WO1982003401A1 - Film forming binder in the form of an aqueous dispersion or emulsion - Google Patents

Film forming binder in the form of an aqueous dispersion or emulsion Download PDF

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Publication number
WO1982003401A1
WO1982003401A1 PCT/DE1982/000067 DE8200067W WO8203401A1 WO 1982003401 A1 WO1982003401 A1 WO 1982003401A1 DE 8200067 W DE8200067 W DE 8200067W WO 8203401 A1 WO8203401 A1 WO 8203401A1
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Prior art keywords
aqueous dispersion
emulsion
weight
water
unsaturated polyester
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PCT/DE1982/000067
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German (de)
French (fr)
Inventor
Farben & Fasern Ag Basf
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Schwarz Guenther
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Priority to BR8207240A priority Critical patent/BR8207240A/en
Publication of WO1982003401A1 publication Critical patent/WO1982003401A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation

Definitions

  • the invention relates to aqueous dispersions or emulsions for reshaping binders, which may contain plasticizers, matting agents, fillers, pigments, additives and additives, for fast-curing coating agents.
  • Aqueous emulsions of unsaturated polyester resins are known from European Patent 3,337. They contain two unsaturated polyesters with ß, ⁇ - ethylenically unsaturated ethers, in addition one of these polyesters contains condensed polyalkylene glycol residues. These known emulsions are free of monomers and contain as blocking agents for prevent the inhibition of polymerization by the oxygen of the air waxes or paraffins. These known emulsions can be hardened in a mixture with photoinitiators with the aid of UV rays or polymerized in a mixture with peroxides at room temperature. They are proposed for open-pore coating on wood or wood-like materials.
  • polyester emulsions have the disadvantage that they require a relatively long drying time and if higher temperatures are used, intermediate drying via an evaporation zone is necessary to remove the water, because otherwise the film becomes milky cloudy due to water inclusions. For continuous operation, where very short hardening times are important, the hardening time is not sufficient until it can be stacked or wound up.
  • the object of the present invention is therefore to create aqueous dispersions or emulsions of this type for fast-curing coating compositions which do not have the known disadvantages.
  • aqueous dispersions or emulsions of film-forming binders for fast-curing coating compositions which are characterized in that they contain at least one acrylate polymer with a film-forming temperature of above 60 ° C. and at least one unsaturated polyester resin.
  • aqueous dispersions or emulsions in which there are 70 to 30% by weight of unsaturated polyester resin per 30 to 70% by weight of acrylate polymer, the sum of acrylate polymer and unsaturated polyester resin being 100% by weight.
  • Another object of the invention is the use of the aqueous dispersion or emulsion for the production of quick-hardening coatings on surfaces made of wood, wood materials, paper, non-woven, hardened or unhardened, impregnated with impregnating resins, woven or non-woven carrier materials, plastic films, asbestos cement boards, mineral fiber boards as well as metals, such as aluminum.
  • the invention also relates to a process for producing a fast-curing coating on a substrate, which is characterized in that the aqueous dispersion or emulsion according to the invention is mixed with a water-soluble peroxide hardener and, after being applied to the substrate, the coating within a few seconds at a temperature of over 80 ° C, preferably over 100 ° C tack-free and stackable.
  • the dispersions or emulsions according to the invention contain no organic solvent and can be diluted with water. They are also free of monomers that would be copolymerizable with the unsaturated polyesters.
  • the dispersions or emulsions according to the invention are practically odorless, they are suitable for fast-curing coatings on many substrates.
  • the hardened coatings are scratch-resistant and resistant to water, alcohol, household chemicals and. Resistant to solvents. Since only water serves as a diluent, the dispersions or emulsions are non-flammable. Tools with which these materials come into contact can be cleaned by rinsing with water. The use of cross-linking agents is unnecessary.
  • Cobalt accelerators and peroxide hardeners are added to the dispersions or emulsions according to the invention for curing. At higher temperatures above 80 ° C, tack-free hardening starts immediately after a short time.
  • acrylate polymers are used in the dispersion or emulsion according to the invention, the film formation temperature of which is above 60 ° C., preferably should be more than 100 ° C.
  • morylate polymers are known and commercially available.
  • acrylate polymers are understood to be homopolymerizates of acrylic acid derivatives and / or methacrylic acid derivatives or copolymers of these compounds with other copolymerizable monomers.
