AU2003290080B2 - Synthetic material dispersions - Google Patents

Synthetic material dispersions Download PDF

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AU2003290080B2
AU2003290080B2 AU2003290080A AU2003290080A AU2003290080B2 AU 2003290080 B2 AU2003290080 B2 AU 2003290080B2 AU 2003290080 A AU2003290080 A AU 2003290080A AU 2003290080 A AU2003290080 A AU 2003290080A AU 2003290080 B2 AU2003290080 B2 AU 2003290080B2
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melamine resin
weight
melamine
water
synthetic resin
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AU2003290080A1 (en
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Daniel Jocham
Manfred Ratzsch
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AMI Agrolinz Melamine International GmbH
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AMI Agrolinz Melamine International GmbH
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/06—Layered products comprising a layer of paper or cardboard specially treated, e.g. surfaced, parchmentised
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B44C5/0461—Ornamental plaques, e.g. decorative panels, decorative veneers used as wall coverings
    • 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
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
    • C08G12/32—Melamines
    • 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
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/40—Chemically modified polycondensates
    • C08G12/42—Chemically modified polycondensates by etherifying
    • C08G12/424—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds
    • C08G12/425—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds based on triazines
    • C08G12/427—Melamine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
    • D21H17/51—Triazines, e.g. melamine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/73—Hydrophobic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2317/00—Animal or vegetable based
    • B32B2317/12—Paper, e.g. cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2317/00—Animal or vegetable based
    • B32B2317/16—Wood, e.g. woodboard, fibreboard, woodchips
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2331/00—Polyvinylesters
    • B32B2331/04—Polymers of vinyl acetate, e.g. PVA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2377/00—Polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/18—Paper- or board-based structures for surface covering
    • D21H27/22—Structures being applied on the surface by special manufacturing processes, e.g. in presses
    • D21H27/26—Structures being applied on the surface by special manufacturing processes, e.g. in presses characterised by the overlay sheet or the top layers of the structures

Abstract

The invention relates to synthetic material dispersions consisting of (a) an aqueous phase of solutions of hydrophilic melamine resin precondensates and a latent hardening catalyst in water or in mixtures of water and alcohols C<SUB>1</SUB>-C<SUB>6</SUB>, (b) an organic nanophase in the form of nanometric droplets and/or nanoparticles derived from 70-99% of the melamine resin precondensates which are insoluble in water and etherifieds and contain hardening acid catalysts and acid impermeability agents, (c) dispersion agents at a concentration of 1-10 mass % in relation to the total mass of the melamine resin precondensates. The synthetic material dispersions are used for producing flat coated products which are externally used in the form of laminates, of coated flat carrying materials or moulded coated bodies for construction or for sports and recreation.

Description

IN THE MATTER OF an Australian Application corresponding to PCT Application PCT/EP2003/014452 RWS Group Ltd, of Europa House, Marsham Way, Gerrards Cross, Buckinghamshire, England, hereby solemnly and sincerely declares that, to the best of its knowledge and belief, the following document, prepared by one of its translators competent in the art and conversant with the English and German languages, is a true and correct translation of the PCT Application filed under No. PCT/EP2003/014452 Date: 19 April 2005 C. E. SITCH Deputy Managing Director UK Translation Division For and on behalf of RWS Group Ltd WO 2004/056899 PCT/EP2003/014452 Synthetic material dispersions The invention relates to synthetic resin dispersions for the production of hydrophilic sheet-like structures or hydrophilic shaped articles provided with hydrophobic surfaces.
The use of solutions of melamine resin precondensates or partly etherified melamine resin precondensates in water or alcohol/water mixture as coating or impregnating compositions for hydrophilic sheet-like structures is known (EP 0 686 665 A2; DE 44 20 013 Al) A disadvantage of hydrophilic sheet-like structures, such as paper or cardboard, impregnated with conventional melamine resin solutions is their low resistance to weathering when used outdoors, since water can diffuse unimpeded into the impregnated surface layer and initiate cracking in the surface layer.
A known process for improving the resistance to weathering of hydrophilic sheet-like structures impregnated with melamine resin is the additional coating of the impregnated sheet-like structures with a hydrophobic top layer of polyvinyl fluoride (US 3 676 290 polyacrylates (DE 33 29 679 Cl; EP 0 824 560 Al; US 3 841 956 A; DE 36 30 315 Al), unsaturated polyesters (EP 0 824 560 Al) or ethylene/propylene rubber (EP 0 206 832 Al). However, the compatibility of these hydrophobic top layers with the hydrophilic layer lying underneath is limited, so that detachment of the layer may occur during exposure to mechanical stresses.
Melamine resin dispersions which comprise completely or partly cured melamine resin particles are furthermore known. According to US 3 945 980 A, an amine resin la precondensate is diluted, with the addition of polyvinyl alcohol, until its water miscibility limit is exceeded and is cured under acid conditions. US 5 344 704 A describes dispersions of cured ground melamine resin particles in water or melamine resin solutions.
However, nanoscale dispersions and hydrophobic surfaces cannot be achieved with these dispersions.
2 The object of the invention is synthetic resin dispersions for the production of hydrophilic sheetlike structures or hydrophilic shaped articles provided with hydrophobic surfaces.
It has been found, surprisingly, that hydrophilic sheet-like structures or hydrophilic shaped articles provided with hydrophobic surfaces can be produced by coating hydrophilic sheet-like structures or hydrophilic shaped articles with aminoplast dispersions which comprise hydrophobic and hydrophilic melamine resin components and hydrophobizing agents.
The inventive object has been achieved by synthetic resin dispersions which, according to the invention, comprise a) an aqueous phase of solutions of hydrophilic melamine resin precondensates and latent curing catalysts in water or in mixtures of water and Cl-C 6 -alcohols and b) an organic nanophase in the form of nanodroplets and/or nanoparticles of 70 to 99 by weight of water-insoluble etherified melamine resin precondensates which contain acid curing catalysts and hydrophobizing agents and c) dispersing agents in a concentration of 1 to by weight, based on the total weight of the melamine resin precondensates, the ratio of hydrophilic melamine resin precondensates to water-insoluble etherified melamine resin precondensates in the synthetic resin dispersions being 10 1 to 1 10 and the water content of the synthetic resin dispersions being 8 to 50 by weight.
The synthetic resin dispersions according to the invention preferably comprise 0.1 to 5 by weight of 2a pigments and/or 0.1 to 5 by weight of flameproofing agents, in each case based on the total weight of the melamine resin precondensates.
Examples of suitable pigments which can be contained in the synthetic resin dispersions according to the invention are iron oxide, isoindoline pigments 3 containing ester groups, anthracene fluorescent dyestuffs, carbazole-dioxazine and delta-indanthrone blue pigment.
Examples of suitable flameproofing agents which can be contained in the synthetic resin dispersions according to the invention are ammonium polyphosphate, melamine cyanurate and zinc borate.
Examples of the melamine resin precondensates in the aqueous and in the organic nanophase are melamine resin precondensates which can contain formaldehyde, acetaldehyde and/or trimethylolacetaldehyde as aldehyde components and, in addition to melamine, also acetoguanamine and/or benzoguanamine as melamine components.
The melamine resin precondensates in the aqueous phase and in the organic nanophase of the synthetic resin dispersions according to the invention are preferably melamine resin precondensates based on melamine and formaldehyde.
The concentration of the curing catalysts both in the hydrophilic and in the water-insoluble melamine resin precondensates is preferably 0.05 to 3 by weight, based on the melamine resin precondensates.
It is furthermore preferable if the molar ratio of aldehyde component melamine component in the hydrophilic melamine resin precondensates is 1.6 1 to 1 and if the concentration of the hydrophilic melamine resin precondensates in the aqueous phase is to 50 by weight.
In a preferred embodiment, the hydrophilic melamine resin precondensates are melamine resin precondensates partly etherified with C 1
-C
4 -alcohols and/or non- 3a etherified melamine resin precondensates and the mixing ratio in the mixtures of water and C 1
-C
6 -alcohols is 5 to 5 It is particularly advantageous here if the content of hydroxyl groups which are not etherified with C-C4alcohols in the melamine resin precondensates partly etherified with Cl-C 4 -alcohols 4 is 5 to 75 mol%, based on the sum of hydroxyl groups and Cl-C 4 -alkoxy groups in the melamine resin precondensates partly etherified with C 1
-C
4 -alcohols.
Examples of melamine resin precondensates partly etherified with Cl-C 4 -alcohols are precondensates which contain 2,4-bis(methoxymethylamino)-6- 2-butoxymethylamino- 4,6-dihydroxymethylamino-l,3,5-triazine or 2ethoxymethyamino-4-methoxymethylamino-6as the main component in a mixture with higher molecular weight oligomers thereof.
Examples of non-etherified melamine resin precondensates are precondensates which contain 2,4,6tris(hydroxymethylamino)-1,3,5-triazine, 2,4bis(hydroxymethylamino)-6-amino-l, 3 ,5-triazine or 2,4bis(hydroxymethylamino)-6-(dihydroxymethyl)imino-1,3,5triazine as the main component in a mixture with higher molecular weight oligomers thereof.
Synthetic resin dispersions in which the aqueous phase contains 1 to 20 by weight, based on the hydrophilic melamine resin precondensates, of further water-soluble polymers and/or water-soluble polyhydric alcohols with molecular weights of 62 to 5,000 are furthermore preferred.
The further water-soluble polymers in the aqueous phase of the synthetic resin dispersions according to the invention are preferably hydroxyalkyl (meth)acrylate copolymers, polyhydroxy esters, polyvinyl alcohol, polypropylene oxides, polycaprolactone and/or ethylene oxide/propylene oxide block copolymers.
