die hierfür benötigte Menge des Beschichtungsharzes vor der Aushärtung ist deshalb durch Vorversuche zu bestimmen, bei denen die Parameter der Weiterbehandlung berücksichtigt werden. In der Regel wird die gewünschte Schichtdicke erreicht, wenn das Beschichtungsharz in einer Menge von mindestens 100 g m-2 auf die imprägnierte Trägerbahn aufgebracht wird.In order to ensure long-term weathering ability, it is necessary that a minimum amount of coating resin is present on the carrier web. However, the layer thickness of the curable coating resin is not to be equated with the layer thickness of the cured coating resin, since the curable coating resin is flowable under the curing conditions and can partially penetrate into the impregnated carrier web, the compression pressure maintained during curing having an influence on the layer thickness of the cured polyester coating resin . Since the layer thickness of the coating resin cured under heat and pressure is thus also determined by parameters which are determined by the processing of the product according to the invention, it is not possible to determine the preferred layer thickness of the coating resin before curing. Such a coated carrier web is therefore preferred, in which the layer thickness of the coating resin after the intended use of the impregnated and coated carrier web and curing of the resins is at least 35 μm. The amount of coating resin required for this before curing must therefore be determined by preliminary tests, in which the parameters of the further treatment are taken into account. As a rule, the desired layer thickness is achieved if the coating resin is applied to the impregnated carrier web in an amount of at least 100 g m 2 .

Die Herstellung der erfindungsgemässen imprägnierten und beschichteten Trägerbahn erfolgt in an sich bekannter Weise dadurch, dass man die Trägerbahnen zunächst mit der wässrigen Lösung eines härtbaren Aminoplastharzvorkondensats imprägniert. Dabei sollen die Cellulosefasern der Trägerbahn vollständig umhüllt werden. Üblicherweise wird man deshalb 50 bis 100% des Papiergewichts an Aminoplastharz, als Festharz gerechnet, in die Trägerbahn einbringen. Die so erhaltenen Trägerbahnen werden unter Vermeidung der vollständigen Aushärtung des Aminoplastharzes getrocknet. Die Beschichtung der imprägnierten Trägerbahnen kann in an sich bekannter Weise dadurch vorgenommen werden, dass man das Polyesterharz in einem Lösungsmittel, wie z.B. Methylenchlorid, Methylethylketon, Tetrahydrofuran, Dioxan, Aceton, Methanol oder deren Gemische, löst und die erhaltene Lösung auf die imprägnierte Trägerbahn aufgiesst. Das Lösungsmittel wird dann abgedunstet.The impregnated and coated carrier web according to the invention is produced in a manner known per se by first impregnating the carrier webs with the aqueous solution of a curable aminoplast resin precondensate. The cellulose fibers of the carrier web are to be completely covered. Usually, 50 to 100% of the paper weight of aminoplast resin, calculated as solid resin, is therefore introduced into the carrier web. The carrier webs obtained in this way are dried while avoiding complete curing of the aminoplast resin. The impregnated carrier webs can be coated in a manner known per se by the polyester resin being dissolved in a solvent such as e.g. Methylene chloride, methyl ethyl ketone, tetrahydrofuran, dioxane, acetone, methanol or mixtures thereof, dissolves and the solution obtained is poured onto the impregnated carrier web. The solvent is then evaporated off.