  • Monomers such as styrene, vinyl toluene and methacrylic acid esters of lower aliphatic alcohols with 1 to 3 C atoms are particularly suitable.
  • the acrylate polymers are generally prepared by the emulsion polymerization process and are then already in the form of an aqueous dispersion.
  • the unsaturated polyester resins which can be used in aqueous dispersions or emulsions are also known and commercially available. Their acid numbers are between 1 and 50, the OH numbers 10 to 120 and the average molecular weights are between 300 and 5,000. In order to obtain particularly good results, those unsaturated polyester resins are preferably also used that contain a polyalkylene glycol residue in a condensed form. Such unsaturated polyester resin types act as emulsifiers for the preparation of the unsaturated polyester resin emulsions. These are, for example, unsaturated polyesters as described, for example, in European patent application 3,337.
  • the dispersions or emulsions according to the invention can be prepared in a simple manner by mixing the acrylate polymer dispersion with the unsaturated polyester emulsion. It is also possible to slowly stir the aqueous acrylate polymer dispersion into the polyester mixture using a stirrer or a dissolver.
  • plasticizers fillers, matting agents, pigments, additives or to the aqueous dispersions or emulsions according to the invention
  • Additives e.g. Defoamers, thickeners and stabilizers, as well as wax or paraffin, and also add acrylic resins with a low film-forming temperature.
  • the acetone resistance of the hardened paint film can also be increased by adding up to 5% by weight of a water-soluble melamine-formaldehyde resin, e.g. Reinforce hexamethoxymethylmelamine, based on the solid resin content.
  • the water-soluble peroxide hardeners suitable for curing are e.g. Hydrogen peroxide, acetylacetone peroxide, methyl ethyl ketone hydroperoxide, cyclohexanone peroxide or aqueous emulsions of non-water-soluble peroxides.
  • the heavy metal salts of are suitable as accelerators
  • Carboxylic acids such as cobalt, manganese or vanacium acetate
  • the accelerators are usually in the form of their aqueous solutions or added as aqueous emulsions.
  • Usual amounts that ensure excellent curing are 0..5 to 5% by weight of peroxide and 0.01 to 0.2% by weight of heavy metal salt, based on the total of the unsaturated polyester resins used.
  • UV absorbers can be added to the dispersions or emulsions, e.g. 2-hydroxy-4-methoxybenzophenone or cinnamic acid derivatives or benzotriazine derivatives.
  • aqueous dispersions or emulsions according to the invention can be applied by the customary application methods
  • Spraying, rolling, casting are applied to the substrate in a wet film layer thickness of up to 200 ⁇ m, preferably up to 100 ⁇ m.
  • the wet film layer thicknesses are smaller.
  • 8 to 15 g / m 2 are applied to gap-proof paper and 15 to 25 g / m 2 to absorbent paper with the aid of the roller application or the knife application.
  • An order of 8 to 15 g / m 2 is usually proposed for an aluminum foil.
  • the coating is cured without intermediate curing or predrying.
  • a hard coating is already achieved with an exposure time of 10 seconds when the coated substrate is exposed to a jet air of 140 ° C. With the help of an infrared heater, drying at 140 ° C object temperature takes less than 5 seconds.
  • polyesters and acrylate polymers used in the examples had the following composition:
  • Acid number 22 27 Viscosity (mPa.s), measured as a 70% by weight solution in styrene at 20 ° C 100 560
  • composition and preparation of the dispersions or emulsions according to the invention in parts by weight.
  • Barium sulfate (Blanc fixe) 8 To prepare the dispersion or emulsion, the acrylate polymer is first processed with the water to form a dispersion in a di-solver, unless the polymerization has already been carried out as an emulsion polymerization in the water.
  • polyester resins A and B were diluted with the paraffin emulsion in water and the acrylic polymer dispersion using a dissolver. The remaining substances were then mixed in.
  • the resulting emulsion is stable. It is catalyzed with 0.25 part by weight of a 30% hydrogen peroxide solution.
  • the emulsions obtained according to Examples 1, 2 and 3 are then rolled or knife-coated onto gap-proof paper. The application amount is approximately 10 g / m 2 . Drying was carried out at 140 ° C object temperature using an infrared heater and an irradiation time of 2 seconds. The resulting clearcoat film was stackable and could be rolled up into a roll using an endless paper web as a substrate base without the individual layers sticking together.
  • Example 4 was applied to a hardboard with a wet film thickness of 150 ⁇ m and cured with a nozzle dryer at 140 ° C. for 60 seconds. The resulting film was scratch-resistant.

Abstract

The film forming binder in the form of an aqueous dispersion or emulsion for quick hardening coating, containing optionally emollients, mat agents, filler materials, pigments, additives, contains at least one acrylic polymer having a film forming temperature exceeding 60<o>C and at least one unsaturated polyester resin. It is used for the preparation of quick hardening coatings of surfaces made of different materials.