4a Examples of hydroxyalkyl (meth)acrylate copolymers as further water-soluble polymers in the aqueous phase of the synthetic resin dispersions according to the invention are hydroxy-ethyl acrylate/methyl methacrylate copolyers and acrylamide/hydroxybutyl acrylate copolymers.
Examples of polyhydroxy esters as further water-soluble polymers in the aqueous phase of the synthetic resin dispersions according to the invention are 5 polyhydroxy esters based on phthalic anhydride and glycerol and polyhydroxy esters based on maleic anhydride and pentaerythritol.
Examples of water-soluble polyhydric alcohols with molecular weights of 62 to 5,000 which can be contained in the aqueous phase of the synthetic resin dispersions are ethylene glycol, tripropylene glycol, hexanediol, pentaerythritol, sorbitol, polyethylene glycols and polytetrahydrofurans.
Preferred synthetic resin dispersions are those in which the water-insoluble etherified melamine resin precondensates in the organic nanophase are melamine resin precondensates completely etherified with C1-C4alcohols, C 2
-C
20 -diols and/or polyalkylene oxides with molecular weights of 250 to 5,000 and/or melamine resin precondensates partly etherified with Cs-C 18 -alcohols,
C
2
-C
20 -diols and/or polyalkylene oxides with molecular weights of 250 to 5,000.
Examples of the melamine resin precondensates which are completely etherified with Cl-C 4 -alcohols and are preferably contained in the organic nanophase as waterinsoluble etherified melamine resin precondensates are precondensates which contain 2,4,6tris(methoxymethylamino)-1,3,5-triazine, 4,6bis(ethoxymethylamino)-2-butoxymethylamino-l,3,5triazine or 2,4,6-tris(dimethoxymethylimino)-1, 3 5 triazine as the main component in a mixture with higher molecular weight oligomers thereof.
Examples of the melamine resin precondensates which are partly etherified with Cs-C 18 -alcohols and are preferably contained in the organic nanophase as waterinsoluble etherified melamine resin precondensates are dihydroxymethylamino-1,3,5-triazine or 2octyloxymethylamino-4-hexyloxymethylamino-6- 5a as the main component in a mixture with higher molecular weight oligomers thereof.
Examples of contained in precondensates etherified
C
2
-C
20 -diol components which can be the water-insoluble melamine resin which are completely or partly with
C
2
-C
20 -diols 6 are ethylene glycol, diglycol, octanediol and dianeethylene oxide adducts.
Examples of polyalkylene oxide components with molecular weights of 250 to 5,000 which can be contained in the water-insoluble melamine resin precondensates which are completely or partly etherified with polyalkylene oxides are polyethylene oxide, polypropylene oxide, ethylene oxide/propylene oxide block copolymers or polytetrahydrofurans.
Advantageous synthetic resin dispersions are those in which the molar ratio of aldehyde component melamine component in the water-insoluble etherified melamine resin precondensates is 3 1 to 6 1 and the average diameter of the nanodroplets or nanoparticles is 50 to 300 nm.
The organic nanophase preferably comprises 0.1 to 2 by weight of stabilizers, 1 to 20 by weight of waterinsoluble polyhydric alcohols with molecular weights of 134 to 5,000 and/or 1 to 30 by weight of laminar silicates, in each case based on the water-insoluble etherified melamine resin precondensates.
Examples of suitable stabilizers which can be contained in the organic nanophase are UV stabilizers, such as 2- (2-hydroxy-3-tert-butyl-5-methylphenyl)benzotriazole, 2,4-dihydroxybenzophenone, sebacic acid bis[2,2,6,6tetramethyl-l-(octyloxy)-4-piperidinyl] ester or bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and/or antioxidants, such as octadecyl 3-(3',5'-di-tert-butyl- 4'-hydroxyphenyl)propionate.
Examples of water-insoluble polyhydric alcohols with molecular weights of 134 to 5,000 which can be contained in the organic nanophase are octanediol, 6a dodecanediol, octadecanediol and polypropylene glycols with molecular weights of 500 to 5,000.
Examples of suitable laminar silicates which can be contained in the organic nanophase are montmorillonite, bentonite, kaolinite, muscovite, hectorite, fluorohectorite, kanemite, revdite, grumantite, ilerite, saponite, beidelite, nontronite, 7 stevensite, laponite, taneolite, vermiculite, halloysite, volkonskoite, magadite, rectorite, kenyaite, sauconite, boron fluorophlogopites and/or synthetic smectites.
The hydrophobizing agents which are contained in the organic nanophase are preferably 30 to 1 by weight of organic silicon compounds of the type of organosilanols, organosiloxanes, organosilanes, organoaminosilanes or polyorganosiloxanes terminated with amino end groups or hydroxyl end groups; surfacefluorinated SiO 2 nanoparticles, polytetrafluoroethylene nanoparticles and/or ethylenically unsaturated C 4
-C
20 dicarboxylic acid anhydride copolymers containing imide groups.
Examples of polyorganosiloxanes terminated with amino end groups or hydroxyl end groups as hydrophobizing agents are aminopropyl-terminated polydimethylsiloxanes or- hydroxybutyl-terminated polydimethylsiloxanes with molecular weights of 1,000 to 6,000.
Examples of organosilanols as hydrophobizing agents are trimethylsilanol, diethylsilanediol, triisopropylsilanol and triphenylsilanol.
Examples of organosiloxanes are tetramethyldisiloxanediol or tetraphenyldisiloxanediol.
Examples of organosilanes are tetraphenylsilane, vinyltrimethoxysilane and tetradodecyl-silane.
Examples of organoaminosilanes are triethylaminosilane and triphenylaminosilane.
Examples of surface-fluorinated SiO 2 nanoparticles are pyrogenic silicic acids which have average particle 7a diameters in the range from 5 to 30 nm and are modified by reaction with fluorinated hydrocarbons.
Suitable ethylenically unsaturated
C
4
-C
20 -dicarboxylic acid anhydride copolymers containing imide groups are styrene/maleic anhydride copolymers which are imidized with amines, such as octylamine, diglycolamine or ethanolamine.
8 Nonionic dispersing agents or mixtures of 50 to 99 by weight of nonionic and 1 to 50 by weight of anionic dispersing agents are advantageously employed as dispersing agents in the synthetic resin dispersions according to the invention.
Etherified melamine resin oligomers with molecular weights of 2,000 to 30,000 are preferably employed as dispersing agents in the synthetic resin dispersions.
Melamine resin oligomers etherified with polyethylene glycols with molecular weights of 1,000 to 8,000 and/or C1-C12-monoalkyl-etherified polyethylene glycols with molecular weights of 1,000 to 8,500 and C1-C10 alcohols are particularly advantageous.
In a particularly preferred embodiment the molar ratio here of polyethylene glycol C1-C10-alcohol is 1 to 2 1 and the molar ratio of melamine formaldehyde etherifying alcohol is 1 2.8 2.5 to 1 These etherified melamine resin oligomers have a hydrophilic and a hydrophobic radical. For this reason they can act as a dispersing agent. The advantage over the use of conventional dispersing agents is that the melamine resin oligomers are bonded covalently and therefore permanently in sheet-like structures.
The hydrophilic sheet-like structures are preferably laminates, pressed laminates or one-layered sheet-like carrier materials based on cellulose and/or polar plastics of the type of polyamide, polyester, polyvinyl acetate and/or polyvinyl alcohol, preferably paper.
The hydrophilic shaped articles are preferably timber products, or semi-finished products or moulded materials produced by thermoplastic processing of polar plastics of the type of polyamide, polyester, polyvinyl 8a acetate and/or polyvinyl alcohol or by processing of blends of 55 to 90 by weight of wood and 45 to 10 by weight of thermoplastics and/or thermosetting plastics.
Examples of hydrophilic shaped articles are timber profiles produced by working by cutting or turned timber objects, or products of polyamide or -9 polyethylene terephthalate produced by injection moulding or profile extrusion, such as cladding elements, covers or circular profiles.
Examples of thermoplastics which can be contained in the hydrophilic shaped articles of blends of 55 to 90 by weight of wood and 45 to 10 by weight of thermoplastics are polyethylene, polypropylene, polystyrene, polyamide 6 polymethyl methacrylate, poly- 2,6-dimethylphenylene oxide and polybutylene terephthalate.
Examples of thermosetting plastics which can be contained in the hydrophilic shaped articles of blends of 55 to 90 by weight of wood and 45 to 10 by weight of thermosetting plastics are phenolic resins, urea resins and unsaturated polyester resins.
The latent curing catalysts contained in the aqueous phase of the synthetic resin dispersions according to the invention are preferably ammonium salts, in particular ammonium peroxydisulphate, ammonium phosphate, ammonium sulphate, ammonium chloride, ammonium oxalate and/or ammonium thiocyanate;
C
1
-C
4 alkylammonium salts of carboxylic acids, in particular methylammonium phthalate, methylammonium maleate and/or the methylamine salt of naphthalenesulphonic acid; and/or esters of phosphoric acid, phosphorous acid, oxalic acid and/or phthalic acid, in particular diethyl phosphate, oxalic acid dimethyl ester and/or phthalic acid dimethyl ester.
