EP0000941A1 - Low-volatility, curable, unsaturated polyester resins with good lamination properties - Google Patents
Low-volatility, curable, unsaturated polyester resins with good lamination properties Download PDFInfo
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- EP0000941A1 EP0000941A1 EP78100727A EP78100727A EP0000941A1 EP 0000941 A1 EP0000941 A1 EP 0000941A1 EP 78100727 A EP78100727 A EP 78100727A EP 78100727 A EP78100727 A EP 78100727A EP 0000941 A1 EP0000941 A1 EP 0000941A1
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- polyester resins
- paraffin
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- unsaturated
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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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 low-evaporation, curable in the presence of conventional polymerization initiators, highly overlaminable unsaturated polyester resins composed of an ethylenically unsaturated polyester, a copolymerizable, ethylenically unsaturated monomeric compound and, if appropriate, further structural components and auxiliaries which contain wax mixtures to reduce monomer evaporation and to improve the ability to be overlaminated.
- Molding and molding compounds made from unsaturated polyester resins usually contain, in addition to unsaturated polyesters and copolymerizable monomeric vinyl compounds, polymerization initiators and inhibitors, and often powdered fillers and glass fibers or flat glass fiber structures.
- Low-shrinkable molding compositions also contain up to 30 percent by weight of thermoplastic polymers.
- small amounts of finely divided alkaline earth oxides are added to the polyester molding compounds before they are mixed with fillers. Thickening takes place due to salt formation with the carboxyl end groups of the unsaturated polyester and complex formation.
- DT-OS 1 956 376 it is proposed to apply a wax-like substance, its dispersion or solution in a thin layer to a lacquer polyester resin shortly before curing, gasoline hydrocarbons and aromatics being mentioned as solvents for these barrier layer formers, which are preferably sprayed on .
- a disadvantage of this process is that the barrier layer formers are dissolved in large amounts of solvents - usually 1% by weight solutions of the wax-like substances are used - and the solutions have to be applied to the films of the unsaturated paint polyester resins in a separate operation. It should also be noted that when coating the paint film too high a pressure, too high a temperature and too much solubility of the process components are avoided with the solution containing the barrier layer former, because otherwise the hardenable lacquer film and the barrier layer could mix.
- polyester resin If only one layer of polyester resin is cured in one operation, such as when painting, then you can achieve as low a styrene loss as possible by adding paraffin.
- paraffins have the disadvantage that they also act as release agents. This means that polyester resin layers cured in the presence of paraffins have a cloudy, inert surface. If further unsaturated polyester resin is applied to such a surface and cured, an inadequate bond is obtained and the two cured resin layers can be separated from one another relatively easily. The better the substrate is hardened, the worse the adhesion.
- the ability to overlaminate unsaturated polyester resins can be increased by adding water-in-oil or oil-in-water emulsifiers with an HBL of 1.5 to 15 or by adding liquid alkanes or their mixtures can be improved to waxy substances.
- a disadvantage of the two methods is that the adhesion between two laminate layers is still not completely satisfactory and that the polyester resins can only be produced with insufficient reproducibility.
- the object of the present invention was to develop unsaturated curable polyester resins in which the olefinically unsaturated monomers do not evaporate or only evaporate to a minor extent during processing without the overlaminability being impaired.
- polyester resins according to the invention surprisingly have the advantage that the release agent effect is eliminated by the special composition of the paraffin mixture without increasing the monomer evaporation.
- Resins are made in a manner known per se by mixing the paraffin mixture with the polyester resin components (a) - (d). It has proven to be expedient to dissolve the paraffin mixture in an ethylenically unsaturated monomer, preferably styrene, and to meter the monomer solution obtained into the polyester resin.
- monohydric, trihydric or higher alcohols e.g. Ethylhexanol, fatty alcohols, benzyl alcohols, 1,2-di- (allyloxy-) propanol (, - 3), Gylcerin, pentaerythritol or trimethylolpropane
- the polyhydric, especially dihydric alcohols are generally reacted in stoichiometric or approximately stoichiometric amounts with polybasic, in particular dibasic carboxylic acids or their condensable derivatives.
- Suitable carboxylic acids or their derivatives are dibasic olefinically unsaturated, preferably ⁇ , ⁇ -olefinically unsaturated carboxylic acids, such as e.g. Maleic acid, fumaric acid, itaconic acid, citraconic acid, methylene glutaric acid and mesaconic acid or their esters or preferably their anhydrides.
- Other modifying dibasic, unsaturated and / or saturated and aromatic carboxylic acids or derivatives such as e.g.
- Succinic acid glutaric acid, cL-methylglutaric acid, adipic acid, sebacic acid, pimelic acid, phthalic anhydride, o-phthalic acid, isophthalic acid, terephthalic acid, dihydrophthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, 3,6-endomethylene-dichloromethloro-methylene-dichloro-thalophthalic acid, 1,2-methylene chloride be condensed in, further mono-, tri-and higher basic carboxylic acids, such as Ethylhexanoic acid, fatty acids, methacrylic acid, propionic acid, benzoic acid, 1,2,4-benzenetricarboxylic acid or 1,2,4,5-benzenetetracarboxylic acid.
- the unsaturated polyesters are generally prepared from their components by melt condensation or condensation under azeotropic conditions.
- amorphous and given if crystallizable unsaturated polyesters are used.
- the unsaturated polyesters have an acid number of 10 to 100, preferably 25 to 60, and an average molecular weight of about 600 to 4,000, preferably 800 to 3,000.
- the molding compositions to be used for the process according to the invention generally contain 10 to 70, preferably 15 to 50 percent by weight, based on component a) to c), of unsaturated polyesters a).
- Suitable copolymerizable olefinically unsaturated monomeric compounds are the vinyl and allyl compounds customarily used for producing unsaturated polyester molding compositions, such as styrene, substituted styrenes, such as p-chlorostyrene or vinyltoluene, esters of acrylic acid and methacrylic acid with alcohols containing 1 to 18 carbon atoms, such as e.g.
- allyl esters e.g. Diallyl phthalate
- vinyl esters e.g. Ethylhexanoic acid vinyl ester, vinyl pivalate and others.