Description

Wäßrige Dispersion oder Emulsion filmbildender Bindemittel Aqueous dispersion or emulsion of film-forming binders
Die Erfindung bezieht sich auf wäßrige Dispersionen oder Emulsionen fUmbildender Bindemittel, die gegebenenfalls Weichmacher, Mattierungsmittel, Füllstoffe, Pigmente, Additive und Zusatzmittel enthalten, für schnellhärtende Überzugsmittel.The invention relates to aqueous dispersions or emulsions for reshaping binders, which may contain plasticizers, matting agents, fillers, pigments, additives and additives, for fast-curing coating agents.
Wäßrige Emulsionen von ungesättigten Polyesterharzen sind aus der europäischen Patentschrift 3 337 bekannt. Sie enthalten zwei ungesättigte Polyester mit ß, γ- ethylenisch ungesättigten Ethcrgruppen, zusätzlich enthält einer von diesen Polyestorn Polyalkylenglykolreste einkondensiert. Diese bekannten Emulsionen sind frei von Monomeren und enthalten als Sperrmittel zum Ver- hindern der Inhibierung der Polymerisation durch den Sauerstoff der Luft Wachse oder Paraffine. Diese bekannten Emulsionen lassen sich im Gemisch mit Fotoinitiatoren mit Hilfe von UV-Strahlen härten oder im Gemisch mit Peroxiden bei Raumtemperatur polymerisieren. Sie werden vorgeschlagen für die offenporige Beschichtung auf Holz oder holzähnlichen Stoffen.Aqueous emulsions of unsaturated polyester resins are known from European Patent 3,337. They contain two unsaturated polyesters with ß, γ- ethylenically unsaturated ethers, in addition one of these polyesters contains condensed polyalkylene glycol residues. These known emulsions are free of monomers and contain as blocking agents for prevent the inhibition of polymerization by the oxygen of the air waxes or paraffins. These known emulsions can be hardened in a mixture with photoinitiators with the aid of UV rays or polymerized in a mixture with peroxides at room temperature. They are proposed for open-pore coating on wood or wood-like materials.
Diese bekannten Polyesteremulsionen haben den Nachteil, das sie eine relativ lange Trockenzeit benötigen und bei Anwendung höherer Temperaturen eine Zwischentrocknung über eine Abdunstzone zur Entfernung des Wassers erforderlich ist, weil der Film sonst durch Wassereinschlüsse milchig trüb wird. Für die kontinuierliche Arbeitsweise, wo es auf sehr kurze Härtungszeiten ankommt, reicht die Härtungszeit bis zur Stapelfähigkeit bzw. Aufwickelbarkeit nicht aus.These known polyester emulsions have the disadvantage that they require a relatively long drying time and if higher temperatures are used, intermediate drying via an evaporation zone is necessary to remove the water, because otherwise the film becomes milky cloudy due to water inclusions. For continuous operation, where very short hardening times are important, the hardening time is not sufficient until it can be stacked or wound up.
Aufgabe der vorliegenden Erfindung ist es deshalb, wäßrige Dispersionen oder Emulsionen dieser Art für schnellhärtende überzugsrnittel zu schaffen, die die bekannten Nachteile nicht aufweisen.The object of the present invention is therefore to create aqueous dispersions or emulsions of this type for fast-curing coating compositions which do not have the known disadvantages.
Diese Aufgabe wurde überraschenderweise gelöst Zurch wäßrige Dispersionen oder Emulsionen filmbildender Bindemittel für schnellhärtende Überzugsmittel, die dadurch gekennzeichnet sind, daß sie mindestens ein Acrylatpolymerisat mit einer Filmbildungstemperatur von über 60° C und mindestens ein ungesättigtes Polyesterharz enthalten.This object was surprisingly achieved by aqueous dispersions or emulsions of film-forming binders for fast-curing coating compositions, which are characterized in that they contain at least one acrylate polymer with a film-forming temperature of above 60 ° C. and at least one unsaturated polyester resin.