Acid curing catalysts which are preferably contained in the water-insoluble melamine resin precondensates of the synthetic resin dispersions according to the invention are: at a molar ratio of aldehyde component/melamine component up to 4 1, blocked sulphonic acids, 9a aliphatic C 4
-C
1 8 -carboxylic acids, alkali metal salts or ammonium salts of phosphoric acid, 0 1 -0 1 2 -alkyl esters or C 2
-C
8 -hydroxyalkyl esters of C 6
-C
1 4 -aromatic carboxylic acids or inorganic acids, salts of melamine or guanarnines with Cl-C 1 8 -aliphatic carboxylic acids, anhydrides, half-esters or half-amides of 0 4
-C
2 0 dicarboxylic acids, half-esters or half-arnides of copolymers of ethylenically unsaturated
C
4 10
C
2 o-dicarboxylic acid anhydrides and ethylenically unsaturated monomers of the type of C 2
-C
20 -olefins and/or C 8
-C
20 -vinylaromatics, (meth)acrylic acid copolyers and/or salts of Cl-C 12 -alkylamines or alkanolamines with Cl-C 1 i-aliphatic,
C
6
-C
14 -aromatic or alkylaromatic carboxylic acids or inorganic acids of the type of hydrochloric acid, sulphuric acid or phosphoric acid, or at a molar ratio above 4 1, strong acids, preferably hydrochloric acid, sulphuric acid, phosphoric acid, p-toluenesulphonic acid, methanesulphonic acid, dodecylbenzenesulphonic acid, dinonylnaphthalenesulphonic acid and/or dinonylnaphthalenedisulphonic acid.
Examples of blocked sulphonic acids as acid curing catalysts in the water-insoluble melamine resin precondensates which have a molar ratio of aldehyde component/melamine component up to 4 1 are benzil monoxime tosylate, a-cyclohexylsulphonyloxyiminophenylacetic acid ethyl ester, acetone oxime pbenzoylbenzenesulphonate, a-(4-nitrobenzenesulphonyloxyimino)benzyl cyanide, 2-nitrobenzyl sulphonate and 2-methylsulphonyloxyimino-4-phenyl-but- 3-enenitrile.
Examples of aliphatic C4-C 18 -carboxylic acids as acid curing catalysts in the water-insoluble melamine resin precondensates which have a molar ratio of aldehyde component/melamine component up to 4 1 are butyric acid, caproic acid, palmitic acid, stearic acid and oleic acid.
Examples of alkali metal salts or ammonium salts of phosphoric acid as acid curing catalysts in the waterinsoluble melamine resin precondensates which have a molar ratio of aldehyde component/melamine component up 1Oa to 4 :1 are ammonium hydrogen phosphate, sodium polyphosphate and potassium hydrogen phosphate.
Examples of C 1
-C
12 -alkyl esters or C 2 -Cs-hydroxyalkyl esters of C 6
-C
14 -aromatic carboxylic acids or inorganic acids as acid curing catalysts in the water-insoluble melamine resin precondensates which have a molar ratio of aldehyde component/melamine component up to 4 1 are dibutyl phthalate, phthalic acid diglycol ester and/or trimellitic acid glycol ester.
11 Examples of salts of melamine or guanamines with Ci-C18aliphatic carboxylic acids as acid curing catalysts in the water-insoluble melamine resin precondensates which have a molar ratio of aldehyde component/melamine component up to 4 1 are melamine formate, melamine citrate and/or acetoguanamine butyrate.
Examples of anhydrides, half-esters or half-amides of
C
4
-C
20 -dicarboxylic acids as acid curing catalysts in the water-insoluble melamine resin precondensates which have a molar ratio of aldehyde component/melamine component up to 4 1 are maleic anhydride, mono-C1-C1ealkyl maleates, such as maleic acid monobutyl ester, maleic acid monoethylhexyl ester or monostearyl maleate, or maleic acid mono-Ci-C 18 -alkylamides, such as maleic acid monoethylamide, maleic acid monooctylamide or maleic acid monostearylamide.
Examples of half-esters or half-amides of copolymers of ethylenically unsaturated
C
4
-C
20 -dicarboxylic acid anhydrides and ethylenically unsaturated monomers of the type of C 2 -C2 0 -olefins and/or C 8
-C
20 -vinylaromatics as acid curing catalysts in the water-insoluble melamine resin precondensates which have a molar ratio of aldehyde component/melamine component up to 4 1 are half-esters or half-amides of copolymers of maleic anhydride and C 3 -Cs-a-olefins of the type of isobutene, diisobutene and/or 4-methylpentene and/or styrene with a molar ratio of maleic anhydride/C3 -Cs-a-olefin or styrene or corresponding monomer mixtures of 1 1 to 1 Examples of salts of C 1
-C
12 -alkylamines or alkanolamines with Cl-C 18 -aliphatic,
C
6
-C
14 -aromatic or alkylaromatic carboxylic acids and inorganic acids of the type of hydrochloric acid, sulphuric acid or phosphoric acid as acid curing catalysts in the water-insoluble melamine resin precondensates which have a molar ratio of lla aldehyde component /melamine component up to 4 1 are ethanolammonium chloride, triethylammonium maleate, diethanolammonium phosphate and/or isopropylammonium ptoluenesulphonate.
Particularly preferred synthetic resin dispersions are those which comprise as nonionic dispersing agents ethylene oxide/propylene oxide block copolymers, poly(C 2
-C
4 -alkylene) oxides monoetherified with C 8 -Ciealcohols, 12 esters of polyhydric alcohols with Cs-C 1 8 -carboxylic acids, C2-C 4 -alkylene oxide adducts on Cs-C 18 -fatty alcohols and/or copolymers of ethylenically unsaturated
C
4
-C
20 -dicarboxylic acid anhydrides and ethylenically unsaturated monomers of the type of C 2
-C
20 -olefins, Cs-
C
20 -vinylaromatics, C 4 -C2 1 -acrylic acid esters and/or C 5
C
22 -methacrylic acid esters, which have been imidized with poly(C 2
-C
4 -alkylene) oxides terminated by amino groups.
Examples of the poly(C 2
-C
4 -alkylene) oxides which are monoetherified with Cs-Cs 1 -alcohols and have molecular weights of 400 to 6,000 and are contained in the synthetic resin dispersions according to the invention as nonionic dispersing agents are polyethylene glycol monostearyl ether and polyethylene glycol monododecyl ether.
Examples of the esters of polyhydric alcohols with Cs-
C
18 -carboxylic acids contained in the synthetic resin dispersions according to the invention as nonionic dispersing agents are sorbitan fatty acid esters and polyethylene glycol glyceryl-stearate.
Examples of the C 2
-C
4 -alkylene oxide adducts on C 8
-C
18 fatty alcohols contained in the synthetic resin dispersions according to the invention as nonionic dispersing agents are oxyethylated fatty alcohols and oxyethylated oxo-alcohols.
Examples of the copolymers of ethylenically unsaturated
C
4
-C
20 -dicarboxylic acid anhydrides and ethylenically unsaturated monomers of the type of C 2
-C
20 -olefins, Cs-
C
20 -vinylaromatics, C 4
-C
21 -acrylic acid esters and/or
C
22 -methacrylic acid esters which have been imidized with amino-terminated poly(C 2
-C
4 -alkylene) oxides and are contained in the synthetic resin dispersions according to the invention as nonionic dispersing 12a agents are maleic anhydride/styrele copolymers or maleic anhydride/ca-methylstyrefle/butyl acrylate copolymers imidized with o-amino-terminated polyethylene oxides.
Examples of anionic dispersing agents in the synthetic resin dispersions according to the invention are alkyl sulphates, oxyethylated alkyl sulphates, ether sulphates, alkanesuipholates, olefinsulphonates and alkylnaphthalenesulphoflates.
13 Preferred anionic dispersing agents in the synthetic resin dispersions according to the invention are alkali metal salts of (meth)acrylic acid copolymers, salts of oxyethylated C6-C 18 -alkylphenol-sulphates and/or alkali metal and/or ammonium salts of Cs-C 18 -carboxylic acids and/or C 8
-C
18 -alkylsulphonates.
Examples of the salts of oxyethylated C 6
-C
18 -alkylphenol sulphates optionally contained in the synthetic resin dispersions according to the invention as anionic dispersing agents are oxyethylated sodium pnonylphenol-sulphate and oxyethylated sodium pdodecylphenol-sulphate.
Examples of the alkali metal and/or ammonium salts of Cs-C 18 -carboxylic acids optionally contained in the synthetic resin dispersions according to the invention as anionic dispersing agents are sodium oleate and ammonium palmitate.
The synthetic resin dispersions for the production of hydrophilic sheet-like structures or hydrophilic shaped articles provided with hydrophobic surfaces are prepared by a multi-stage process in which in the first process stage mixtures of hydrophilic melamine resin precondensates, water-insoluble melamine resin precondensates and hydrophobizing agents are homogenized as highly viscous liquids or melts at 50 to 130°C over residence times of 2 to 15 minutes and in the second process stage the mixtures are introduced at high shear rates over residence times of 3 minutes to 15 minutes into 8.7 to 100 by weight, based on the sum of the melamine resin precondensates, of water which contains 0.5 to by weight, based on the sum of the melamine resin precondensates, of dispersing agents and the 13a dispersions are cooled to room temperature at low shear rates, with further stirring, latent curing agents and acid curing catalysts being added after the cooling to room temperature.
It is preferable here if the water in the second process stage contains 1 to 25 by weight, based on the total weight of the melamine resin precondensates, of C3-C6- 14 alcohols as dispersing auxiliaries and/or water-soluble polymers and/or water-soluble polyhydric alcohols and is heated to temperatures up to 90 0 C, and if pigments and/or flameproofing agents are added after the cooling to room temperature.