- component (b) is generally preferred in an amount of 5 to 60% in the polyester resins as from 10 to 45 percent by weight, based on the mixture of components a) + b).
- paraffins instead of the paraffins, however, other wax-like substances, for example the paraffin oxidation products known as so-called montan wax, or their esters, carnauba wax, long-chain fatty acids such as stearic acid, stearyl stearate, ceresine and the like can also be used.
- montan wax or their esters
- carnauba wax long-chain fatty acids
- stearic acid stearyl stearate
- ceresine and the like can also be used.
- the unsaturated polyester resins contain 0.01 to 5 percent by weight, preferably 0.05 to 1 percent by weight, in particular 0.1 to 0.5 percent by weight, of the paraffin mixture, based on the Total weight of components (a) and (b).
- Paraffin waxes which consist of 0.01 to 0.5 percent by weight of a paraffin with a melting point of 25 ° to 50 ° C., preferably 46 ° to 48 ° C. and 0.01 to 0.5 percent by weight of one, are particularly proven and therefore preferably used Paraffins with a melting point of 51 ° to 100 ° C, preferably 56 ° to 58 ° C, the weight percentages being based in each case on the total weight of the polyester resin components a) and b).
- Point d As structural components and auxiliaries accordingly Point d, as they are usually used in unsaturated polyester resins, are, for example, suitable: thickeners, inhibitors, fillers, reinforcing agents and, if appropriate, inert solvents, polymerization accelerators, shrinkage-reducing additives and other auxiliaries customarily used in the processing of polyester resins.
- thickeners are: alkaline earth metal oxides or hydroxides, such as calcium oxide, calcium hydroxide, magnesium hydroxide and preferably magnesium oxide, and mixtures of these oxides and / or hydroxides.
- the alkaline earth oxides can also be partially replaced by zinc oxide.
- the content of thickeners in the polyester resins is generally 0.5 to 5, preferably 1 to 3 percent by weight, based on the mixture of components (a) and (b).
- the usual inhibitors come into question, e.g. Hydroquinone, tert-butyl catechol, p-benzoquinone, chloranil, nitrobenzenes, such as m-dinitrobenzene, thiodiphenylamine or salts of N-nitroso-N-cyclohexylhydroxylamine and mixtures thereof.
- the inhibitors are generally present in the polyester resins in an amount of 0.005 to 0.2, preferably 0.01 to 0.1 percent by weight, based on components a) and b).
- Suitable fillers are e.g. Usual fine powdery or granular inorganic or organic fillers, such as chalk, kaolin, quartz powder, dolomite, heavy spar, metal powder, cement, talc, diatomaceous earth, wood powder, wood chips, pigments and the like.
- Inorganic or organic fibers or flat structures optionally woven therefrom, for example those made of glass, asbestos, cellulose and synthetic organic high polymers, such as polyesters and polyamides.
- the fillers and reinforcing materials can be used in amounts of 5 to 200 percent by weight, based on components a) and b).
- inert solvents include ketones, esters, hydrocarbons in amounts of up to 100 percent by weight, based on component a).
- the unsaturated polyester resins of the invention can be pre-accelerated.
- Possible polymerization accelerators are, for example, heavy metal salts such as cobalt and vanadium salts, tertiary aromatic amines, 1,3-diketone compounds such as acetylacetone, ⁇ -keto esters such as ethyl acetoacetate and ⁇ -ketoamides such as diethyl acetoacetic acid and combinations of these compounds.
- Contrast-reducing additives that can also be used are, for example, thermoplastic polymers such as polystyrene, styrene copolymers, polyvinyl acetates and / or poly (meth) acrylates.
- Thermoplastic polymers which contain carboxyl groups in amounts of 1 to 5 percent by weight, based on the total weight, bound in the polymer chain are preferably used.
- the shrinkage-reducing additives are usually used in amounts of 1 to 30, preferably 8 to 15 percent by weight, based on the weight of components (a) and (b).
- paraffin mixtures are incorporated into the structural components (a) to (d) of the low-evaporation, easily overlaminable, curable unsaturated polyester resins.
- Suitable paraffin mixtures are those which contain paraffins, the melting point of which is below and once above 50 ° C.
- the mixing of the individual components (a) to (d) and the admixing of the paraffin mixtures can be carried out using conventional mixing units, for example with an agitator or a roller mill.
- Unsaturated polyester resins produced in this way can be polymerized with initiators such as peroxides, azo compounds, etc., possibly in the presence of polymerisation accelerators or co-accelerators or promoters, or by irradiation, for example with light, by UV radiation or accelerated electron beams, possibly in the presence of light initiators and Harden sensitizers.
- the unsaturated polyester resins according to the invention are suitable for the production of coatings, fine layers and molded materials with and without reinforcing materials and optionally fillers.
- Polyester resin A is a 66% styrenic solution of an unsaturated polyester with an acid number of 50, stabilized with 0.01% hydroquinone, which by melt condensation at 190 to 210 ° C in the presence of an inert gas atmosphere of maleic acid, o-phthalic acid and 1,2-propylene glycol was produced in a molar ratio of 1: 2: 3. The degree of isomerization of maleic acid - fumaric acid was 95%.
- Polyester resin 3 is produced analogously to the specifications of polyester resin A, but the starting components maleic acid, o-phthalic acid and propylene glycol-1,2 are condensed in a molar ratio of 1: 0.5: 1.5 to produce the unsaturated polyester. The degree of isomerization was 95%.
- Polyester resin C is produced analogously to the specifications of polyester resin A, but the starting components maleic acid, isophthalic acid, neopentyl glycol are condensed in a molar ratio of 1: 1: 2 to produce the unsaturated polyester.
- the degree of isomerization was 90
- Polyester resin D is produced analogously to the specifications of polyester resin A, but the starting components maleic acid, tetrahydrophthalic acid, phthalic acid, diethylene glycol, propylene glycol are condensed in a molar ratio of 1: 0.5: 0.5: 1.0: 1.0 to produce the unsaturated polyester.
- the degree of isomerization was 95%.
- Polyester resin E is produced analogously to the specifications for polyester resin A, but the starting components maleic acid, isophthalic acid, diethylene glycol, propylene glycol are condensed in a molar ratio of 1: 1: 1: 1 to produce the unsaturated polyester. The degree of isomerization was 95%.