Die Verarbeitung der erfindungsgemässen, kunstharzbeschichteten, klebfreien Trägerbahn erfolgt in an sich bekannter Weise z.B. in ein- oder mehretagigen Flächenpressen sowie in Form- bzw. Profilpressen in kontinuierlich arbeitenden Pressanlagen, wie Doppelstahlbandanlagen. Der erforderliche Druck beträgt 0,3 bis 2,0 N/mm2, vorzugsweise 0,5 bis 1,6 N/mm2. Die Temperatur, gemessen an der Oberfläche der kunstharzbeschichteten Trägerbahn, soll 130 bis 180 °C betragen. Die erforderliche Verarbeitungszeit richtet sich nach dem zu vergütenden Werkstoff, der Verarbeitungstemperatur und den Besonderheiten des jeweiligen Verarbeitungsverfahrens. Die Richtwerte liegen zwischen 0,5 und 10 Minuten. Bezüglich Druck, Temperatur und Verarbeitungszeit sind im Einzelfall zum Teil erhebliche Abweichungen möglich. Die optimalen Verarbeitungsbedingungen müssen deshalb in Vorversuchen jeweils ermittelt werden.The processing of the resin-coated, tack-free carrier web according to the invention is carried out in a manner known per se, for example in single or multi-day surface presses and in molding or profile presses in continuously operating press systems, such as double steel belt systems. The required pressure is 0.3 to 2.0 N / mm 2 , preferably 0.5 to 1.6 N / mm 2. The temperature, measured on the surface of the resin-coated carrier web, should be 130 to 180 ° C. The processing time required depends on the material to be tempered, the processing temperature and the special features of the respective processing method. The guidelines are between 0.5 and 10 minutes. Considerable deviations are possible in individual cases with regard to pressure, temperature and processing time. The optimal processing conditions must therefore be determined in preliminary tests.

Die gebildete Oberfläche entspricht in ihrer Struktur bzw. ihrem Glanzgrad dem verwendeten Pressblech.The structure or gloss level of the surface formed corresponds to the press plate used.

In den folgenden Beispielen wird der Gegenstand vorliegender Erfindung noch näher erläutert.The subject matter of the present invention is explained in more detail in the following examples.

Beispiel 1example 1 A) Herstellung einer PolyesterharzlösungA) Preparation of a polyester resin solution

In einem Gemisch aus 140 g Aceton und 60 g Methanol werden 138 g eines Polyesterharzes auf Basis von 2,7 Mol Maleinsäureanhydrid, 2,5 Mol i-Phthalsäure, 4 Mol Neopentylglykol, 1 Mol Propylenglykol und 20,8 g Diallylphthalat-Prepolymer gelöst. Dazu werden unter Rühren 20,8g Diallylphthalat-Monomer, 10,4g Acrylamid und 4,2g Methoxymethylmethacrylamid gegeben. Zu der klaren Lösung werden 7 g butylverethertes Melaminharz, 1,4 g p-Toluolsulfonsäure, 10,3 g einer pyrolytisch gewonnenen Kieselsäure, 4,1 g eines handelsüblichen Trennmittels, 0,015 g Hydrochinon und 0,7 g eines handelsüblichen Lichtschutzmittels gegeben. Die auf diese Weise hergestellte Lösung ist lagerstabil und verändert ihre Viskosität während längerer Zeit nicht. Kurz vor Beschichtung der Trägerbahn werden 5,4 g Dicumylperoxid eingerührt.138 g of a polyester resin based on 2.7 moles of maleic anhydride, 2.5 moles of i-phthalic acid, 4 moles of neopentyl glycol, 1 mole of propylene glycol and 20.8 g of diallyl phthalate prepolymer are dissolved in a mixture of 140 g of acetone and 60 g of methanol. 20.8 g of diallyl phthalate monomer, 10.4 g of acrylamide and 4.2 g of methoxymethyl methacrylamide are added with stirring. 7 g of butyl etherified melamine resin, 1.4 g of p-toluenesulfonic acid, 10.3 g of pyrolytically obtained silica, 4.1 g of a commercially available release agent, 0.015 g of hydroquinone and 0.7 g of a commercially available light stabilizer are added to the clear solution. The solution prepared in this way is stable in storage and does not change its viscosity for a long time. 5.4 g of dicumyl peroxide are stirred in shortly before coating the carrier web.