Besonders gute Ergebnisse werden erreicht und deshalb bevorzugt sind solche wäßrigen Dispersionen oder Emulsionen, in denen auf 30 bis 70 Gew-% Acrylatpolymerisat 70 bis 30 Gew-% ungesättigtes Polyesterharz kommen, wobei die Summe von Acrylatpolymerisat und ungesättigtem Polyesterharz 100 Gew-% beträgt. Ein weiterer Gegenstand der Erfindung ist die Verwendung der wäßrigen Dispersion oder Emulsion für die Herstellun von schnellhärtenden Überzügen auf Oberflächen aus Holz, Holzwerkstoffen, Papier, Vlies, gehärteten oder ungehärteten, mit Tränkharzen imprägnierten, gewebten oder ungewebten Trägermaterialien, Kunststoff-Folien, Asbestzementplatten, Mineralfaserplatten sowie Metallen, wie z.B. Aluminium.Particularly good results are achieved and therefore preferred are aqueous dispersions or emulsions in which there are 70 to 30% by weight of unsaturated polyester resin per 30 to 70% by weight of acrylate polymer, the sum of acrylate polymer and unsaturated polyester resin being 100% by weight. Another object of the invention is the use of the aqueous dispersion or emulsion for the production of quick-hardening coatings on surfaces made of wood, wood materials, paper, non-woven, hardened or unhardened, impregnated with impregnating resins, woven or non-woven carrier materials, plastic films, asbestos cement boards, mineral fiber boards as well as metals, such as aluminum.
Gegenstand der Erfindung ist auch ein Verfahren zur Herstellung eines schnellhärtenden Überzuges auf einem Substrat, das sich dadurch auszeichnet, daß man die erfindungsgemäße wäßrige Dispersion oder Emulsion mit einem wasserlöslichen Peroxidhärter vermischt und nach dem Aufbringen auf das Substrat den Überzug innerhalb weniger Sekunden bei einer Temperatur von über 80° C, vorzugsweis über 100° C klebfrei und stapelfähig härtet.The invention also relates to a process for producing a fast-curing coating on a substrate, which is characterized in that the aqueous dispersion or emulsion according to the invention is mixed with a water-soluble peroxide hardener and, after being applied to the substrate, the coating within a few seconds at a temperature of over 80 ° C, preferably over 100 ° C tack-free and stackable.
Die erfindungsgemäßen Dispersionen oder Emulsionen enthalten kein organisches Lösungsmittel und sind mit Wasser verdünnbar. Sie sind ferner frei von Monomeren, die mit den ungesättigten Polyestern copolymerisierbar wären.The dispersions or emulsions according to the invention contain no organic solvent and can be diluted with water. They are also free of monomers that would be copolymerizable with the unsaturated polyesters.
Die erfindungsgemäßen Dispersionen oder Emulsionen sind praktisch geruchsfrei, sie eignen sich für schnellhärtende Überzüge auf vielen Substraten. Die gehärteten Überzüge sind kratzfest und gegen Wasser, Alkohol, Haushaltschemikalien und. Lösungsmittel beständig. Da nur Wasser als Verdünnungsmittel dient, sind die Dispersionen oder Emulsionen unbrennbar. Arbeitsgeräte, mit denen diese Materialien in Berührung kommen, können durch Abspülen mit Wasser gereinigt werden. Die Mitverwendung von Vernetzungsmitteln ist entbehrlich. Für die Härtung werden den erfindungsgemäßen Dispersionen oder Emulsionen Kobaltbeschleuniger und Peroxidhärter zugesetzt. Bei höheren Temperaturen über 80° C setzt sofort nach kurzer Zeit eine klebfreie Härtung ein. Die sehr schnell einsetzende klebfreie Filmbildung wird unterstützt und stabilisiert durch eine zusätzliche durch chemische Härtung in Gang gesetzte Vernetzung. Natürlich ist es auch möglich., nach Zusatz von Kobaltbeschleuniger und Peroxidhärter den Überzug nur bei Raumtemperatur zu härten. Es entsteht in diesem Falle jedoch nur ein Film mit nicht ausreichenden technologischen Eigenschaften.The dispersions or emulsions according to the invention are practically odorless, they are suitable for fast-curing coatings on many substrates. The hardened coatings are scratch-resistant and resistant to water, alcohol, household chemicals and. Resistant to solvents. Since only water serves as a diluent, the dispersions or emulsions are non-flammable. Tools with which these materials come into contact can be cleaned by rinsing with water. The use of cross-linking agents is unnecessary. Cobalt accelerators and peroxide hardeners are added to the dispersions or emulsions according to the invention for curing. At higher temperatures above 80 ° C, tack-free hardening starts immediately after a short time. The very quick, tack-free film formation is supported and stabilized by an additional crosslinking set in motion by chemical hardening. Of course it is also possible to harden the coating only at room temperature after adding the cobalt accelerator and peroxide hardener. In this case, however, only a film is produced with insufficient technological properties.