- Polyester resin is distributed in a flat bowl with a low rim (e.g. 25 x 25 x 0.3 cm) so that a uniform 2 mm thick layer is created.
- the weight loss is determined within one hour at 23 + 1 ° C.
- a 3 mm thick glass fiber reinforced unsaturated polyester resin layer consisting of 3 layers of glass fiber mat is made using 1% methyl ethyl ketone peroxide (50% in dimethyl phthalate) and 0.2 to 0.5% 1% cobalt octoate solution in styrene (1% cobalt content) Room temperature hardened from 23 + 1 ° C.
- polyester resins A and B were mixed with paraffins, the softening range of which was between 32 ° and 96 ° C.
- paraffins used and the amounts added in percent by weight, based on the weight of polyester resin are summarized in the following table.
- comparative examples a, b, d and e which are not produced according to the invention have good layer adhesion, but high styrene evaporation and comparative examples c and f have low styrene evaporation and poor layer adhesion.
Abstract
Description
Die Erfindung betrifft verdunstungsarme, in Gegenwart üblicher Polymerisationsinitiatoren härtbare, gut überlaminierbare ungesättigte Polyesterharze aus einem äthylenisch ungesättigten Polyester, einer copolymerisierbaren, äthylenisch ungesättigten monomeren Verbindung sowie gegebenenfalls weiteren Aufbaukomponenten und Hilfsstoffen, die zur Verminderung der Monomerverdunstung und zur Verbesserung der Überlaminierbarkeit Paraffingemische enthalten.The invention relates to low-evaporation, curable in the presence of conventional polymerization initiators, highly overlaminable unsaturated polyester resins composed of an ethylenically unsaturated polyester, a copolymerizable, ethylenically unsaturated monomeric compound and, if appropriate, further structural components and auxiliaries which contain wax mixtures to reduce monomer evaporation and to improve the ability to be overlaminated.
Form- und Preßmassen aus ungesättigten Polyesterharzen enthalten üblicherweise, außer ungesättigten Polyestern und damit copolymerisierbaren monomeren Vinyl verbindungen, Polymerisationsinitiatoren und Inhibitoren sowie häufig pulverförmige Füllstoffe und Glasfasern oder flächige Glasfasergebilde. Schrumpfarm härtbare Formmassen enthalten außerdem bis zu 30 Gewichtsprozent thermoplastische Polymere. Um klebfreie Produkte mit optimalen Fließverhalten bei den erforderlichen Aushärtungsbedingungen herzustellen, werden den Polyesterformmassen vor dem Vermischen mit Füllstoffen geringe Mengen feinteiliger Erdalkalioxide zugemischt. Dabei findet durch Salzbildung mit den Carboxylendgruppen des ungesättigten Polyesters und Komplexbildung eine Eindickung statt.Molding and molding compounds made from unsaturated polyester resins usually contain, in addition to unsaturated polyesters and copolymerizable monomeric vinyl compounds, polymerization initiators and inhibitors, and often powdered fillers and glass fibers or flat glass fiber structures. Low-shrinkable molding compositions also contain up to 30 percent by weight of thermoplastic polymers. In order to produce tack-free products with optimal flow behavior under the necessary curing conditions, small amounts of finely divided alkaline earth oxides are added to the polyester molding compounds before they are mixed with fillers. Thickening takes place due to salt formation with the carboxyl end groups of the unsaturated polyester and complex formation.
Durch den Zusatz der für die anwendungstechnische Verwertbarkeit unentbehrlichen flüchtigen, olefinisch ungesättigten Monomeren, wie Styrol, treten bei der Verarbeitung von ungesättigten, härtbaren Polyesterformmassen zwangsläufig bei allen Verarbeitungstechniken, beispielsweise beim Hand-, Faserspritz- oder Wickelverfahren, Monomerenverluste auf, sobald die ungesättigten, härtbaren Polyesterformmassen mit der Atmosphäre in Berührung kommen. Der Verlust an Monomeren ist nicht nur aus wirtschaftlichen Gründen unerwünscht, die Monomerenkonzentration in der AtmosPhäre bedeutet auch eine Belästigung und Gefährdung des Verarbeiters am Arbeitsplatz, so daß die Monomerenkonzentration durch aufwendige technische Einrichtungen, wie Absaugvorrichtungen, intensive Belüftung usw., vermindert werden muß.Due to the addition of the volatile, olefinically unsaturated monomers, such as styrene, which are indispensable for their usability in application technology, the processing of unsaturated, curable polyester molding compositions inevitably results in monomer losses in all processing techniques, for example in hand, fiber spraying or winding processes, as soon as the unsaturated, curable ones Polyester molding compounds come into contact with the atmosphere. The loss of monomers is not only undesirable for economic reasons, the monomer concentration in the atmosphere also means annoyance and danger to the processor at the workplace, so that the monomer concentration must be reduced by complex technical equipment such as suction devices, intensive ventilation, etc.
Aus der DT-PS 948 816 ist bekannt, daß Zusätze von wachsar- tigen Stoffen, beispielsweise Paraffin, zu ungesättigten, härtbaren Polyesterformmassen nicht nur die Verdunstung von olefinisch ungesättigten Monomeren, wie Styrol, sondern auch die polymerisationshemmende Wirkung des Sauerstoffs vermindern.From DT-PS 948 816 it is known that additions of wax - like substances, for example paraffin, to unsaturated, curable polyester molding compositions not only reduce the evaporation of olefinically unsaturated monomers such as styrene, but also reduce the polymerization-inhibiting effect of oxygen.