B) Beschichtung einer TrägerbahnB) coating a carrier web

Ein uni-dunkelbraunes Dekorpapier mit einem Flächengewicht von 80 g/m2 wird mit einer 50 Gew.-%igen wässrigen Lösung eines handelsüblichen Melaminharzvorkondensates getränkt und bei 140°C 1 Minute lang getrocknet. Die imprägnierte Papierbahn enthält noch 5 Gew.-% flüchtige Bestandteile, vorwiegend Wasser. Ihr Gewicht beträgt 140 g/m2.A plain-dark brown decorative paper with a weight per unit area of 80 g / m 2 is impregnated with a 50% by weight aqueous solution of a commercially available melamine resin precondensate and dried at 140 ° C. for 1 minute. The impregnated paper web still contains 5% by weight of volatile constituents, predominantly water. Its weight is 140 g / m 2 .

Auf die so imprägnierte Papierbahn wird mittels einer Giessrakel die gemäss A) hergestellte Polyesterharzlösung aufgegossen. Nach Abdampfen des Lösungsmittels besitzt die beschichtete und imprägnierte Papierbahn ein Gewicht von 250 g/m2. Der Anteil flüchtiger Bestandteile beträgt 7 Gew.-%.The polyester resin solution prepared according to A) is poured onto the paper web thus impregnated using a casting knife. After evaporation of the solvent, the coated and impregnated paper web has a weight of 250 g / m 2 . The proportion of volatile constituents is 7% by weight.

Beide Seiten des beschichteten Films sind klebfrei. Der Film ist flexibel und von guter mechanischer Festigkeit; er kann bei 20 °C mindestens für drei Monate ohne wesentliche Veränderungen gelagert werden.Both sides of the coated film are non-tacky. The film is flexible and has good mechanical strength; it can be stored at 20 ° C for at least three months without significant changes.

C) Verarbeitung der kunstharzbeschichteten Trägerbahn (Vergütung einer Sperrholzplatte)C) Processing of the resin-coated carrier web (coating of a plywood board)

Die gemäss B) hergestellte polyesterharzbeschichtete Trägerbahn wird zur Vergütung einer Sperrholzplatte verwendet. Hierzu wird eine beheizte, hydraulische Stahlplattenpresse unter Verwendung eines siliconisierten Trennpapieres eingesetzt. Als Barriere zwischen kunstharzbeschichteter Trägerbahn und Sperrholzplatte dienen eine mit einem handelsüblichen Melaminharzvorkondensat imprägnierte Papierbahn mit einem Papiergewicht von 80 g/m2 und einem Filmgewicht von 200 g/m2 sowie unmittelbar auf der Sperrholzplatte eine mit einem handelsüblichen Phenolharzvorkondensat imprägnierte Papierbahn mit einem Papiergewicht von 80 g/m2 und einem Filmgewicht von 180 g/m2. Die Verpressung erfolgt mit einer Temperatur von 140 °C und mit einem Druck von 1,5 N/mm2 für 10 Minuten.The polyester resin-coated carrier web produced according to B) is used to temper a plywood panel. A heated, hydraulic steel plate press using a siliconized release paper is used for this. A paper web impregnated with a commercially available melamine resin precondensate with a paper weight of 80 g / m 2 and a film weight of 200 g / m 2 as well as a paper web impregnated with a commercially available phenolic resin precondensate with a paper weight of 80 serve as a barrier between the resin-coated carrier web and the plywood board g / m 2 and a film weight of 180 g / m 2 . The pressing takes place at a temperature of 140 ° C and with a pressure of 1.5 N / mm 2 for 10 minutes.

D) Prüfung der vergüteten SperrholzplatteD) Checking the tempered plywood panel

Die vergütete Sperrholzplattenoberfläche ist völlig geschlossen; es werden keinerlei Vergrauungserscheinungen festgestellt. Bei der Prüfung auf Fleckenempfindlichkeit gemäss DIN 68 861, Teil 1, wird die Beanspruchungsgruppe 1 B erfüllt; beim Wasserdampftest gemäss DIN 53 799 tritt keine Veränderung auf. Der gemäss DIN 53 799 durchgeführte Abriebtest ergibt bei 300 bis 400 Umdrehungen einen Abrieb von 0,66 mg/U; das Ende der Prüfung wird gemäss DIN 53 799 nach 375 Umdrehungen erreicht.The coated plywood surface is completely closed; no signs of graying are found. When testing for stain sensitivity in accordance with DIN 68 861, Part 1, stress group 1 B is met; no change occurs in the water vapor test according to DIN 53 799. The abrasion test carried out in accordance with DIN 53 799 shows an abrasion of 0.66 mg / rev at 300 to 400 revolutions; The end of the test is reached after 375 revolutions in accordance with DIN 53 799.