Nur solche Acrylatpolymerisate finden in der erfindungs- gemäßen Dispersion oder Emulsion Verwendung, deren Filmbildungstemperatur über 60° C beträgt, vorzugsweise soll sie mehr als 100° C betragen. Solche Morylatpoly- merisate sind bekannt und handelsüblich. Unter Acrylat- polymerisaten im Sinne der Erfindung werden Homopolyme- risate von Acrylsäurederivaten und/oder Methacrylsäure- derivaten oder Copolymerisate dieser Verbindungen mit anderen mischpolymerisierbaren Monomeren verstanden. Bevorzugt geeignet sind Monomere, wie Styrol, Vinyl- toluol und Methacrylsäureester niederer aliphatischer Alkohole mit 1 bis 3 C-Atomen. Andere Monomere können in geringen Anteilen bis zu insgesamt 25 Gew-%, bezogen auf 100 % der Gesamtmonomeren, mitverwendet werden. Die Acrylatpolymerisate werden in der Regel nach dem Verfahren der Emulsionspolymerisation hergestellt und liegen dann bereits in Form einer wäßrigen Dispersion vor.Only those acrylate polymers are used in the dispersion or emulsion according to the invention, the film formation temperature of which is above 60 ° C., preferably should be more than 100 ° C. Such morylate polymers are known and commercially available. For the purposes of the invention, acrylate polymers are understood to be homopolymerizates of acrylic acid derivatives and / or methacrylic acid derivatives or copolymers of these compounds with other copolymerizable monomers. Monomers such as styrene, vinyl toluene and methacrylic acid esters of lower aliphatic alcohols with 1 to 3 C atoms are particularly suitable. Other monomers can be used in small proportions up to a total of 25% by weight, based on 100% of the total monomers. The acrylate polymers are generally prepared by the emulsion polymerization process and are then already in the form of an aqueous dispersion.
Die in wäßrigen Dispersionen oder Emulsionen einsetzbaren ungesättigten Polyesterharze sind ebenfalls bekannt und handelsüblich. Ihre Säurezahlen betragen zwischen 1 und 50, die OH-Zahlen 10 bis 120 und die mittleren Molekulargewichte liegen zwischen 300 und 5 000. Um besonders gute Resultate zu erhalten, werden vorzugsweise noch solche ungesättigten Polyesterharze mitverwen det, die Polyalkylenglykolreste ein kondensiert enthalten. Derartige ungesättigte Polyesterharztypen wirken als Emulgatoren für die Herstellung der ungesättigten Polyesterharzemulsionen. Es handelt sich z.B. um ungesättigte Polyester, wie sie z.B. in der europäischen Patentanmeldung 3 337 beschrieben sind.The unsaturated polyester resins which can be used in aqueous dispersions or emulsions are also known and commercially available. Their acid numbers are between 1 and 50, the OH numbers 10 to 120 and the average molecular weights are between 300 and 5,000. In order to obtain particularly good results, those unsaturated polyester resins are preferably also used that contain a polyalkylene glycol residue in a condensed form. Such unsaturated polyester resin types act as emulsifiers for the preparation of the unsaturated polyester resin emulsions. These are, for example, unsaturated polyesters as described, for example, in European patent application 3,337.
Die Herstellung der erfindungsgemäßen Dispersionen oder Emulsionen kann auf einfache Weise durch Mischen der Acrylatpolymerisat-Dispersion mit der ungesättigten Polyester-Emulsion erfolgen. Es ist auch möglich, die wäßrige Acrylatpolymerisat-Dispersion iη das Polyestergemisch langsam mit Hilfe eines Rührers oder eines Dissolvers einzurühren.The dispersions or emulsions according to the invention can be prepared in a simple manner by mixing the acrylate polymer dispersion with the unsaturated polyester emulsion. It is also possible to slowly stir the aqueous acrylate polymer dispersion into the polyester mixture using a stirrer or a dissolver.
In vielen Fällen ist es zweckmäßig, den erfindungsgemäßen wäßrigen Dispersionen oder Emulsionen noch Weichmacher, Füllstoffe, Mattierungsmittel, Pigmente, Additive oderIn many cases it is expedient to add plasticizers, fillers, matting agents, pigments, additives or to the aqueous dispersions or emulsions according to the invention