In der DT-OS 1 956 376 wird vorgeschla.gen, auf ein Lackpolyesterharz kurz vor der Härtung einen wachsartigen Stoff, dessen Dispersion oder Lösung in dünner Schicht aufzubringen, wobei als Lösungsmittel für diese Sperrschichtbildner, die vorzugsweise aufgesprüht werden, Benzinkohlenwasserstoffe und Aromaten genannt werden. Nachteilig an diesem Verfahren ist, daß die Sperrschichtbildner in großen Mengen Lösungsmitteln gelöst - üblicherweise werden 1-gewichtsprozentige Lösungen der wachsartigen Stoffe verwendet - und die Lösungen in einem separaten Arbeitsgang auf die Filme der ungesättigten Lackpolyesterharze aufgebracht werden müssen. Zu beachten ist ferner, daß beim Beschichten des Lackfilms mit der sperrschichtbildnerhaltigen Lösung ein zu hoher Druck, eine zu hohe Temperatur und eine zu große Löslichkeit der Verfahrenskomponenten vermieden wird, weil sich sonst der härtbare Lackfilm und die Sperrschicht vermischen könnten.In DT-OS 1 956 376 it is proposed to apply a wax-like substance, its dispersion or solution in a thin layer to a lacquer polyester resin shortly before curing, gasoline hydrocarbons and aromatics being mentioned as solvents for these barrier layer formers, which are preferably sprayed on . A disadvantage of this process is that the barrier layer formers are dissolved in large amounts of solvents - usually 1% by weight solutions of the wax-like substances are used - and the solutions have to be applied to the films of the unsaturated paint polyester resins in a separate operation. It should also be noted that when coating the paint film too high a pressure, too high a temperature and too much solubility of the process components are avoided with the solution containing the barrier layer former, because otherwise the hardenable lacquer film and the barrier layer could mix.
Wird nur eine Polyesterharzschicht in einem Arbeitsgang ausgehärtet, wie etwa beim Lackieren, so erzielt man durch Paraffinzusätze beliebig niedere Styrolverluste. Paraffine weisen jedoch den Nachteil auf, daß sie zusätzlich als Trennmittel wirken. Dies bedeutet, daß in Gegenwart von Paraffinen ausgehärtete Polyesterharzschichten ein trübe, inerte Oberfläche aufweisen. Wird auf eine derartige Oberfläche weiteres ungesättigtes Polyesterharz aufgebracht und ausgehärtet, so erhält man einen ungenügenden Verbund und die beiden ausgehärteten Harzschichten lassen sich verhältnismäßig leicht voneinander trennen. Die Haftung wird um so schlechter, je besser ausgehärtet die Unterlage ist.If only one layer of polyester resin is cured in one operation, such as when painting, then you can achieve as low a styrene loss as possible by adding paraffin. However, paraffins have the disadvantage that they also act as release agents. This means that polyester resin layers cured in the presence of paraffins have a cloudy, inert surface. If further unsaturated polyester resin is applied to such a surface and cured, an inadequate bond is obtained and the two cured resin layers can be separated from one another relatively easily. The better the substrate is hardened, the worse the adhesion.
Die Überlaminierbarkeit von ungesättigten Polyesterharzen kann nach Angaben der deutschen Patentanmeldungen P 25 54 930.8 und P 27 05 966.1 durch den Zusatz von Wasserin-Öl oder Öl-in-Wasser-Emulgatoren mit einem HBL von 1,5 bis 15 bzw. durch den Zusatz von flüssigen Alkanen oder deren Gemische zu wachsartigen Stoffen verbessert werden. Nachteilig an den beiden Methoden ist, daß die Haftung zwischen zwei Laminatschichten immer noch nicht voll befriedigend ist und daß die Polyesterharze nur ungenügend reproduzierbar hergestellt werden können.According to the German patent applications P 25 54 930.8 and P 27 05 966.1, the ability to overlaminate unsaturated polyester resins can be increased by adding water-in-oil or oil-in-water emulsifiers with an HBL of 1.5 to 15 or by adding liquid alkanes or their mixtures can be improved to waxy substances. A disadvantage of the two methods is that the adhesion between two laminate layers is still not completely satisfactory and that the polyester resins can only be produced with insufficient reproducibility.
Aufgabe der vorliegenden Erfindung war es, ungesättigte härtbare Polyesterharze zu entwickeln, bei denen die olefinisch ungesättigten Monomeren bei der Verarbeitung nicht oder nur in untergeordnetem Maß verdunsten, ohne daß die Überlaminierbarkeit beeinträchtigt wird.The object of the present invention was to develop unsaturated curable polyester resins in which the olefinically unsaturated monomers do not evaporate or only evaporate to a minor extent during processing without the overlaminability being impaired.
Überraschenderweise wurde gefunden, daß der Zusatz von Paraffinmischungen, bestehend aus einem Paraffin mit einem Schmelzpunkt zwischen 25 und 50°C und einem Paraffin mit einem Schmelzpunkt zwischen 51 und 100°C, zu ungesättigten Polyesterharzen die oben gestellten Anforderungen erfüllt.Surprisingly, it was found that the addition of paraffin mixtures, consisting of a paraffin with a melting point between 25 and 50 ° C and a paraffin with a melting point between 51 and 100 ° C, to unsaturated polyester resins meets the requirements set out above.
Gegenstand der vorliegenden Erfindung sind somit verdunstungsarme, gut Uberlaminierbare, in Gegenwart üblicher Polymerisationsinitiatoren härtbare, ungesättigte Polyesterharze aus
- a) mindestens einem äthylenisch ungesättigten copolymerisierbaren Polyester,
- b) mindestens einer äthylenisch ungesättigten copolymerisierbaren monomeren Verbindung,
- c) einem wachsartigen Stoff sowie gegebenenfalls
- d) Aufbaukomponenten und Hilfsstoffen, wie sie üblicherweise bei ungesättigten Polyesterharzen Anwendung finden, die dadurch gekennzeichnet sind, daß sie als wachsartige Stoffe eine Paraffinmischung enthalten, die im wesentlich besteht aus mindestens einem Paraffin mit einem Schmelzpunkt zwischen 250C und 50°C und mindestens einem Paraffin mit einem Schmelzpunkt zwischen 51°C und 100°C.
- a) at least one ethylenically unsaturated copolymerizable polyester,
- b) at least one ethylenically unsaturated copolymerizable monomeric compound,
- c) a waxy substance and optionally
- d) structural components and excipients, such as those used commonly in unsaturated polyester resins, which are characterized in that they contain a paraffin mixture as a waxy materials which substantially consists of at least one paraffin having a melting point between 25 0 C and 50 ° C and at least a paraffin with a melting point between 51 ° C and 100 ° C.