A second process for the preparation of the synthetic resin dispersions according to the invention is a multi-stage process in which in the first process stage water-insoluble melamine resin precondensates are introduced as highly viscous liquids or melts at 50 to 1300C at high shear rates over residence times of 3 minutes to 15 minutes into 8.7 to 100 by weight, based on the water-insoluble melamine resin precondensates, of water which contains 0.5 to by weight, based on the water-insoluble melamine resin precondensates, of dispersing agents and the dispersions are cooled to room temperature at low shear rates, with further stirring, and in the second process stage hydrophilic melamine resin precondensates are added as solutions to the aqueous dispersion of the water-insoluble melamine resin precondensates and the mixture is homogenized, latent curing agents and acid curing catalysts being added to the aqueous solutions.
It is preferable here if the water-insoluble melamine resin precondensates in the first process stage and/or the aqueous solutions of the second process stage contain up to 30 by weight of hydrophobizing agent and the water in the first process stage contains 1 to by weight, based on the water-insoluble melamine resin precondensates, of C 3 -C6-alcohols as dispersing auxiliaries and/or water-soluble polymers and/or watersoluble polyhydric alcohols and is heated to temperatures up to 9000C, and if pigments and/or 14a flameproofing agents are added to the aqueous solutionS of the second process stage.
15 In a further multi-stage process for the preparation of the synthetic resin dispersions according to the invention in the first process stage melamine resins etherified with Cl-ClO-alcohols are reacted, in the presence or in the absence of acid curing catalysts, with polyethylene glycols with molecular weights of 500 to 8,000 at temperatures of 50 to 165 0 C to give etherified melamine resin oligomers, in the second process stage, at temperatures of to 200 0 C, mixtures of 15 to 40 by weight of etherified melamine resin oligomers and 85 to 60 by weight of melamine resins etherified with C1- C10-alcohols and with molecular weights of 300 to 800 are introduced at a high shear gradient into water, which is preheated to 20 to 800C, 0 to 8 by weight of hydrophobizing agent being added to the melt of etherified melamine resin oligomers and melamine resins etherified with C1-C10alcohols and/or the aqueous phase in the second process stage, and in the third process stage 10 to 40 by weight of hydrophilic melamine resin precondensates are mixed in the form of a 30 to 70 strength aqueous solution with 90 to 60 by weight of the mixture of melamine resin oligomers and etherified melamine resins of the second process stage.
For all three process variants, suitable dispersing units with a high shear action are in-line dispersers with a circulation, stirred reactors with highperformance dispersers for stirring speeds up to 25,000 revolutions per minute or ultrasonic dispersers.
The invention furthermore relates to hydrophilic sheetlike structures or hydrophilic shaped articles which 15a are provided with hydrophobic surfaces and are produced using the synthetic resin dispersions described above.
The application of the synthetic resin dispersions according to the invention to the hydrophilic sheetlike structure can be carried out by conventional application processes, such as roller application, doctor blade application, fluidized bed coating, dip coating, brushing and 16 spraying processes and electrostatic spraying.
Favourable drying and curing temperatures are in the range from 100 to 2200C.
During the application and drying operation, a substantial concentration of the organic nanophase takes place at the coating surface, so that after drying and curing the coating surface virtually exclusively comprises crosslinked melamine resins based on the water-insoluble etherified melamine resin precondensates. The hydrophobic surface layer produced on the hydrophilic sheet-like structures or hydrophilic shaped articles has a high adhesive strength on the hydrophilic sheet-like structures, since during the crosslinking operation it is linked chemically to the melamine resins which are based on the hydrophilic melamine resin precondensates and are absorbed into the hydrophilic sheet-like structures.
The thickness of the hydrophobic surfaces of the hydrophilic sheet-like structures or hydrophilic shaped articles provided with hydrophobic surfaces is preferably 1 to 40 pm.
Thin layer thicknesses of the hydrophobic surfaces on the hydrophilic sheet-like structures or hydrophilic shaped articles have the effect in the case of rough surfaces of good gluing properties of the products and an adequate permeability to water vapour.
In the production of the hydrophobic surfaces on the hydrophilic sheet-like structures, excluding laminates, or hydrophilic shaped articles, the synthetic resin dispersions are preferably applied by spraying on after preheating of the hydrophilic sheet-like structures or hydrophilic shaped articles to 50 to 950C, and the sheet-like structures or shaped articles impregnated with the synthetic resin dispersions are dried and 16a cured at 100 to 145°C. It is of particular advantage to carry out the drying and curing by infra-red irradiation of the impregnated sheet-like structures or shaped articles.
In the case of production of laminates based on hydrophilic sheet-like structures coated with hydrophobic surfaces, curing is preferably carried out by 17 conventional pressing technology under pressures of to 150 bar at temperatures in the range from 140 to 170 0
C.
In the case of shaped articles, such as profiles, which are produced by extrusion of blends of 55 to 90 by weight of wood and 45 to 10 by weight of thermoplastics or thermosetting plastics, or polar plastics of the type of polyamide, polyester, polyvinyl acetate and/or polyvinyl alcohol, for production of the hydrophobic surfaces it is of advantage to spray the synthetic resin dispersions on to the profile directly after the extruder die.
Preferred fields of use of the sheet-like structures or shaped articles coated with synthetic resin dispersions are uses in the construction sector, in particular as cladding panels, and in the sport and leisure sector where an improved resistance to weathering and the ability to be glued are required.
The invention is explained by the following examples: Example 1 330 g of a hydrophilic melamine-formaldehyde precondensate partly etherified with methanol, molar ratio of melamine/formaldehyde/bonded methanol 1 3 2.1, which contains 30 g of isobutanol, as a hydrophilic melamine resin precondensate, are melted at 120 0 C in a 2.5 1 stirred reactor with the addition of 100 g of an imidized styrene/maleic anhydride copolymer (molar ratio of styrene/maleic anhydride 2 1, imidized with a mixture of 70 mol% of octylamine and mol% of diglycolamine), as a hydrophobizing agent, and the components are homogenized.
17a 600 g of a water-insoluble melamine resin precondensate which contains 2,4,6-tris(methoxy-methylamino)-1,3,5triazine as the main component in a mixture with the corresponding higher molecular weight oligomers are metered into the low-viscosity melt in the course of minutes at 1000C and the components are homogenized.
The homogeneous melt obtained is dispersed in the course of 15 minutes in a 2.5 1 stirred reactor with a high-speed disperser (Ultra-Turrax, 18 Janke&Kunkel, Staufen), which contains 990 g of water and 18 g of a 75:25 dispersing agent mixture of an oxyethylated
C
16
-C
18 -alcohol mixture (80 mol of ethylene oxide/mol of alcohol) and an oxyethylated sodium pnonylphenol-sulphate (ethylene oxide content 23 by weight) at 700C, and, after the emulsion has cooled to 350C, 100 g of butanol, as a dispersing auxiliary, 1.2 g of methylammonium phthalate, as a latent curing agent, and 8 g of monostearyl maleate, as an acid curing catalyst, are added.
The average particle size of the nanophase in the dispersion, determined with a particle size detector (Zeta-Sizer), is 130 nm.
For production of a decorative paper (weight per unit area 80 g/m 2 provided with a hydrophobic surface, the decorative paper is coated with the synthetic resin dispersion by means of a doctor blade. Analysis of the decorative paper surface by ATR spectroscopy results in a content of etherified hydroxyl groups of the melamine resin precondensates of 98 mol%. After drying in a circulating air oven at 1400C to a volatile content of 5.9 by weight, the decorative paper has a resin content of 56 by weight.
A layer of the coated decorative paper is subsequently pressed together with 3 layers of core paper (weight per unit area 180 g/m 2 resin content 45 by weight of melamine-formaldehyde precondensate, molar ratio of melamine/formaldehyde 1 1.65) in a Collin laboratory press with a specific pressure of 90 bar at 1550C for 180 seconds.
The contact angle of distilled water on the laminate surface is 102 degrees.
18a If in a comparison experiment the hydrophilic melamineformaldehyde precondensate partly etherified with methanol (molar ratio of melamine/formaldehyde/bonded methanol 1 3 2.1) is applied, after addition of 1 by weight, based on the precondensate, of methylammonium phthalate, as a latent curing agent, to the decorative paper surface, analysis of the decorative paper surface by ATR spectroscopy results in a content of etherified hydroxyl groups of the 19 melamine resin precondensates of 75 mol%. After drying in a circulating air oven at 1400C to a volatile content of 5.9 by weight and lamination with kraft paper, the contact angle of distilled water on the surface of the laminate produced under analogous conditions is 69 degrees.
Example 2 A mixture of 250 g of a hydrophilic melamineformaldehyde precondensate partly etherified with methanol, molar ratio of melamine/formaldehyde/bonded methanol 1 3 2.1, which contains 30 g of isobutanol, is melted at 950C in a 2.5 1 stirred reactor with the addition of 75 g of an imidized styrene/maleic anhydride copolymer (molar ratio of styrene/maleic anhydride 2.6 1, imidized with a mixture of 60 mol% of octylamine and 40 mol% of ethanolamine), as a hydrophobizing agent, and the components are homogenized. 500 g of a water-insoluble etherified melamine resin precondensate which contains bis-2,4(dodecyloxy-methylamino)-6-hydroxymethylamino- 1,3,5-triazine as the main component in a mixture with higher molecular weight oligomers are metered into the low-viscosity melt in the course of 15 minutes at 950C and the components are homogenized.
The homogeneous melt obtained is dispersed in the course of 15 minutes in a 2.5 1 stirred reactor with a high-speed disperser (Ultra-Turrax, Janke&Kunkel, Staufen), which contains 950 g of water and 24 g of an oxyethylated cetyl alcohol/stearyl alcohol mixture (27 mol of ethylene oxide/mol of alcohol, molecular weight about 1,450) at 300C, and, after the emulsion has cooled to 200C, 80 g of isobutanol, as a dispersing auxiliary, 3 g of ammonium oxalate, as a latent curing agent, and 5.4 g of acetoguanamine butyrate, as an acid curing catalyst, are added.