Zusatzmittel, wie z.B. Entschäumungsmittel, Verdickungsmittel und Stabilisatoren, sowie Wachs oder Paraffin, ferner auch Acrylatharze mit niedriger Filmbildungstemperatur zuzusetzen. Die Aceton-Beständigkeit des gehärteten Lackfilms läßt sich noch durch einen Zusatz von bis zu 5 Gew-% eines wasserlöslichen Melamin-Formaldehyd-Harzes, z.B. Hexamethoxymethylmelamin, auf den Festharzanteil bezogen, verstärken.Additives, e.g. Defoamers, thickeners and stabilizers, as well as wax or paraffin, and also add acrylic resins with a low film-forming temperature. The acetone resistance of the hardened paint film can also be increased by adding up to 5% by weight of a water-soluble melamine-formaldehyde resin, e.g. Reinforce hexamethoxymethylmelamine, based on the solid resin content.
Die für die Härtung geeigneten wasserlöslichen Peroxidhärter sind z.B. Wasserstoffperoxid, Acetylacetonperoxid, Methylethylketonhydroperoxid, Cyclohexanonperoxid oder wäßrige Emulsionen nicht wasserlöslicher Peroxide. Als Beschleuniger sind geeignet die Schwermetallsalze vonThe water-soluble peroxide hardeners suitable for curing are e.g. Hydrogen peroxide, acetylacetone peroxide, methyl ethyl ketone hydroperoxide, cyclohexanone peroxide or aqueous emulsions of non-water-soluble peroxides. The heavy metal salts of are suitable as accelerators
Carbonsäuren, wie Kobalt-, Mangan- oder Vanaciumacetat,Carboxylic acids, such as cobalt, manganese or vanacium acetate,
-naphtenat oder -acetylacetonat. Die Beschleuniger werden in der Regel in Form ihrer wäßrigen Lösungen oder als wäßrige Emulsionen zugesetzt.-naphtenate or -acetylacetonate. The accelerators are usually in the form of their aqueous solutions or added as aqueous emulsions.
übliche Mengen, die eine ausgezeichnete Härtung gewährleisten, sind 0..5 bis 5 Gew-% Peroxid und 0,01 bis 0,2 Gew-% Schwermetallsalz, bezogen auf die Summe der eingesetzten ungesättigten Polyesterharze.Usual amounts that ensure excellent curing are 0..5 to 5% by weight of peroxide and 0.01 to 0.2% by weight of heavy metal salt, based on the total of the unsaturated polyester resins used.
Zum Schutz von lichtempfindlichen Untergründen können den Dispersionen oder Emulsionen geringe Mengen der bekannten UV-Absorber zugesetzt werden, z.B. 2-Hydroxy- 4-methoxybenzophenon oder Zimtsäurederivate oder Benzo- triazinderivate.To protect light-sensitive substrates, small amounts of the known UV absorbers can be added to the dispersions or emulsions, e.g. 2-hydroxy-4-methoxybenzophenone or cinnamic acid derivatives or benzotriazine derivatives.
Die erfindungsgemäßen wäßrigen Dispersionen oder Emul- sionen können nach den üblichen Auftragsverfahren desThe aqueous dispersions or emulsions according to the invention can be applied by the customary application methods
Spritzens, Walzens, Gießens auf das Substrat aufgebracht werden in einer Naßfilmschichtdicke bis zu 200 μm, vorzugsweise bis 100 μm. In der Regel sind die Naßfilmschichtdicken geringer. So werden beispielsweise mit Hilfe des Walzauftrages oder des Rakelauftrages auf spaltfestes Papier 8 bis 15 g/m2 und auf saugfähiges Papier 15 bis 25 g/m2 aufgebracht. Für eine Aluminiumfolie wird in der Regel ein Auftrag von 8 bis 15 g/m2 vorgeschlagen.Spraying, rolling, casting are applied to the substrate in a wet film layer thickness of up to 200 μm, preferably up to 100 μm. As a rule, the wet film layer thicknesses are smaller. For example, 8 to 15 g / m 2 are applied to gap-proof paper and 15 to 25 g / m 2 to absorbent paper with the aid of the roller application or the knife application. An order of 8 to 15 g / m 2 is usually proposed for an aluminum foil.
Ohne Zwischenhärtung oder Vortrocknung erfolgt die Härtung des Überzuges. So wird bereits ein harter Überzug erreicht bei einer Einwirkungsdauer von 10 Sekunden, wenn das beschichtete Substrat einer Düsenluft von 140°C ausgesetzt wird. Mit Hilfe eines Infrarotstrahlers erfolgt die Trocknung bei 140° C Objekttemperatur bereits schon unter 5 Sekunden.The coating is cured without intermediate curing or predrying. A hard coating is already achieved with an exposure time of 10 seconds when the coated substrate is exposed to a jet air of 140 ° C. With the help of an infrared heater, drying at 140 ° C object temperature takes less than 5 seconds.