Die erfindungsgemäßen Polyesterharze weisen überraschenderweise den Vorteil auf, daß durch die spezielle Zusammensetzung der Paraffinmischung die Trennmittelwirkung aufgehoben wird, ohne daß die Monomerverdunstung verstärkt wird.The polyester resins according to the invention surprisingly have the advantage that the release agent effect is eliminated by the special composition of the paraffin mixture without increasing the monomer evaporation.
Die Herstellung der erfindungsgemäßen verdunstungsarmen, gut überlaminierbaren, härtbaren, ungesättigten Polyesterharze erfolgt in an sich bekannter Weise durch Vermischen des Paraffingemischs mit den Polyesterharzkomponenten (a) - (d). Es hat sich als zweckmäßig erwiesen, das Paraffingemisch in einem äthylenisch ungesättigten Monomer, vorzugsweise Styrol, zu lösen und die erhaltene Monomerlösung dem Polyesterharz zuzudosieren.The production of the low-evaporation, easily overlaminatable, curable, unsaturated polyester according to the invention Resins are made in a manner known per se by mixing the paraffin mixture with the polyester resin components (a) - (d). It has proven to be expedient to dissolve the paraffin mixture in an ethylenically unsaturated monomer, preferably styrene, and to meter the monomer solution obtained into the polyester resin.
Zu den zur Herstellung der erfindungsgemäßen verdunstungsarmen, gut überlaminierbaren, in Gegenwart üblicher Polymerisationsinitiatoren härtbaren ungesättigten Polyesterharze verwendbaren Ausgangskomponenten a) bis d) ist folgendes auszuführen:
- a) Als ungesättigte Polyester eignen sich die üblichen Polykondensationsprodukte aus mehrwertigen, insbesondere zweiwertigen Carbonsäuren und deren veresterbare Derivate, insbesondere deren Anhydride, die mit mehrwertigen, insbesondere zweiwertigen Alkoholen esterartig verknüpft sind, und gegebenenfalls zusätzlich Reste einwertiger Carbonsäuren und/oder Reste einwertiger Alkohole und/ oder Reste von Hydroxycarbonsäuren enthalten, wobei zumindest ein Teil der Reste über äthylenisch ungesättigte copolymerisierbare Gruppen verfügen muß.
- a) Suitable unsaturated polyesters are the customary polycondensation products of polybasic, in particular dibasic carboxylic acids and their esterifiable derivatives, in particular their anhydrides, which are linked in ester form with polybasic, in particular dihydric alcohols, and optionally additionally residues of monohydric carboxylic acids and / or residues of monohydric alcohols and / or contain residues of hydroxycarboxylic acids, at least some of the residues must have ethylenically unsaturated copolymerizable groups.
Als mehrwertige, insbesondere zweiwertige, gegebenenfalls ungesättigte Alkohole eignen sich die üblichen, insbesondere acyclische Gruppen, cyclische Gruppen als auch beide Arten von Gruppen aufweisende Alkandiole und Oxalkandiole, wie z.B. Äthylenglykol, Propylenglykol-1,2, Propandiol-1,3, Butylenglykol-1,3, Butandiol-1,4, Hexandiol=1,6, 2,2-Dimethylenpropandiol-1,3, Diäthylenglykol, Triäthylenglykol, Polyäthylenglykol, Cyclohexandiol-1,2, 2,2-Bis-(p-hydroxycyclohexyl-)propan, 1,4-Bis-methylolcyclohexan, Vinylglykol, Trimethylolpropanmonoallyläther oder Butendiol-1,4.Suitable polyhydric, in particular dihydric, optionally unsaturated alcohols are the customary, in particular acyclic groups, cyclic groups and also alkanediols and oxalkanediols which have both types of groups, such as, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol and 1-butylene glycol , 3, butanediol-1,4, hexanediol = 1,6, 2,2-dimethylene-propanediol-1,3, diethylene glycol, triethylene glycol, polyethylene glycol, cyclohexanediol- 1 , 2 , 2,2-bis (p-hydroxycyclohexyl) propane , 1,4-bis-methylolcyclohexane, vinyl glycol, trimethylolpropane monoallyl ether or 1,4-butenediol.
Ferner können ein-, drei- oder höherwertige Alkohole, wie z.B. Äthylhexanol, Fettalkohole, Benzylalkohole, 1,2-Di-(allyloxy-)propanol(,-3), Gylcerin, Pentaerythrit oder Trimethylolpropan, in untergeordneten Mengen mitverwendet werden. Die mehrwertigen, insbesondere zweiwertigen Alkohle werden im allgemeinen in stöchiometrischen oder annähernd stöchiometrischen Mengen mit mehrbasischen, insbesondere zweibasischen Carbonsäuren bzw. deren kondensierbaren Derivaten umgesetzt.Furthermore, monohydric, trihydric or higher alcohols, e.g. Ethylhexanol, fatty alcohols, benzyl alcohols, 1,2-di- (allyloxy-) propanol (, - 3), Gylcerin, pentaerythritol or trimethylolpropane, can also be used in minor amounts. The polyhydric, especially dihydric alcohols are generally reacted in stoichiometric or approximately stoichiometric amounts with polybasic, in particular dibasic carboxylic acids or their condensable derivatives.