19a The average particle size of the nanophase in the dispersion, determined with a particle size detector (Zeta-Sizer), is 55 nm.
For production of a decorative paper (weight per unit area 80 g/m 2 provided with a hydrophobic surface, the decorative paper is coated with the synthetic resin dispersion by means of a doctor blade. Analysis of the decorative paper surface by ATR spectroscopy results in a content of etherified hydroxyl groups 20 of the melamine resin precondensates of 70 mol%. After drying in a circulating air oven at 1400C to a volatile content of 6.1 by weight, the decorative paper has a resin content of 59 by weight.
A layer of the coated decorative paper is subsequently pressed together with 3 layers of core paper (weight per unit area 180 g/m 2 resin content 45 by weight of melamine-formaldehyde precondensate, molar ratio of melamine/formaldehyde 1 1.65) in a Collin laboratory press with a specific pressure of 90 bar at 155°C for 180 seconds.
The contact angle of distilled water on the laminate surface is 102 degrees.
If in a comparison experiment a hydrophilic melamineformaldehyde precondensate partly etherified with methanol, molar ratio of melamine/formaldehyde/bonded methanol 1 3 2.1, which contains 30 g of isobutanol, is applied, after addition of 1 by weight, based on the precondensate, of ammonium oxalate, as a latent curing agent, to the decorative paper surface, analysis of the decorative paper surface by ATR spectroscopy results in a content of etherified hydroxyl groups of the melamine resin precondensates of 51 mol%. After drying in a circulating air oven at 1400C to a volatile content of 5.9 by weight and lamination with kraft paper, the contact angle of distilled water on the surface of the laminate produced under analogous conditions is 65 degrees.
Example 3 A mixture of 260 g of a hydrophilic melamineformaldehyde precondensate partly etherified with methanol, molar ratio of melamine/formaldehyde/bonded methanol 1 5 3.2, 600 g of a water-insoluble 20a precondensate which contains 2,4bis(methoxymethylamino)-6-butoxymethyl-amino-l,3,5triazine as the main component in a mixture with higher molecular weight oligomers, and 40 g of polytetrafluoroethylene particles (average particle diameter 30 nm) is melted at 90 0 C in a 2.5 1 stirred reactor and the components are homogenized.
21 The melt obtained is dispersed in the course of minutes in a 2.5 1 stirred reactor with a high-speed disperser (Ultra-Turrax, Janke&Kunkel, Staufen), which contains 850 g of water and 17 g of oxyethylated oleyl alcohol (80 mol of ethylene oxide/mol of oleyl alcohol) at 65°C, and, after the emulsion has cooled to 350C, 2.9 g of ammonium phosphate, as a latent curing agent, and 8 g of phthalic acid diglycol ester, as an acid curing catalyst, are added.
The average particle size of the nanophase in the dispersion, determined with a particle size detector (Zeta-Sizer), is 55 nm.
For production of a decorative paper (weight per unit area 80 g/m 2 provided with a hydrophobic surface, the decorative paper is coated with the synthetic resin dispersion by means of a doctor blade. Analysis of the decorative paper surface by ATR spectroscopy results in a content of etherified hydroxyl groups of the melamine resin precondensates of 95 mol%. After drying of the decorative film in a circulating air oven at 1400C to a volatile content of 5.7 by weight, the decorative paper has a resin content of 58 by weight.
A layer of the coated decorative paper is subsequently pressed together with 3 layers of core paper (weight per unit area 180 g/m 2 resin content 45 by weight of melamine-formaldehyde precondensate, molar ratio of melamine/formaldehyde 1 1.65) in a Collin laboratory press with a specific pressure of 90 bar at 1600C for 150 seconds.
The contact angle of distilled water on the laminate surface is 94 degrees.
If in a comparison experiment a hydrophilic melamineformaldehyde precondensate partly etherified with 21a methanol, molar ratio of melamine/formaldehyde/bonded methanol 1 5 3.2, which contains 1 by weight, based on the precondensate, of ammonium phosphate, as a latent curing agent, is applied to the decorative paper surface, analysis of the decorative paper surface by ATR spectroscopy results in a content of etherified hydroxyl groups of the 22 melamine resin precondensates of 65 mol%. After drying in a circulating air oven at 140 0 C to a volatile content of 5.7 by weight, a contact angle of distilled water on the surface of the laminate produced under analogous conditions is 58 degrees results.
Example 4 A mixture of 320 g of a hydrophilic melamineformaldehyde precondensate partly etherified with methanol, molar ratio of melamine/formaldehyde/bonded methanol 1 3 2.1, 650 g of a water-insoluble melamine resin precondensate, which contains 2,4bis(dioctyloxymethyl-imino)-6-hydroxy-methylamino- 1,3,5-triazine as the main component in a mixture with higher molecular weight oligomers, and 35 g of hydroxypropyl-terminated polydimethylsiloxane(molecular weight 3,000) is melted at 100 0 C in a 2.5 1 stirred reactor and the components are homogenized.
The homogeneous melt obtained is dispersed in the course of 8 minutes in a 2.5 1 stirred reactor with a high-speed disperser (Ultra-Turrax, Janke&Kunkel, Staufen), which contains 810 g of water and 24 g of a propylene oxide/ethylene oxide block copolymer (ethylene oxide content 77 by weight) at 50°C, and, after the emulsion has cooled to 20 0 C, 3 g of ammonium peroxydisulphate, as a latent curing agent, and 3.5 g of p-toluenesulphonic acid, as an acid curing catalyst, are added.
The average particle size of the nanophase in the dispersion, determined with a particle size detector (Zeta-Sizer), is 90 nm.
For production of a decorative paper (weight per unit area 80 g/m 2 provided with a hydrophobic surface, the 22a decorative paper is coated with the synthetic resin dispersion by means of a doctor blade. Analysis of the decorative paper surface by ATR spectroscopy results in a content of etherified hydroxyl groups of the melamine resin precondensates of 72 mol%. After drying in a circulating air oven at 1400C to a volatile content of 5.9 by weight, the decorative paper has a resin content of 56 by weight.
23 A layer of the coated decorative paper is subsequently pressed together with 3 layers of core paper (weight per unit area 180 g/m 2 resin content 45 by weight of melamine-formaldehyde precondensate, molar ratio of melamine/formaldehyde 1 1.65) in a Collin laboratory press with a specific pressure of 90 bar at 1550C for 130 seconds.
The contact angle of distilled water on the laminate surface is 101 degrees.
If in a comparison experiment a hydrophilic melamineformaldehyde precondensate partly etherified with methanol, molar ratio of melamine/formaldehyde/bonded methanol 1 3 2.1, which contains 1 by weight, based on the precondensate, of ammonium peroxydisulphate, as a latent curing agent, is applied to the decorative paper surface, analysis of the decorative paper surface by ATR spectroscopy results in a content of etherified hydroxyl groups of the melamine resin precondensates of 64 mol%. After drying in a circulating air oven at 1400C to a volatile content of 5.7 by weight, a contact angle of distilled water on the surface of the laminate produced under analogous conditions is 57 degrees results.
Example 330 g of a hydrophilic melamine-formaldehyde precondensate partly etherified with methanol, molar ratio of melamine/formaldehyde/bonded methanol 1 3 2.1, which contains 30 g of isobutanol, as a hydrophilic melamine resin precondensate, are melted at 1080C in a 2.5 1 stirred reactor with the addition of 12.3 g of aminopropyl-terminated polydimethylsiloxane (molecular weight 3,000, amine content 1.1 mol%), as a hydrophobizing agent, and the components are homogenized. 600 g of a water-insoluble melamine resin 23a precondensate which contains 2,4,6-tris(methoxymethylamino)-1,3,5-triazine as the main component in a mixture with the corresponding higher molecular weight oligomers are metered into the low-viscosity melt in the course of 20 minutes at 1080C and the components are homogenized.
24 The homogeneous melt obtained is dispersed in the course of 15 minutes in a 2.5 1 stirred reactor with a high-speed disperser (Ultra-Turrax, Janke&Kunkel, Staufen), which contains 990 g of water and 18 g of a 75:25 dispersing agent mixture of an oxyethylated C16- Cls-alcohol mixture (80 mol of ethylene oxide/mol of alcohol) and an oxyethylated sodium p-nonylphenolsulphate (ethylene oxide content 23 by weight) at 700C, and, after the emulsion has cooled to 350C, 100 g of butanol, as a dispersing auxiliary, 1,2 g of methylammonium phthalate, as a latent curing agent, and 8 g of monostearyl maleate, as an acid curing catalyst, are added.
The average particle size of the nanophase in the dispersion, determined with a particle size detector (Zeta-Sizer), is 50 nm.
For production of a decorative paper (weight per unit area 80 g/m 2 provided with a hydrophobic surface, the decorative paper is coated with the synthetic resin dispersion by means of a doctor blade. Analysis of the decorative paper surface by ATR spectroscopy results in a content of etherified hydroxyl groups of the melamine resin precondensates of 98 mol%. After drying in a circulating air oven at 1400C to a volatile content of 5.9 by weight, the decorative paper has a resin content of 56 by weight.
A layer of the coated decorative paper is subsequently pressed together with 3 layers of core paper (weight per unit area 180 g/m 2 resin content 45 by weight of melamine-formaldehyde precondensate, molar ratio of melamine/formaldehyde 1 1.65) in a Collin laboratory press with a specific pressure of 90 bar at 1550C for 170 seconds.
24a The contact angle of distilled water on the laminate surface is 108 degrees.