Aufgrund dieser extrem kurzen Trocknungszeiten werden Bandgeschwindigkeiten von ca. 100 m/min. erreicht. Dies ermöglicht eine kontinuierliche und rasche Arbeitsweise in Lackieranlagen. BeispieleDue to these extremely short drying times, belt speeds of approx. 100 m / min. reached. This enables continuous and rapid operation in paint shops. Examples
Die in den Beispielen verwendeten Polyester und Acrylatpolymerisate hatten folgende Zusammensetzung:The polyesters and acrylate polymers used in the examples had the following composition:
Polvester (in Molen) A BNew Year's Eve (in moles) A B
Maleinsäureanhydrid 1,0 1,0Maleic anhydride 1.0 1.0
Propandiol-1,2 0,55 Polyethylenglykol (MG 400) 0,79Propanediol-1.2 0.55 polyethylene glycol (MW 400) 0.79
Trimethylolpropandiallylether 1,0 0,4Trimethylolpropane diallyl ether 1.0 0.4
Säurezahl 22 27 Viskosität (mPa.s), gemessen .als 70 Gew-%-ige Lösung in Styrol bei 20° C 100 560Acid number 22 27 Viscosity (mPa.s), measured as a 70% by weight solution in styrene at 20 ° C 100 560
Acrylatpolymerisat (in Gewichtsteilen) ausAcrylate polymer (in parts by weight)
Styrol 50 Methylmethacrylat 38Styrene 50 methyl methacrylate 38
Ethylacrylat 10Ethyl acrylate 10
Methacrylsäure 2Methacrylic acid 2
Zusammensetzung und Herstellung der erfindungsgemäßen Dispersionen bzw. Emulsionen in Gewichtsteilen.Composition and preparation of the dispersions or emulsions according to the invention in parts by weight.
Beispiel 1 2 3 4Example 1 2 3 4
Polyester A 25 20 20 20Polyester A 25 20 20 20
Polyester B 5 5 5Polyester B 5 5 5
Acrylatpolymerisat 20 20 16 20Acrylate polymer 20 20 16 20
Hexamethoxymethylmelamin 5Hexamethoxymethylmelamine 5
Entschäumer 0,5 0,5 0,5 0,5Defoamer 0.5 0.5 0.5 0.5
Paraffin (Fp57-60°C)-Emulsion 30 30 30 30 in Wasser (10 %-ig)Paraffin (mp57-60 ° C) emulsion 30 30 30 30 in water (10%)
Kobaltacetat (1-%-ige Lösung 0,5 0,5 0,5 0,5 in Wasser)Cobalt acetate (1% solution 0.5 0.5 0.5 0.5 in water)
Wasser 15 15 15 -15Water 15 15 15 -15
Titandioxid (Rutil) 7Titanium dioxide (rutile) 7
Bariumsulfat (Blanc fixe) 8 Zur Herstellung der Dispersion bzw. Emulsion wird zunächst in einem Di≤solver das Acrylatpolymerisat mit dem Wasser zu einer Dispersion verarbeitet, sofern nicht die Polymerisation bereits schon als Emulsionspolymerisation in dem Wasser ausgeführt wurde.Barium sulfate (Blanc fixe) 8 To prepare the dispersion or emulsion, the acrylate polymer is first processed with the water to form a dispersion in a di-solver, unless the polymerization has already been carried out as an emulsion polymerization in the water.
Die Polyesterharze A und B wurden mittels eines Dissolvers mit der Paraffin-Emulsion in Wasser und- der Acrylatpolymerisat-Dispersion verdünnt. Danach wurden die übrigen Stoffe zugemischt.The polyester resins A and B were diluted with the paraffin emulsion in water and the acrylic polymer dispersion using a dissolver. The remaining substances were then mixed in.
Die entstandene Emulsion ist stabil. Sie wird mit 0,25 Gewichtsteilen einer 30-%-igen Wasserstoffperoxidlösung katalysiert. Anschließend werden die gemäß Beispiel 1, 2 und 3 erhaltenen Emulsionen auf spaltfestes Papier aufgewalzt oder aufgerakelt. Die Auftragsmenge beträgt etwa 10 g/m2. Die Trocknung erfolgte bei 140° C Objekttemperatur mittels eines Infrarotstrahlers und einer Bestrahlungszeit von 2 Sekunden. Der entstandene Klarlackfilm war stapelfest und ließ sich bei Verwendung einer endlosen Papierbahn als Substratunterlage zu einer Rolle aufrollen, ohne daß die einzelnen Schichten miteinander verklebten.The resulting emulsion is stable. It is catalyzed with 0.25 part by weight of a 30% hydrogen peroxide solution. The emulsions obtained according to Examples 1, 2 and 3 are then rolled or knife-coated onto gap-proof paper. The application amount is approximately 10 g / m 2 . Drying was carried out at 140 ° C object temperature using an infrared heater and an irradiation time of 2 seconds. The resulting clearcoat film was stackable and could be rolled up into a roll using an endless paper web as a substrate base without the individual layers sticking together.
Beispiel 4 wurde mit einer Naßfilmschichtdicke von 150 μm auf eine Hartfaserplatte aufgebracht und mit einem Düsentrockner bei 140° C 60 Sekunden gehärtet. Der entstandende Film war kratzfest. Example 4 was applied to a hardboard with a wet film thickness of 150 μm and cured with a nozzle dryer at 140 ° C. for 60 seconds. The resulting film was scratch-resistant.