Geeignete Carbonsäuren bzw. deren Derivate sind zweibasische olefinisch ungesättigte, vorzugsweise α,β-olefinisch ungesättigte Carbonsäuren, wie z.B. Maleinsäure, Fumarsäure, Itaconsäure, Citraconsäure, Methylenglutarsäure und Mesaconsäure bzw. deren Ester oder vorzugsweise deren Anhydride. In die Polyester können weiterhin zusätzlich andere modifizierend wirkende zweibasiche, ungesättigte und/oder gesättigte sowie aromatische Carbonsäuren oder -derivate, wie z.B. Bernsteinsäure, Glutarsäure, cL-Methylglutarsäure, Adipinsäure, Sebacinsäure, Pimelinsäure, Phthalsäureanhydrid, o-Phthalsäure, Isophthalsäure, Terephthalsäure, Dihydrophthalsäure, Tetrahydrophthalsäure, Tetrachlorphthalsäure, 3,6-Endomethylen-1,2,3,6-tetrahydrophthalsäure, Endomethylentetrachlorphthalsäure oder Hexachlorendomethylentetrahydrophthalsäure, einkondensiert sein, ferner ein-, drei-und höherbasische Carbonsäuren, wie z.B. Äthylhexansäure, Fettsäuren, Methacrylsäure, Propionsäure, Benzoesäure, 1,2,4-Benzoltricarbonsäure oder 1,2,4,5-Benzoltetracarbonsäure.Suitable carboxylic acids or their derivatives are dibasic olefinically unsaturated, preferably α, β-olefinically unsaturated carboxylic acids, such as e.g. Maleic acid, fumaric acid, itaconic acid, citraconic acid, methylene glutaric acid and mesaconic acid or their esters or preferably their anhydrides. Other modifying dibasic, unsaturated and / or saturated and aromatic carboxylic acids or derivatives, such as e.g. Succinic acid, glutaric acid, cL-methylglutaric acid, adipic acid, sebacic acid, pimelic acid, phthalic anhydride, o-phthalic acid, isophthalic acid, terephthalic acid, dihydrophthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, 3,6-endomethylene-dichloromethloro-methylene-dichloro-thalophthalic acid, 1,2-methylene chloride be condensed in, further mono-, tri-and higher basic carboxylic acids, such as Ethylhexanoic acid, fatty acids, methacrylic acid, propionic acid, benzoic acid, 1,2,4-benzenetricarboxylic acid or 1,2,4,5-benzenetetracarboxylic acid.
Die ungesättigten Polyester werden im allgemeinen durch Schmelzkondensation oder Kondensation unter azeotropen Bedingungen aus ihren Komponenten hergestellt. Für das erfindungsgemäße Verfahren können amorphe und gegebenenfalls kristallisierbare ungesättigte Polyester verwendet werden.The unsaturated polyesters are generally prepared from their components by melt condensation or condensation under azeotropic conditions. For the process according to the invention, amorphous and given if crystallizable unsaturated polyesters are used.
Es hat sich im allgemeinen als zweckmäßig erwiesen, wenn die ungesättigten Polyester eine Säurezahl von 10 bis 100, vorzugsweise von 25 bis 60 sowie ein mittleres Molekulargewicht von etwa 600 bis 4 000, vorzugsweise von 800 bis 3 000, aufweisen.It has generally proven to be expedient if the unsaturated polyesters have an acid number of 10 to 100, preferably 25 to 60, and an average molecular weight of about 600 to 4,000, preferably 800 to 3,000.
Bezüglich der Zusammensetzung ungesättigter Polyester sei beispielsweise auch auf das Buch von H.V. Boenig, Unsaturated Polyesters: Structure and Properties, Amsterdam, 1964, verwiesen. Die für das erfindungsgemäße Verfahren zu verwendenden Formmassen enthalten im allgemeinen 10 bis 70, vorzugsweise 15 bis 50 Gewichtsprozent, bezogen auf die Komponente a) bis c) an ungesättigten Polyestern a).Regarding the composition of unsaturated polyesters, for example, the book by H.V. Boenig, Unsaturated Polyesters: Structure and Properties, Amsterdam, 1964. The molding compositions to be used for the process according to the invention generally contain 10 to 70, preferably 15 to 50 percent by weight, based on component a) to c), of unsaturated polyesters a).
b) Als copolymerisierbare olefinisch ungesättigte monomere Verbindungen kommen die üblicherweise zum Herstellen ungesättigter Polyesterformmassen verwendeten Vinyl- und Allylverbindungen in Frage, wie Styrol, substituierte Styrole, wie p-Chlorstyrol oder Vinyltoluol, Ester der Acrylsäure und Methacrylsäure mit 1 bis 18 Kohlenstoffatome enthaltenden Alkoholen, wie z.B. Methacrylsäuremethylester, Acrylsäurebutylester, Äthylhexylacrylat, Hydroxypropylacrylat, Dicyclopentadienylacrylat, Butandioldiacrylat und (Meth)-acrylsäureamide, Allylester, wie z.B. Diallylphthalat und Vinylester, wie z.B. Äthylhexansäurevinylester, Vinylpivalat und andere.b) Suitable copolymerizable olefinically unsaturated monomeric compounds are the vinyl and allyl compounds customarily used for producing unsaturated polyester molding compositions, such as styrene, substituted styrenes, such as p-chlorostyrene or vinyltoluene, esters of acrylic acid and methacrylic acid with alcohols containing 1 to 18 carbon atoms, such as e.g. Methyl methacrylate, butyl acrylate, ethylhexyl acrylate, hydroxypropyl acrylate, dicyclopentadienyl acrylate, butanediol diacrylate and (meth) acrylamide, allyl esters, e.g. Diallyl phthalate and vinyl esters, e.g. Ethylhexanoic acid vinyl ester, vinyl pivalate and others.
Desgleichen eignen sich Gemische der genannten olefinisch ungesättigten Monomeren. Bevorzugt geeignet als Komponente (b) sind Styrol, Vinyltoluol, α-Methylstyrol und Diallylphthalat. Die Komponente b) ist in den Polyesterharzen im allgemeinen in einer Menge von 5 bis 60, vorzugsweise von 10 bis 45 Gewichtsprozent, bezogen auf die Mischung der Komponenten a) + b), enthalten.Mixtures of the olefinically unsaturated monomers mentioned are likewise suitable. Styrene, vinyl toluene, α-methylstyrene and diallyl phthalate are particularly suitable as component (b). Component b) is generally preferred in an amount of 5 to 60% in the polyester resins as from 10 to 45 percent by weight, based on the mixture of components a) + b).
c) Als unter den Punkt c) fallende wachsartige Stoffe, die für die Paraffinmischung verwendbar sind, werden erfindungsgemäß mindestens ein Paraffin mit einem Schmelzpunkt von 25 bis 50°C, vorzugsweise von 46° bis 48°c und mindestens ein Paraffin mit einem Schmelzpunkt von 51° bis 100°C, vorzugsweise 56° bis 58°C gemischt.c) As wax-like substances falling under point c) which can be used for the paraffin mixture, according to the invention at least one paraffin with a melting point of 25 to 50 ° C, preferably from 46 ° to 48 ° c and at least one paraffin with a melting point of 51 ° to 100 ° C, preferably 56 ° to 58 ° C mixed.