Die Härte, ermittelt durch ein Erichsen-Prüfgerät, bei dem eine Kunststoffrolle verwendet wird, beträgt etwa 180 bis 220 p.The hardness, determined by an Erichsen tester using a plastic roller, is approximately 180 to 220 p.

Die Prüfung der Kratzbeständigkeit nach DIN 68 861 und DIN 53 799 ergibt ein Ergebnis, welches der Beanspruchungsgruppe 4 C (über 1,5 bis 2,0 N) entspricht.Testing the scratch resistance according to DIN 68 861 and DIN 53 799 gives a result which corresponds to the stress group 4 C (over 1.5 to 2.0 N).

Beispiel 2Example 2 A) Herstellung eines vergüteten SpanformlingsA) Production of a tempered chip mold

Ein gemäss Beispiel 1 A) und 1 B) hergestellter Film wird zur Beschichtung einer mit einem Melaminharzkondensat gebundenen Spänemischung, wobei der Anteil an mit Melamin verstärktem Harnstoffharz 25 Gew.-% beträgt, verwendet. Hierzu wird eine beheizte Edelstahlform verwendet, wobei die Beschichtung und die Ausformung eines Formlings aus einem Spankuchen gleichzeitig geschieht. Als Barriere zwischen dem kunstharzbeschichteten Film und der Spanplatte dienen eine mit einem handelsüblichen Melaminharzvorkondensat imprägnierte Papierbahn mit einem Papiergewicht von 80 g/m2 und einem Filmgewicht von 180 g/m2 sowie unmittelbar auf der Spanplatte eine mit einem handelsüblichen Phenolharzvorkondensat imprägnierte Papierbahn mit einem Papiergewicht von 80 g/m2 und einem Filmgewicht von 180 g/M 2. Die Verpressung erfolgt mit einer Temperatur von 150 °C und mit einem Druck von 1,3 N/mm2 für 3,5 Minuten.A film produced according to Examples 1 A) and 1 B) is used to coat a chip mixture bonded with a melamine resin condensate, the proportion of urea resin reinforced with melamine being 25% by weight. A heated stainless steel mold is used for this purpose, with the coating and the molding of a molded part from a chip cake taking place simultaneously. A paper web impregnated with a commercially available melamine resin precondensate with a paper weight of 80 g / m 2 and a film weight of 180 g / m 2 as well as a paper web impregnated with a commercial phenolic resin precondensate with a paper weight serve as a barrier between the synthetic resin-coated film and the particle board of 80 g / m 2 and a film weight of 180 g / M 2 . The pressing takes place at a temperature of 150 ° C and with a pressure of 1.3 N / mm 2 for 3.5 minutes.

B) Prüfung des vergüteten SpanformlingsB) Checking the tempered chip mold

Eine Probe des gemäss 2 A) vergüteten Spanformlings wird im V-100-Kochtest nach DIN 68 763 (Flachpressplatten für das Bauwesen) bei 100°C für 2 Stunden in Wasser gelagert. Nach Entnahme der so behandelten Probe aus dem Wasserbad werden keine Bläschen, keine Trübung und keine Ablösung des ausgehärteten Polyesterharzes vom Untergrund beobachtet.A sample of the chip mold which is tempered in accordance with 2A) is stored in water in the V-100 cooking test according to DIN 68 763 (flat pressed panels for the building trade) at 100 ° C. for 2 hours. After taking the sample treated in this way from the water bath, no bubbles, no turbidity and no detachment of the cured polyester resin from the substrate are observed.