If in a comparison experiment the hydrophilic melamineformaldehyde precondensate partly etherified with methanol (molar ratio of melamine/formaldehyde/bonded methanol 1 3 2.1) is applied, after addition of 1 by weight, based on the precondensate, of methylammonium phthalate, as a latent curing agent, to the decorative paper surface, 25 analysis of the decorative paper surface by ATR spectroscopy results in a content of etherified hydroxyl groups of the melamine resin precondensates of 74 mol%. After drying in a circulating air oven at 1400C to a volatile content of 5.9 by weight and lamination with kraft paper, the contact angle of distilled water on the surface of the laminate produced under analogous conditions is 68 degrees.
Example 6 360 g of a low molecular weight melamine-formaldehyde precondensate completely etherified with methanol (molar ratio of melamine/formaldehyde/methanol 1:3:3) are melted at 105°C in a 2.5 1 stirred reactor with the addition of 20 g of surface-fluorinated highly disperse silicic acid (average particle size 12 nm) and the mixture is mixed as a melt into 355 g of water, which has been heated to 45 0 C and contains 6.5 g of an oxyethylated C 16
-C
18 -alcohol mixture (80 mol of ethylene oxide per mol of alcohol), as a dispersing agent, by means of a high-speed disperser (Ultra-Turrax, Janke&Kunkel, Staufen). After cooling to 28 0 C, first g of a 50 strength aqueous mixture of a precondensate based on a melamine-formaldehyde impregnating resin (molar ratio of melamine/formaldehyde 1:1.69) and finally also 1.15 g of a block copolymer of ethylene oxide and dimethylsiloxane (ethylene oxide content approx. 20 by weight; molecular weight about 950) are added and the components are distributed homogeneously. A storage-stable low-viscosity mixture is formed and, after addition of 2.5 g of maleic acid, is used as an impregnating resin for decorative paper.
The average particle size of the nanophase in the dispersion, determined with a particle size detector (Zeta-Sizer), is 120 nm.
25a For production of a decorative paper (weight per unit area 80 g/m 2 provided with a hydrophobic surface, the decorative paper is coated with the synthetic resin dispersion by means of a doctor blade. Analysis of the decorative paper surface by ATR spectroscopy results in a content of etherified hydroxyl groups of the melamine resin precondensates of 99 mol%. After drying in a circulating air oven at 26 1400C to a volatile content of 5.4 by weight, the decorative paper has a resin content of 48 by weight.
A layer of the coated decorative paper is subsequently pressed together with 3 layers of core paper (weight per unit area 180 g/m 2 resin content 48 by weight of melamine-formaldehyde precondensate, molar ratio of melamine/formaldehyde 1 1.65) in a Collin laboratory press with a specific pressure of 90 bar at 1500C for 180 seconds.
The contact angle of distilled water on the laminate surface is 98 degrees.
Example 7 The preparation of the emulsion according to example 6 is repeated. However, 3.5 g of the ethylene oxide/dimethylsiloxane block copolymer are added at the same batch size. 3.5 g of maleic acid monobutyl ether instead of maleic acid, as a curing agent, are now added to 400 g of this emulsion using a high-speed disperser (Ultra-Turrax, Janke&Kunkel, Staufen). 400 g of this emulsion are mixed with 800 g of a 50 strength aqueous precondensate solution based on a nonetherified melamine-formaldehyde impregnating resin (molar ratio of melamine/formaldehyde 1:1.65) using a simple stirrer and the mixture is employed directly for impregnating a decorative paper (weight per unit area 110 g/m 2 The average particle size of the nanophase in the dispersion, determined with a particle size detector (Zeta-Sizer), is 125 nm.
Analysis of the decorative paper surface by ATR spectroscopy results in a content of etherified hydroxyl groups of the melamine resin precondensates of 98 mol%. After drying in a circulating air oven at 26a 1400C to a volatile content of 5.5 by weight, the decorative paper has a resin content of 51 by weight.
A layer of the coated decorative paper is subsequently pressed together with 3 layers of core paper (weight per unit area 180 g/m 2 resin content 48 by weight of melamine-formaldehyde precondensate, molar ratio of melamine/formaldehyde 1 1.65) in a 27 Collin laboratory press with a specific pressure of bar at 150 0 C for 180 seconds.
The contact angle of distilled water on the laminate surface is 96 degrees.
Example 8 The emulsion was prepared analogously to example 6, but no polysiloxane block copolymer and maleic acid were added.
g of a 1:1 mixture of an imidized styrene/maleic anhydride copolymer (molar ratio of styrene/MSA 2:1; imidized with a mixture of 60 mol% dodecylamine and mol% ethanolamine) and dipropylene glycol monobutyl ether are added to 360 g of the etherified resin according to example 6 and the mixture is melted at 1100C. Thereafter, the procedure is the same as in example 6. The low-viscosity stable emulsion is then mixed with 600 g of a 50 strength aqueous precondensate solution based on a non-etherified impregnating resin (molar ratio of melamine/formaldehyde 1:1.65) using a simple stirrer and the mixture is employed directly for impregnating a decorative paper (weight per unit area 80 g/m 2 The average particle size of the nanophase in the dispersion, determined with a particle size detector (Zeta-Sizer), is 95 nm. Maleic acid monobutyl ether is employed as the curing agent in an amount of 3 g (0.6 by weight, based on the total resin solids).
Analysis of the decorative paper surface by ATR spectroscopy results in a content of etherified hydroxyl groups of the melamine resin precondensates of 97 mol%. After drying in a circulating air oven at 140 0 C to a volatile content of 5.4 by weight, the decorative paper has a resin content of 50 by weight.
27a A layer of the coated decorative paper is subsequently pressed together with 3 layers of core paper (weight per unit area 180 g/m 2 resin content 48 by weight of melamine-formaldehyde precondensate, molar ratio of melamine/formaldehyde 1 1.65) in a Collin laboratory press with a specific pressure of 90 bar at 1500C for 180 seconds.
28 The contact angle of distilled water on the laminate surface is 94 degrees.
Example 9 360 g of a low molecular weight melamine-formaldehyde precondensate completely etherified with methanol (molar ratio of melamine/formaldehyde/methanol 1:3:3) are melted at 1100C in a 2.5 1 stirred reactor and are mixed as a melt into 365 g of water, which has been heated to 500C and contains 6 g of an oxyethylated C16-
C
18 -alcohol mixture (72 mol of ethylene oxide per mol of alcohol), as a dispersing agent, by means of a highspeed disperser (Ultra-Turrax, Janke&Kunkel, Staufen).
After cooling to 250C, first 70 g of a 50 strength aqueous mixture of a precondensate based on a melamineformaldehyde impregnating resin (molar ratio of melamine/formaldehyde 1:1.8) and finally also 10 g of an aqueous dispersion of polytetrafluoroethylene nanoparticles (solids content 60 by weight, average particle diameter 75 nm) are added and the components are distributed homogeneously. A storage-stable lowviscosity mixture is formed and, after addition of 3 g of maleic acid, is used as an impregnating resin for decorative paper.
The average particle size of the nanophase in the dispersion, determined with a particle size detector (Zeta-Sizer), is 105 nm.
For production of a decorative paper (weight per unit area 80 g/m 2 provided with a hydrophobic surface, the decorative paper is coated with the synthetic resin dispersion by means of a doctor blade. Analysis of the decorative paper surface by ATR spectroscopy results in a content of etherified hydroxyl groups of the melamine resin precondensates of 98 mol%. After drying in a circulating air oven at 1450C to a volatile content of 5.2 by weight, the decorative paper has a resin content of 52 by weight.
28a A layer of the coated decorative paper is subsequently pressed together with 3 layers of core paper (weight per unit area 180 g/m 2 resin content 48 by weight of melamine-formaldehyde precondensate, molar ratio of melamine/formaldehyde 1 1.65) in a Collin laboratory press with a specific pressure of 90 bar at 155 0 C for 200 seconds.
29 The contact angle of distilled water on the laminate surface is 106 degrees.
Example Sawdust (residual moisture content 7 by weight, average particle diameter 100 pm, composition 90 by weight of spruce and 10 by weight of fir, pH 5.5 at 100 g/l in H 2 0 and 20 0 C) at 6.2 kg/hour and a butene/ethylene copolymer modified with 0.2 by weight of maleic anhydride (melt index 0.85 g/10 minutes at 190°C/5 kg, average particle size 0.08 mm) at 3.8 kg/hour are metered into the feed hopper of a Werner&Pfleiderer ZSK 30 extruder with vacuum devolatilization, profile die 6 x 6 mm and belt takeoff device, temperature profile 90/140/185/210/200/165, and the mixture is melted, homogenized, devolatilized and discharged as a square profile. Before being laid on the belt take-off device, the square profile is passed through an annular nozzle spray head and coated with the synthetic resin dispersion according to example 1.
The contact angle of distilled water on the surface of the coated square profile from the sawdust/polyolefin blend is 90 degrees.

Claims (22)

1. Synthetic resin dispersions for the production of hydrophilic sheet-like structures or hydrophilic shaped articles provided with hydrophobic surfaces, characterized in that the synthetic resin dispersions comprise a) an aqueous phase of solutions of hydrophilic melamine resin precondensates and latent curing catalysts in water or in mixtures of water and C 1 -C 6 -alcohols and b) an organic nanophase in the form of nanodroplets and/or nanoparticles of 70 to 99 by weight of water-insoluble etherified melamine resin precondensates which contain acid curing catalysts and hydrophobizing agents and c) dispersing agents in a concentration of 1 to by weight, based on the total weight of the melamine resin precondensates, the ratio of hydrophilic melamine resin precondensates to water-insoluble etherified melamine resin precondensates in the synthetic resin dispersions being 10:1 to 1:10 and the water content of the synthetic resin dispersions being 8 to 50 by weight.