Anstelle der Paraffine können jedoch auch andere wachsartige Stoffe, beispielsweise die als sogenanntes Montanwachs bekannten Paraffinoxidationsprodukte, bzw. deren Ester, Carnaubawachs, langkettige Fettsäuren, wie Stearinsäure, Stearylstearat, Ceresin und dgl. eingesetzt werden.Instead of the paraffins, however, other wax-like substances, for example the paraffin oxidation products known as so-called montan wax, or their esters, carnauba wax, long-chain fatty acids such as stearic acid, stearyl stearate, ceresine and the like can also be used.
Zur Verminderung der Monomerenverdunstung und zur Ausbildung einer klebfreien Oberfläche sowie zur Erzielung einer guten Überlaminierbarkeit enthalten die ungesättigten Polyesterharze 0,01 bis 5 Gewichtsprozent, vorzugsweise 0,05 bis 1 Gewichtsprozent, insbesondere 0,1 bis 0,5 Gewichtsprozent des Paraffingemisches, bezogen auf das Gesamtgewicht der Komponenten (a) und (b).To reduce the monomer evaporation and to form a tack-free surface and to achieve good overlaminability, the unsaturated polyester resins contain 0.01 to 5 percent by weight, preferably 0.05 to 1 percent by weight, in particular 0.1 to 0.5 percent by weight, of the paraffin mixture, based on the Total weight of components (a) and (b).
Besonders bewährt und daher vorzugsweise verwendet werden Paraffinwachse, die bestehen aus 0,01 bis 0,5 Gewichtsprozent eines Paraffins mit einem Schmelzpunkt von 25° bis 50°C, vorzugsweise 46° bis 48°C und 0,01 bis 0,5 Gewichtsprozent eines Paraffins mit einem Schmelzpunkt von 51° bis 100°C, vorzugsweise 56° bis 58°C, wobei die Gewichtsprozente jeweils bezogen sind auf das Gesamtgewicht der Polyesterharzkomponenten a) und b).Paraffin waxes which consist of 0.01 to 0.5 percent by weight of a paraffin with a melting point of 25 ° to 50 ° C., preferably 46 ° to 48 ° C. and 0.01 to 0.5 percent by weight of one, are particularly proven and therefore preferably used Paraffins with a melting point of 51 ° to 100 ° C, preferably 56 ° to 58 ° C, the weight percentages being based in each case on the total weight of the polyester resin components a) and b).
d) Als Aufbaukomponenten und Hilfsstoffe entsprechend Punkt d, wie sie gegebenenfalls üblicherweise bei ungesättigten Polyesterharzen Anwendung finden, kommen beispielsweise in Betracht: Verdickungsmittel, Inhibitoren, Füllstoffe, Verstärkungsmittel sowie gegebenenfalls inerte Lösungsmittel, Polymerisationsbeschleuniger, schrumpfungsmindernde Zusätze und weitere üblicherweise bei der Verarbeitung von Polyesterharzen verwendete Hilfsstoffe.d) As structural components and auxiliaries accordingly Point d, as they are usually used in unsaturated polyester resins, are, for example, suitable: thickeners, inhibitors, fillers, reinforcing agents and, if appropriate, inert solvents, polymerization accelerators, shrinkage-reducing additives and other auxiliaries customarily used in the processing of polyester resins.
Als Verdickungsmittel seien beispielhaft genannt: Erdalkalioxide oder -hydroxide, wie Calciumoxid, Calciumhydroxid, Magnesiumhydroxid und vorzugsweise Magnesiumoxid sowie Gemische dieser Oxide und/oder Hydroxide. Die Erdalkalioxide können auch teilweise durch Zinkoxid ersetzt sein. Der Gehalt an Verdickungsmitteln in den Polyesterharzen beträgt im allgemeinen 0,5 bis 5, vorzugsweise 1 bis 3 Gewichtsprozent, bezogen auf die Mischung der Komponenten (a) und (b).Examples of thickeners are: alkaline earth metal oxides or hydroxides, such as calcium oxide, calcium hydroxide, magnesium hydroxide and preferably magnesium oxide, and mixtures of these oxides and / or hydroxides. The alkaline earth oxides can also be partially replaced by zinc oxide. The content of thickeners in the polyester resins is generally 0.5 to 5, preferably 1 to 3 percent by weight, based on the mixture of components (a) and (b).
Als Inhibitoren kommen die üblichen in Frage, wie z.B. Hydrochinon, tert.-Butylbrenzkatechin, p-Benzochinon, Chloranil, Nitrobenzole, wie m-Dinitrobenzol, Thiodiphenylamin oder Salze von N-Nitroso-N-cyclohexylhydroxylamin sowie deren Gemische. Die Inhibitoren sind in den Polyesterharzen im allgemeinen in einer Menge von 0,005 bis 0,2, vorzugsweise 0,01 bis 0,1 Gewichtsprozent, bezogen auf die Komponenten a) und b), enthalten.The usual inhibitors come into question, e.g. Hydroquinone, tert-butyl catechol, p-benzoquinone, chloranil, nitrobenzenes, such as m-dinitrobenzene, thiodiphenylamine or salts of N-nitroso-N-cyclohexylhydroxylamine and mixtures thereof. The inhibitors are generally present in the polyester resins in an amount of 0.005 to 0.2, preferably 0.01 to 0.1 percent by weight, based on components a) and b).
Geeignete Füllstoffe sind z.B. übliche feinpulverige oder körnige anorganische oder organische Füllstoffe, wie Kreide, Kaolin, Quarzmehl, Dolomit, Schwerspat, Metallpulver, Zement, Talkum, Kieselgur, Holzmehl, Holzspäne, Pigmente und dergleichen.Suitable fillers are e.g. Usual fine powdery or granular inorganic or organic fillers, such as chalk, kaolin, quartz powder, dolomite, heavy spar, metal powder, cement, talc, diatomaceous earth, wood powder, wood chips, pigments and the like.