Claims

Patentansprüche Claims
1. Wäßrige Dispersion oder Emulsion filmbildender Bindemittel für schnellhärtende überzugsmittel mit gegebenenfalls Weichmachern, Mattierungsmitteln, Füllstoffen, Pigmenten, Additiven und Zusatzstoffen, dadurch gekennzeichnet, daß sie mindestens ein Acrylatpolymerisat mit einer Filmbildungstemperatur von über 60° C und mindestens ein ungesättigtes Polyesterharz enthält.1. Aqueous dispersion or emulsion of film-forming binders for fast-curing coating agents, optionally with plasticizers, matting agents, fillers, pigments, additives and additives, characterized in that they contain at least one acrylate polymer with a film-forming temperature of over 60 ° C and at least one unsaturated polyester resin.
2. Wäßrige Dispersion oder Emulsion nach Anspruch 1, dadurch gekennzeichnet, daß auf 30 bis 70 Gew-% Acrylatpolymerisat 70 bis 30 Gew-% ungesättigtes Polyesterharz verwendet werden, wobei die Summe von Acrylatpolymerisat und ungesättigtem Polyesterharz 100 Gew-% beträgt.2. Aqueous dispersion or emulsion according to claim 1, characterized in that 70 to 30% by weight of unsaturated polyester resin are used on 30 to 70% by weight of acrylate polymer, the sum of acrylate polymer and unsaturated polyester resin being 100% by weight.
3. Wäßrige Dispers-ion oder Emulsion nach den Ansprüchen 1 oder 2, dadurch gekennzeichnet, daß sie zusätzlich bis zu 5 Gew-% eines wasserlöslichen Melamin-Formal- dehyd-Harzes oder Harnstoff-Formaldehyd-Harzes, auf den Festharzanteil bezogen, enthält.3. Aqueous dispersion or emulsion according to claims 1 or 2, characterized in that it additionally contains up to 5% by weight of a water-soluble melamine-formaldehyde resin or urea-formaldehyde resin, based on the proportion of solid resin.
4. Verwendung der wäßrigen Dispersion oder Emulsion gemäß den Ansprüchen 1 bis 3 für die Herstellung von schnellhärtenden Überzügen auf Oberflächen aus Holz, HolzWerkstoffen, Papier, Vlies, Kunststoff-Folien, Asbestzementplatten, Mineralfaserplatten, sowie Metallen, insbesondere Aluminium, gehärteten oder ungehärteten, mit Tränkharzen imprägnierten, gewebten oder ungewebten Trägermaterialien. 4. Use of the aqueous dispersion or emulsion according to claims 1 to 3 for the production of quick-curing coatings on surfaces made of wood, wood materials, paper, nonwoven, plastic films, asbestos cement boards, mineral fiber boards, and metals, in particular aluminum, hardened or uncured, with Impregnation impregnated, woven or non-woven backing materials.
5. Verfahren zum Herstellen eines schnellhärtenden5. Process for making a fast-curing
Überzuges auf einem Substrat unter Verwendung der wäßrigen Dispersion oder Emulsion gemäß den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß man die Dispersion oder Emulsion mit einem wasserlöslichen Kobaltbeschleuniger und einem wasserlöslichen Peroxidhärter vermischt und nach dem Aufbringen auf das Substrat den Überzug bei einer Temperatur von über 80° C zu einem klebfreien und stapelfähigen Film aushärtet. Coating on a substrate using the aqueous dispersion or emulsion according to Claims 1 to 3, characterized in that the dispersion or emulsion is mixed with a water-soluble cobalt accelerator and a water-soluble peroxide hardener and, after application to the substrate, the coating at a temperature of above 80 ° C hardens into a tack-free and stackable film.
PCT/DE1982/000067 1981-03-31 1982-03-24 Film forming binder in the form of an aqueous dispersion or emulsion WO1982003401A1 (en)

Priority Applications (1)

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BR8207240A BR8207240A (en) 1981-03-31 1982-03-24 WATER DISPERSION OR EMULSION OF FILM-MAKING BINDERS

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DE3112694810331 1981-03-31
DE3112694A DE3112694C2 (en) 1981-03-31 1981-03-31 Aqueous dispersion or emulsion of film-forming binders

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US (1) US4459379A (en)
EP (1) EP0062245B1 (en)
JP (1) JPS58500410A (en)
AT (1) ATE8910T1 (en)
BR (1) BR8207240A (en)
CA (1) CA1214895A (en)
DE (2) DE3112694C2 (en)
ES (1) ES511017A0 (en)
MX (1) MX161462A (en)
WO (1) WO1982003401A1 (en)
ZA (1) ZA822112B (en)

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MX161462A (en) 1990-09-28
ES8302759A1 (en) 1983-02-01
JPS58500410A (en) 1983-03-17
EP0062245A1 (en) 1982-10-13
DE3260521D1 (en) 1984-09-13
ES511017A0 (en) 1983-02-01
US4459379A (en) 1984-07-10
ATE8910T1 (en) 1984-08-15
CA1214895A (en) 1986-12-02
ZA822112B (en) 1983-03-30
DE3112694A1 (en) 1982-10-28
JPH0240101B2 (en) 1990-09-10
EP0062245B1 (en) 1984-08-08
BR8207240A (en) 1983-06-21
DE3112694C2 (en) 1984-10-25

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