Ebensowenig werden Veränderungen im Wechseltest festgestellt, bei dem eine Probe für 4 Stunden im kochenden Wasser und bei 70 °C für 20 Stunden in einem Trockenschrank mit fünffacher Wiederholung dieses Cyclus behandelt wird.Changes in the alternating test, in which a sample is treated for 4 hours in boiling water and at 70 ° C. for 20 hours in a drying cabinet with this cycle repeated five times, are also not found.

Gemäss DIN 53 387 wird ein Kurzbewitterungstest vorgenommen, wobei eine Probe des vergüteten Spanformlings bei einer Schwarztafeltemperatur von 45 °C im Cyclus 17 Minuten Bestrahlung/3 Minuten Bestrahlung und Beregnung exponiert wird. Erste Zeichen eines Angriffs in Form eines Glanzverlustes und einzelner Flekken können erst nach einer Expositionsdauer von 9000 Stunden festgestellt werden.A short weathering test is carried out in accordance with DIN 53 387, in which a sample of the tempered chip mold is exposed at a black panel temperature of 45 ° C. in the cycle for 17 minutes of irradiation / 3 minutes of irradiation and irrigation. The first signs of an attack in the form of a loss of gloss and individual spots can only be detected after an exposure period of 9000 hours.

Vergleichsbeispiel 1Comparative Example 1

Es wird gemäss Beispiel 1 A) und 1 B) ein Film hergestellt mit der Ausnahme, dass auf die Verwendung von Acrylamid; Methoxymethylmethacrylamid und des butylveretherten Melaminharzes verzichtet wird. Der erhaltene Film wird gemäss Beispiel 2 verarbeitet.A film is produced according to Example 1 A) and 1 B) with the exception that the use of acrylamide; Methoxymethyl methacrylamide and the butyl etherified melamine resin is dispensed with. The film obtained is processed according to Example 2.

Eine Probe des vergüteten Spanformlings wird im V-100-Kochtest nach DIN 68 763 bei 100 °C für 2 Stunden in Wasser gelagert. Nach Entnahme der so behandelten Probe aus dem Wasserbad werden Ablösungen des ausgehärteten Polyesterharzes vom Untergrund sowie unregelmässig auftretende Bläschen und eine leichte Vergrauung beobachtet.A sample of the tempered chip mold is stored in water in the V-100 cooking test according to DIN 68 763 at 100 ° C for 2 hours. After taking the sample treated in this way from the water bath, detachments of the cured polyester resin from the substrate as well as irregular bubbles and a slight graying are observed.

Gemäss DIN 53 387 wird ein Kurzbewitterungstest vorgenommen, wobei eine Probe des vergüteten Spanformlings bei einer Schwarztafeltemperatur von 45 °C im Cyclus 17 Minuten Bestrahlung/3 Minuten Bestrahlung und Beregnung exponiert wird. Erste Anzeichen eines Angriffs in Form eines erheblichen Glanzverlustes und Bläschen im Polyesterharz können nach einer Expositionsdauer von 5000 Stunden festgestellt werden.A short weathering test is carried out in accordance with DIN 53 387, in which a sample of the tempered chip mold is exposed at a black panel temperature of 45 ° C. in the cycle for 17 minutes of irradiation / 3 minutes of irradiation and irrigation. The first signs of an attack in the form of a significant loss of gloss and bubbles in the polyester resin can be seen after an exposure period of 5000 hours.

Vergleichsbeispiel 2 (zu DE-PS-2 734 669)Comparative Example 2 (to DE-PS-2 734 669)

Es wird bei der Herstellung der Tränkharzlösung wie in Beispiel 1 A) verfahren mit der Ausnahme, dass zusätzlich 45 g eines Polyvinylformals, enthaltend je ca. 10% Acetat- und freie Hydroxylgruppen, zugegeben werden. Nach kurzer Zeit Lagerung der Lösung zeigt sich eine Trennung in zwei Phasen, deren eine im wesentlichen die Polyesterkomponente und Diallylphthalat- ' Prepolymer, die andere im wesentlichen Polyvinylformal enthält. Eine Weiterverarbeitung durch Vergiessen des enthaltenen Gemisches zu einem homogenen Film ist wegen der Unverträglichkeit der Komponenten nicht möglich.The procedure for preparing the impregnating resin solution is as in Example 1A), with the exception that an additional 45 g of a polyvinyl formal, each containing about 10% acetate and free hydroxyl groups, are added. After the solution has been stored for a short time, there is a separation into two phases, one essentially containing the polyester component and diallyl phthalate prepolymer and the other essentially containing polyvinyl formal. Further processing by pouring the contained mixture into a homogeneous film is not possible due to the incompatibility of the components.