2. Synthetic resin dispersions according to Claim 1, characterized in that they comprise 0.1 to 5 by weight of pigments and/or 0.1 to 5 by weight of flameproofing agents, in each case based on the total weight of the melamine resin precondensates.
3. Synthetic resin dispersions according to Claim 1 or 2, characterized in that the melamine resin precondensates in the aqueous phase and in the organic phase are based on melamine and formaldehyde. 00
4. Synthetic resin dispersions according to any one of the preceding claims, characterized in that the concentration of the curing catalysts is 0.05 to 3 by weight, based on the melamine resin precondensates. 00 cl (N AH21(1228761 1):RTK 00 O 0 5. Synthetic resin dispersions according to any one of the preceding claims, characterized in that the molar ratio of aldehyde component melamine component in the hydrophilic melamine resin precondensaes is 1.6 1 to 4.5 1 and the concentration of the hydrophilic melamine resin precondensates in the aqueous phase is 10 to 50 00 Sby weight. C0 10 6. Synthetic resin dispersions according to any Sone of the preceding claims, characterized in that C- the hydrophilic melamine resin precondensates are melamine resin precondensates partly etherified with C 1 -C 4 -alcohols and/or non-etherified melamine resin precondensates and in that the mixing ratio in the mixtures of water and CI-C 6 -alcohols is to 5
7. Synthetic resin dispersions according to Claim 6, characterized in that the content of hydroxyl groups which are not etherified with C 1 -C 4 -alcohols in the melamine resin precondensates partly etherified with C 1 -C4-alcohols is 5 to 75 mol%, based on the sum of hydroxyl groups and C 1 -C 4 alkoxy groups in the melamine resin precondensates partly etherified with Ci-C 4 -alcohols.
8. Synthetic resin dispersions according to any one of the preceding claims, characterized in that the aqueous phase contains 1 to 20 by weight, based on the hydrophilic melamine resin precondensates, of further water-soluble polymers and/or water-soluble polyhydric alcohols with molecular weights of 62 to 5,000.
9. Synthetic resin dispersions according to any one of the preceding claims, characterized in that the water-insoluble etherified melamine resin A1121(1228761 I):RTK 31a precondensates are melamine resin precondensates completely etherified with C1-C 4 -alcohols, C2-C20- diols and/or polyalkylene oxides with molecular weights of 250 to 5,000 and/or melamine resin precondensates partly etherified with C 5 -Ces- alcohols, C 2 -C2 0 -diols and/or polyalkylene oxides with molecular weights of 250 to 5,000. 00 Synthetic resin dispersions according to any C one of the preceding claims, characterized in that the molar ratio of aldehyde component melamine component in the water-insoluble etherified melamine resin precondensates is 3 1 to 6 1 and in that the average diameter of the Snanodroplets or nanoparticles is 50 to 300 nm. 00 S11. Synthetic resin dispersions according to any C< 1 0 one of the preceding claims, characterized in that the organic nanophase comprises 0.1 to 2 by weight of stabilizers, 1 to 20 by weight of water-insoluble polyhydric alcohols with molecular weights of 134 to 5,000 and/or 1 to 30 by weight of laminar silicates, in each case based on the water-insoluble etherified melamine resin precondensates.
12. Synthetic resin dispersions according to any one of the preceding claims, characterized in that the hydrophobizing agents are organic silicon compounds of the type of organosilanols, organosiloxanes, organosilanes, organoaminosilanes or polyorganosiloxanes terminated with amino end groups or hydroxyl end groups; surface-fluorinated Si02 nanoparticles, polytetrafluoroethylene nanoparticles and/or ethylenically unsaturated C 4 acid anhydride copolymers containing imide groups.
13. Synthetic resin dispersions according to any one of the preceding claims, characterized in that nonionic dispersing agents or mixtures of 50 to 99 by weight of nonionic and 1 to 50 by weight of anionic dispersing agents are employed as dispersing agents. AH21(1228761 I):RTK 00 S14. Synthetic resin dispersions according to any one of Claims 1 to 12, characterized in that etherified melamine resin oligomers with molecular weights of 2,000 to 30,000 are employed as dispersing agents. S15. Synthetic resin dispersions according to Claim 14, 00 Scharacterized in that the etherified melamine resin oligomers are melamine resin oligomers M 10 etherified with polyethylene glycols with molecular weights of (N AH21(1228761 I):RTK 33 00 1,000 to 8,000 and/or Cl-C1 2 -monoalkyl-etherified (C polyethylene glycols with molecular weights of 1,000 to 8,500 and C1-C10 alcohols.
16. Synthetic resin dispersions according to Claim characterized in that the molar ratio of polyethylene glycol C1-C10 alcohol is 1 10 to 00 2 :1 and the molar ratio of melamine 0 formaldehyde etherifying alcohol is 1 :2.8 2.5 to 1 4.5
17. Synthetic resin dispersions according to any one of the preceding claims, characterized in that the hydrophilic sheet-like structures are laminates, pressed laminates or sheet-like carrier materials based on cellulose, preferably paper, wood, and/or polar plastics of the type of polyamide, polyester, polyvinyl acetate and/or polyvinyl alcohol.
18. Synthetic resin dispersions according to any one of the preceding claims, characterized in that the hydrophilic shaped articles are timber products, or semi-finished products or moulded materials produced by thermoplastic processing of polar plastics of the type of polyamide, polyester, polyvinyl acetate and/or polyvinyl alcohol or by processing of blends of 55 to 90 by weight of wood and 45 to 10 by weight of thermoplastics and/or thermosetting plastics.
19. Synthetic resin dispersions according to any one of the preceding claims, characterized in that the latent curing catalysts contained in the aqueous phase are ammonium salts, preferably methylammonium phthalate, methylammonium maleate and/or the methylamine salt of naphthalenesulphonic acid, and/or esters of AH21(1228761 1)RTK 33a phosphoric acid, phosphorous acid, oxalic acid and/or phthalic acid, preferably diethyl phosphate, oxalic acid dimethyl ester and/or phthalic acid dimethyl ester. 34 00 0 20. Synthetic resin dispersions according to any one of the preceding claims, N, characterized in that S- at a molar ratio of aldehyde component/melamine component up to 4 1, blocked sulphonic acids, aliphatic C 4 -Cl8-carboxylic acids, alkali metal salts or ammonium salts of phosphoric acid, Ci-Ci2-alkyl esters or C 2 -C 8 -hydroxyalkyl esters of C 6 -C 1 4 -aromatic carboxylic acids or inorganic acids, salts of melamine or 0 guanamines with Ci-C 1 8 -aliphatic carboxylic acids, anhydrides, half-esters or half- 00 Samides of C 4 -C 20 -dicarboxylic acids, half-esters or half-amides of copolymers of ethylenically unsaturated C 4 -C 2 0-dicarboxylic acid anhydrides and ethylenically to unsaturated monomers of the type of C 2 -C 20 -olefins and/or C 8 -C 2 0 -vinylaromatics, S(meth) acrylic acid copolymers and/or salts of Ci-Cl2-alkylamines or alkanolamines with Ci-Cis-aliphatic, C6-CI 4 -aromatic or alkylaromatic carboxylic acids or inorganic acids of the type of hydrochloric acid, sulphuric acid or phosphoric acid, of aldehyde component/melamine component or at a molar ratio are employed as acid curing catalysts in the water-insoluble melamine resin precondensates above 4 1, strong acids, preferably hydrochloric acid, sulphuric acid, phosphoric acid, p-toluenesulphonic acid, methanesulphonic acid, dodecylbenzenesulphonic acid, dinonylnaphthalenesulphonic acid and/or dinonylnaphthalenedisulphonic acid are employed as acid curing catalysts in the water-insoluble melamine resin precondensates.
21. Synthetic resin dispersions according to Claim 13, characterized in that the nonionic dispersing agents are ethylene oxide/propylene oxide block copolymers, poly(C 2 -C 4 -alkylene) oxides monoetherified with Cs-Cis-alcohols, esters of polyhydric alcohols with C 8 -Cis-carboxylic acids, C 2 -C 4 -alkylene oxide adducts AH21(1228761 1:RTK -34a on C 8 -0 8 -fatty alcohols and/or copolymers of ethylenically unsaturated C 4 -0 2 0 -dicarboxylic acid anhydrides and ethylenically unsaturated monomers of the type of C 2 -C 2 0 -olef ins, C 8 -0 20 vinylaromatics, 0 4 -C 2 1-acrylic acid esters and/or 0 5 -C 2 2 -methacrylic acid esters, which have been imidized with Po1Y (0 2 -C 4 alkylene) oxides terminated by amino groups. 00 S22. Synthetic resin dispersions according to Claim 13, C\ characterized in that the anionic dispersing agents are alkali metal salts of (meth)acrylic acid copolymers, salts of oxyethylated C 6 -Cl 8 alkylphenol-sulphates and/or alkali metal and/or ammonium salts of Cs-C 18 -carboxylic acids and/or C 8 C18-alkylsulphonates. 00
23. Process for the preparation of synthetic resin dispersions according to any one of the Spreceding claims, characterized in that they are Sprepared by a multi-stage process in which in the first process stage mixtures of hydrophilic melamine resin precondensates, water-insoluble melamine resin precondensates and hydrophobizing agents are homogenized as highly viscous liquids or melts at 50 to 130 0 C over residence times of 2 to 15 minutes and -in the second process stage the mixtures are introduced at high shear rates over residence times of 3 minutes to 15 minutes into 8.7 to 100 by weight, based on the sum of the melamine resin precondensates, of water which contains 0.5 to 10 by weight, based on the sum of the melamine resin precondensates, of dispersing agents and the dispersions are cooled to room temperature at low shear rates, with further stirring, latent curing agents and acid curing catalysts being added after the cooling to room temperature.
