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 such monomeric compounds in the curable coating resin which on the one hand are suitable for copolymerization with the curable polyester resin and on the other hand are 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 can be stored prior to curing and in particular are non-tacky and, in the cured state, form surfaces which, particularly under the conditions of external weathering, result in crack-resistant, glossy, hard and haze-free surfaces and also on 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. Often one can observe splitting off of the hardened polyester resin layer from the hardened aminoplast resin in smaller or larger areas.
• the Beschich Tung resin system contains as a main component 49 to 80 wt .-% 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 cause the crosslinking of the polyester and 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 lower vapor pressure, such as e.g. Diallyl phthalate or 1,4-divinylbenzene. 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-alkoxymethylacrylamide 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) thus have a different function than component d) of DE-PS 27 34 669, 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 monanere compound takes place both with the polyester and with the thermoplastic.
• 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 amino plastic 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).
• organic peroxides such as dibenzoyl peroxide, dicumyl peroxide, tert-butyl perbenzoate or 1.1Di- (tert.butylperaxy) -3.3.5-trimethyl cyclohexane, 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.
• dyes In addition to components a) to f), dyes, UV stabilizers, pigments, metal powders, fillers, antistatic agents and / or release agents can be added to the coating resin. 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 also depends on parameters is determined, which are determined by the processing of the P ro- domestic product according to the invention, it is not possible to define the preferred layer thickness of the coating resin prior to curing.
• Such a coated carrier web is therefore preferred in which the layer thickness of the coating resin is at least 35 ⁇ m after the intended use of the impregnated and coated carrier web and curing of the resins.
• 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 present in an amount of at least 100 g. m -2 is applied to the impregnated carrier web.
• 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 the 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 one-day or multi-day surface presses and in molding or profile presses in continuously operating press systems, such as double steel belt systems.
• the pressure required is 0.3 to 2.0 N / mm, 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 peculiarities of each 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 basis weight of 80 g / m 2 is soaked with a 50% aqueous solution of a commercially available melamine resin precondensate and dried at 140 ° C. for 1 minute.
• the impregnated paper web still contains 5% volatile components, mainly water. Its weight is 140 g / m 2 .
• the polyester resin solution prepared according to A) is poured onto the paper web thus impregnated by means of a casting knife. After evaporation of the solvent, the coated and impregnated paper web has a weight of 250 g / m 2 . The volatile content is 7%.
• 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.
• As a barrier between resin coated carrier web and plywood serve an impregnated with a commercially available melamine resin paper web with a paper weight of 80 g / m 2 and a film weight of 200 g / m 2 as well as directly to the plywood board an impregnated with a commercially available Phenolharzvorkondensat paper web having a P apiercausing of 80 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.
• the stress group 1 B is met; no change occurs in the water vapor test according to DIN 53 799.
• the according to DIN 53 799 conducted abrasion test shows an abrasion of 0.66 mg / rev at 300 to 400 revolutions; The end of the test is reached according to DIN 53 799 after 375 revolutions.
• 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 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 has been tempered in accordance with 2A) is stored in water in the V-100 cooking test according to DIN 68 763 (flat pressed plates for the building industry) at 100 ° C. for 2 hours. After removing the so be no water bubbles, no turbidity and no detachment of the hardened polyester resin from the substrate are observed.
• a short weathering test is carried out in accordance with DIN 53 387, a sample of the tempered chip mold being 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, methoxyrrethylmthacrylamide 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 hardened 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, it is separated into two phases, one essentially containing the polyester component and diallyl phthalate prepolymer, the other essentially containing polyvinyl formal. Further processing by pouring the 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 the unsaturated polyester used there, 110 g of a polyester based on 2.7 mol of maleic anhydride, 2.5 mol of i-phthalic acid and 5 mol of propylene glycol Use came (as was the case in Example 1 a) of DE-PS 27 34 669).
• 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 Example 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 content is 6.5%.
• the film obtained is processed according to Example 2.
• a short weathering test is carried out, whereby 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.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Dispersion Chemistry (AREA)
• Laminated Bodies (AREA)

Applications Claiming Priority (2)

Publications (3)

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ID=6226622

Family Applications (1)

Country Status (2)

Cited By (1)

Families Citing this family (3)

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• 1984
  • 1984-02-03 DE DE19843403691 patent/DE3403691C1/de not_active Expired
• 1985
  • 1985-01-22 EP EP19850100603 patent/EP0152781B1/fr not_active Expired

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