Vergleichsbeispiel 3Comparative Example 3

Es wird gemäss Beispiel 1 A) und 1 B) ein Film hergestellt mit der Ausnahme, dass anstelle des dort verwendeten ungesättigten Polyesters 110 g eines Polyesters auf Basis von 2,7 Mol Maleinsäureanhydrid, 2,5 Mol i-Phthalsäure und 5 Mol Propylenglykol zum Einsatz kommen (so wie dies im Beispiel 1 a) der DE-PS-2 734 669 der Fall war). Der erhaltene Film wird gemäss Beispiel 2 verarbeitet.A film is produced according to Example 1 A) and 1 B) with the exception that instead of Unsaturated polyester used there 110 g of a polyester based on 2.7 moles of maleic anhydride, 2.5 moles of i-phthalic acid and 5 moles of propylene glycol are used (as is the case in Example 1 a) of DE-PS-2 734 669 was). The film obtained is processed according to Example 2.

Gemäss DIN 53 387 wird ein Kurzbewitterungstest vorgenommen, wobei eine Probe des vergüteten Spanformlings bei einer Schwarztafeltemperatur von 45 °C im Cyclus 17 Minuten Bestrahlung/3 Minuten Bestrahlung und Beregnung exponiert wird. Erste Anzeichen eines Angriffs in Form eines erheblichen Glanzverlustes können nach einer Expositionsdauer von 5500 Stunden festgestellt werden.A short weathering test is carried out in accordance with DIN 53 387, in which a sample of the tempered chip mold is exposed at a black panel temperature of 45 ° C. in the cycle for 17 minutes of irradiation / 3 minutes of irradiation and irrigation. The first signs of an attack in the form of a significant loss of gloss can be seen after an exposure period of 5500 hours.

Vergleichsbeispiel 4Comparative Example 4

Es wird gemäss Beispiel 1 A) und 1 B) ein Film hergestellt, jedoch weniger Polyesterharzlösung aufgegossen, so dass das Flächengewicht der beschichteten und imprägnierten Papierbahn nur 190 g/m2 beträgt. Der Anteil flüchtiger Bestandteile beträgt 6,5 Gew.-%. Der erhaltene Film wird gemäss Beispiel 2 verarbeitet.A film is produced according to Examples 1 A) and 1 B), but less polyester resin solution is poured on, so that the weight per unit area of the coated and impregnated paper web is only 190 g / m 2 . The volatile constituents are 6.5% by weight. The film obtained is processed according to Example 2.

Gemäss DIN 53 387 wird ein Kurzbewitterungstest vorgenommen, wobei eine Probe des vergüteten Spanformlings bei einer Schwarztafeltemperatur von 45 °C im Cyclus 17 Minuten Bestrahlung/3 Minuten Bestrahlung und Beregnung exponiert wird. Erste Anzeichen eines Angriffs in Form einzelner Flecken können nach einer Expositionsdauer von 6000 Stunden festgestellt werden.A short weathering test is carried out in accordance with DIN 53 387, in which a sample of the tempered chip mold is exposed at a black panel temperature of 45 ° C. in the cycle for 17 minutes of irradiation / 3 minutes of irradiation and irrigation. The first signs of an attack in the form of single spots can be seen after an exposure period of 6000 hours.