24. Process for the preparation of synthetic resin dispersions according to Claim 23, characterized in that the water in the second process stage contains 1 to 25 by weight, based on the total weight of the melamine resin precondensates, of C 3 -C 6 -alcohols as dispersing auxiliaries and/or water-soluble polymers alcohols and is heated AH21(1228761 I):RTK 35a to temperatures up to 90 0 C, and in that pigments and/or flameproofing agents are added after the cooling to room temperature. 00 Process for the preparation of synthetic resin dispersions according to any one of Claims 1 to 22, characterized in that they are prepared by a multi-stage process in which 5 in the first process stage water-insoluble melamine resin precondensates are introduced as highly viscous liquids or melts at 50 to 130 0 C 00 at high shear rates over residence times of 3 Sminutes to 15 minutes into 8.7 to 100 by C 10 weight, based on the water-insoluble melamine g3 resin precondensates, of water which contains to 10 by weight, based on the water- insoluble melamine resin precondensates, of dispersing agents and the dispersions are cooled to room temperature at low shear rates, with further stirring, and in the second process stage hydrophilic melamine resin precondensates are added as solutions to the aqueous dispersion of the water-insoluble melamine resin precondensates and the mixture is homogenized, latent curing agents and acid curing catalysts being added to the aqueous solutions.
26. Process for the preparation of synthetic resin dispersions according to Claim 25, characterized in that the water-insoluble melamine resin precondensates in the first process stage and/or the aqueous solutions of the second process stage contain up to 30 by weight of hydrophobizing agent and the water in the first process stage contains 1 to 25 by weight, based on the water- insoluble melamine resin precondensates, of C 3 -C 6 alcohols as dispersing auxiliaries and/or water- soluble polymers and/or water-soluble polyhydric alcohols and is heated to temperatures up to 90 0 C, and in that pigments and/or flameproofing agents are added to the aqueous solutions of the Al12111228761 11:RTK 36a 00 second process stage. S27. Process for the preparation of synthetic resin dispersions according to any one of Claims 1 5 to 22, characterized in that they are prepared by a multi-stage process in which 00 0O aO (N A1121(1228761 I:RTK 00 0 in the first process stage melamine resins C etherified with Cl-ClO-alcohols are reacted, in the presence or in the absence of acid curing catalysts, with polyethylene glycols with M 5 molecular weights of 500 to 8,000 at temperatures of 50 to 165 0 C to give etherified melamine resin oligomers, 0 00 in the second process stage, at temperatures of to 200 0 C, mixtures of 15 to 40 by weight of etherified melamine resin oligomers and to 60 by weight of melamine resins etherified Swith Ci-ClO-alcohols and with molecular weights of 300 to 800 are introduced at a high shear gradient into water, which is preheated to to 80 0 C, 0 to 8 by weight of hydrophobizing agent being added to the melt of etherified melamine resin oligomers and melamine resins etherified with Cl-ClO-alcohols and/or the aqueous phase in the second process stage, after which in the third process stage 10 to 40 by weight of hydrophilic melamine resin precondensates are mixed in the form of a 30 to 70 strength aqueous solution with 90 to 60 by weight of the mixture of melamine resin oligomers and etherified melamine resins of the second process stage.
28. Hydrophilic sheet-like structures or hydrophilic shaped articles provided with hydrophobic surfaces, produced using synthetic resin dispersions according to any one of Claims 1 to 22.
29. Hydrophilic sheet-like structures or hydrophilic shaped articles provided with hydrophobic surfaces, according to Claim 28, characterized in that the thickness of the hydrophobic AH21(122B761 I):RTK 37a surfaces is 1 to 40 tm. Hydrophilic sheet-like structures or hydrophilic shaped articles provided with hydrophobic surfaces, according to Claim 28 or 29, characterized in that for production of the hydrophobic surfaces, the synthetic resin dispersions are applied to the hydrophilic sheet- like structures, excluding laminates, or hydrophilic shaped articles by spraying on after preheating of the hydrophilic sheet-like structures 00 or hydrophilic shaped articles to 50 to 95 0 C, and the sheet-like structures or shaped articles impregnated with the synthetic resin dispersions are dried and cured at 100 to S145 0 C.
31. Use of sheet-like structures or shaped articles coated with synthetic resin dispersions, according to any one of Claims 28 to 30, for uses in the construction sector, in particular as cladding panels, and in the sport and leisure sector where an improved 0 resistance to weathering and the ability to be glued are required.
32. A synthetic resin dispersion for the production of hydrophilic sheet-like i structures or hydrophilic shaped articles, said dispersion being substantially as o0 hereinbefore described with reference to any one of the examples but excluding the i comparative examples.
33. A process for making a synthetic resin dispersion for the production of hydrophilic sheet-like structures or hydrophilic shaped articles, said process being substantially as hereinbefore described with reference to any one of the examples but excluding the comparative examples. Dated 12 May, 2008 AMI -Agrolinz Melamine International GmbH Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON AH21(1228761 I):RTK
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Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10333892A1 (en) * 2003-07-22 2005-02-10 Ami-Agrolinz Melamine International Gmbh Plastic product of high strength and flexibility
DE10333893A1 (en) * 2003-07-22 2005-02-10 Kompetenzzentrum Holz Gmbh Plastics and wood composites
DE10360320A1 (en) * 2003-12-18 2005-07-21 Ami-Agrolinz Melamine International Gmbh Melamine resin dispersion
IL165219A (en) 2004-11-15 2008-12-29 Delta Galil Ind Ltd Moisture-management in hydrophilic fibers
DE102005022370A1 (en) * 2005-05-10 2006-11-16 Merck Patent Gmbh Nanoscale fluorescent melamine particles
US9169157B2 (en) 2006-06-16 2015-10-27 Georgia-Pacific Chemicals Llc Formaldehyde free binder
US7803879B2 (en) 2006-06-16 2010-09-28 Georgia-Pacific Chemicals Llc Formaldehyde free binder
US7795354B2 (en) 2006-06-16 2010-09-14 Georgia-Pacific Chemicals Llc Formaldehyde free binder
WO2008098069A1 (en) * 2007-02-06 2008-08-14 Nanodynamics, Inc. Directed migration of hydrophobic nanomaterials at surfaces
US20080234423A1 (en) * 2007-03-21 2008-09-25 Alberta Research Council Inc. Phyllosilicate modified resins for lignocellulosic fiber based composite panels
US20100249309A1 (en) * 2007-04-05 2010-09-30 Menachem Lewin Nanocomposites and their surfaces
DE102007052764A1 (en) * 2007-05-04 2008-11-06 Cetelon Lackfabrik Gmbh Hydrophobic and scratch-resistant paints for metallic surfaces and brake dust-repellent wheel coatings
MY160132A (en) * 2008-11-11 2017-02-28 Akzo Nobel Coatings Int Bv Intumescent composition
CN102001116B (en) * 2010-10-21 2013-09-04 东北林业大学 Method for union modification of wood by treating cell walls through silicon-containing compound and filling cell cavities with polymer
CN102001117A (en) * 2010-10-21 2011-04-06 东北林业大学 Method for preparing hydrophobic wood
TWI671343B (en) * 2014-06-27 2019-09-11 日商富士軟片股份有限公司 Thermosetting resin composition, cured film, method for producing cured film, and semiconductor device
CN104356594B (en) * 2014-11-27 2016-05-25 长春工业大学 A kind of preparation method of organosilicon melamine resin compound particle
CN104786333A (en) * 2015-04-30 2015-07-22 湖南栋梁木业有限公司 Wood reinforced waterproof modification fluid and preparation method thereof
CN105348462B (en) * 2015-12-14 2017-12-12 武汉工程大学 A kind of organic mesoporous polymer of triazine radical and its preparation method and application
CN106009506B (en) * 2016-07-29 2018-01-19 神盾防火科技有限公司 A kind of anti-strike-through of clear water and preparation method and application

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002000429A1 (en) * 2000-06-21 2002-01-03 Agrolinz Melamin Gmbh Fibre composites with excellent dimensional stability, weather resistance and flameproofing properties
WO2002048261A2 (en) * 2000-12-15 2002-06-20 Agrolinz Melamin Gmbh Method for curing aminoplast resins
EP1247837A2 (en) * 2001-04-07 2002-10-09 Agrolinz Melamin GmbH Modified amino resins for semifinished products and molded bodies having an improved resilience

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3676290A (en) * 1969-05-15 1972-07-11 Westinghouse Electric Corp Polyvinyl fluoride surfaced laminates
US3841956A (en) * 1970-12-03 1974-10-15 Westinghouse Electric Corp Bonded weather resistant decorative laminate with slightly grained acrylic surface
JPS5227679B2 (en) * 1972-10-04 1977-07-21
US5344704A (en) * 1993-04-07 1994-09-06 Nevamar Corporation Abrasion-resistant, aesthetic surface layer laminate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002000429A1 (en) * 2000-06-21 2002-01-03 Agrolinz Melamin Gmbh Fibre composites with excellent dimensional stability, weather resistance and flameproofing properties
WO2002048261A2 (en) * 2000-12-15 2002-06-20 Agrolinz Melamin Gmbh Method for curing aminoplast resins
EP1247837A2 (en) * 2001-04-07 2002-10-09 Agrolinz Melamin GmbH Modified amino resins for semifinished products and molded bodies having an improved resilience

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