Claims (6)

1. Tack-free carrier web, impregnated with a curable aminoplast resin and coated with a heat- curable polyester resin, for the surface finishing of sheet-like materials based on cellulose, in particular modified wooden panels and laminated panels, characterized in that the coating resin consists of
a) 49 to 80% by weight of a curable polyester resin prepared from neopentyl glycol and isophthalic acid and/or maleic acid,
b) 1 to 15% by weight of one or more monomers containing at least one polymerizable double bond,
c) 1 to 15% by weight of one or more monomers containing in each case a polymerizable double bond and a group reactive to aminoplast resins,
d) 1 to 10% by weight of one or more etherified aminoplast resins,
e) 0.1 to 8% by weight of one or more organic peroxides, and
f) 0.05 to 3% by weight of one or more organic acids.
2. Coated carrier web according to Claim 1, characterized in that the coating resin is applied in an amount such that the film thickness of the coating resin after the use, as designated, of the impregnated and coated carrier web and after the curing of the resins is at least 35 J.1m.
3. Coated carrier web according to Claim 1, characterized in that the coating resin contains diallyl phthalate or 1,4-divinylbenzene as the component b).
4. Coated carrier web according to Claim 1 or 3, characterized in that the coating resin contains, as the component c), monomers containing an amide or alkoxymethylamide group adjacent to the polymerizable double bond.
5. Coated carrier web according to Claim 4, characterized in that the coating resin contains, as the component c), acrylamide, methacrylamide, N-alkoxymethylacrylamide and/or N-alkoxyme- thylmethacrylamide.
6. Sheet-like material based on cellulose, in particular a modified wooden panel or laminated panel, having a surface formed from a carrier web, according to one or more of Claims 1 to 5, which contains cured resins and has been impregnated and coated.
EP19850100603 1984-02-03 1985-01-22 Non-tacky carrier web impregnated with a curable aminoplast resin and coated with a heat-curable polyester resin for the modification of the surface of flat materials Expired EP0152781B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3403691 1984-02-03
DE19843403691 DE3403691C1 (en) 1984-02-03 1984-02-03 Tack-free backing sheet impregnated with curable aminoplast resin and coated with thermosetting coating resin for the surface finishing of flat cellulosic materials

Publications (3)

Publication Number Publication Date
EP0152781A2 EP0152781A2 (en) 1985-08-28
EP0152781A3 EP0152781A3 (en) 1987-02-04
EP0152781B1 true EP0152781B1 (en) 1988-06-01

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP19850100603 Expired EP0152781B1 (en) 1984-02-03 1985-01-22 Non-tacky carrier web impregnated with a curable aminoplast resin and coated with a heat-curable polyester resin for the modification of the surface of flat materials

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Country Link
EP (1) EP0152781B1 (en)
DE (1) DE3403691C1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102076764B (en) * 2008-07-01 2013-05-01 凯得装饰有限公司 Impregnation with hybrid resins

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3730051C1 (en) * 1987-09-08 1988-12-08 Goldschmidt Ag Th Carrier sheet suitable for transfer printing for decorative surface coating of flat materials
DE102005021156A1 (en) 2005-05-09 2006-11-16 Kaindl Flooring Gmbh Multilayer board
WO2022008671A1 (en) * 2020-07-10 2022-01-13 Basf Se Resin-impregnated fibrous material in the form of a sheet or a web

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2228936B2 (en) * 1972-06-14 1976-06-16 CARRIER FABRIC SHEETS IMPRAEGNED AND COATED WITH HARDARABLE RESIN FOR THE SURFACE FINISHING OF WOOD-BASED MATERIALS AND THE PROCESS FOR THEIR PRODUCTION
DE2734669C2 (en) * 1977-08-01 1982-03-25 Th. Goldschmidt Ag, 4300 Essen Carrier sheets coated with thermosetting polyester resin for the surface treatment of wood-based panels or laminates

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102076764B (en) * 2008-07-01 2013-05-01 凯得装饰有限公司 Impregnation with hybrid resins

Also Published As

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DE3403691C1 (en) 1985-04-11
EP0152781A2 (en) 1985-08-28
EP0152781A3 (en) 1987-02-04

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