Als Verstärkungsmittel kommen in Frage anorganische oder organische Fasern oder flächige, gegebenenfalls daraus gewebte Gebilde, z.B. solche aus Glas, Asbest, Zellulose und synthetischen organischen Hochpolymeren, wie Polyestern und Polyamiden.Inorganic or organic fibers or flat structures, optionally woven therefrom, for example those made of glass, asbestos, cellulose and synthetic organic high polymers, such as polyesters and polyamides.
Die Füll- und Verstärkungsstoffe können in Mengen von 5 bis 200 Gewichtsprozent, bezogen auf die Komponenten a) und b), verwendet werden.The fillers and reinforcing materials can be used in amounts of 5 to 200 percent by weight, based on components a) and b).
Als weiterhin gegebenenfalls mitzuverwendende inerte Lösungsmittel kommen Ketone, Ester, Kohlenwasserstoffe in Mengen bis zu 100 Gewichtsprozent, bezogen auf die Komponente a), in Frage.Other possible inert solvents to be used include ketones, esters, hydrocarbons in amounts of up to 100 percent by weight, based on component a).
Die erfindungsgemäßen ungesättigten Polyesterharze können vorbeschleunigt sein. Als Polymerisationsbeschleuniger kommen beispielsweise Schwermetallsalze wie Kobalt-und Vanadinsalze, tertiäre aromatische Amine, 1,3-Diketonverbindungen wie Acetylaceton, ß-Ketoester, wie Acetessigsäureäthylester und ß-Ketoamide wie Acetessigsäurediäthylamid und Kombinationen dieser Verbindungen in Frage.The unsaturated polyester resins of the invention can be pre-accelerated. Possible polymerization accelerators are, for example, heavy metal salts such as cobalt and vanadium salts, tertiary aromatic amines, 1,3-diketone compounds such as acetylacetone, β-keto esters such as ethyl acetoacetate and β-ketoamides such as diethyl acetoacetic acid and combinations of these compounds.
Gegegenenfalls mitzuverwendende schrumpfungsmindernde Zusätze sind beispielsweise thermoplastische Polymere wie Polystyrol, Styrolcopolymerisate, Polyvinylacetate und/oder Poly(meth)acrylate. Vorzugsweise verwendet werden thermoplastische Polymerisate, die Carboxylgruppen in Mengen von 1 bis 5 Gewichtsprozent, bezogen auf.das Gesamtgewicht, in der Polymerkette gebunden enthalten. Die schrumpfungsmindernden Zusätze werden üblicherweise in Mengen von 1 bis 30, vorzugsweise 8 bis 15 Gewichtsprozent, bezogen auf das Gewicht der Komponenten (a) und (b), verwendet.Contrast-reducing additives that can also be used are, for example, thermoplastic polymers such as polystyrene, styrene copolymers, polyvinyl acetates and / or poly (meth) acrylates. Thermoplastic polymers which contain carboxyl groups in amounts of 1 to 5 percent by weight, based on the total weight, bound in the polymer chain are preferably used. The shrinkage-reducing additives are usually used in amounts of 1 to 30, preferably 8 to 15 percent by weight, based on the weight of components (a) and (b).
Erfindungsgemäß werden den Aufbaukomponenten (a) bis (d) der verdunstungsarmen, gut überlaminierbaren, härtbaren ungesättigten Polyesterharze Paraffingemische einverleibt. Als Paraffingemische kommen solche in Betracht, die Paraffine enthalten, deren Schmelzpunkt einmal unter und einmal über 50°C liegt.According to the invention, paraffin mixtures are incorporated into the structural components (a) to (d) of the low-evaporation, easily overlaminable, curable unsaturated polyester resins. Suitable paraffin mixtures are those which contain paraffins, the melting point of which is below and once above 50 ° C.
Das Vermischen der Einzelkomponenten (a) bis (d) und das Zumischen der Paraffingemische kann unter Verwendung üblicher Mischaggregate erfolgen, beispielsweise mit einem Rührwerk oder einem Walzenstuhl. Derartig hergestellte ungesättigte Polyesterharze lassen sich mit Polymerisationsinitiatoren, wie Peroxide, Azoverbindungen u.a., evtl. in Gegenwart von Polymerisationsbeschleunigern oder Co-beschleunigern bzw. Promotoren oder durch Bestrahlung, beispielsweise mit Licht, durch UV-Strahlung oder beschleunigte Elektronenstrahlen evtl. in Gegenwart von Lichtinitiatoren und Sensibilisatoren härten.The mixing of the individual components (a) to (d) and the admixing of the paraffin mixtures can be carried out using conventional mixing units, for example with an agitator or a roller mill. Unsaturated polyester resins produced in this way can be polymerized with initiators such as peroxides, azo compounds, etc., possibly in the presence of polymerisation accelerators or co-accelerators or promoters, or by irradiation, for example with light, by UV radiation or accelerated electron beams, possibly in the presence of light initiators and Harden sensitizers.
Die erfindungsgemäßen ungesättigten Polyesterharze eignen sich zur Herstellung von Überzügen, Feinschichten und Formstoffen ohne und mit Verstärkungsmaterialien sowie gegebenenfalls Füllstoffen.The unsaturated polyester resins according to the invention are suitable for the production of coatings, fine layers and molded materials with and without reinforcing materials and optionally fillers.
Besonders vorteilhaft ist ihre Verwendung zur Herstellung von Formteilen durch Laminieren, beispielsweise im Handverfahren oder Faserspritzverfahren sowie überall dort, wo bei Verwendung praffinfreier ungesättigter Polyesterharze eine besonders hohe Konzentration flüchtiger Monomerer am Arbeitsplatz auftritt bzw. die Monomerenemission sehr hoch ist.Their use for the production of molded parts by lamination is particularly advantageous, for example in the manual process or fiber spraying process, and wherever a particularly high concentration of volatile monomers occurs at the workplace or the monomer emission is very high when using praffin-free unsaturated polyester resins.
Die in den Beispielen angegebenen Teile und Prozente sind Gewichtsteile bzw. Gewichtsprozente.The parts and percentages given in the examples are parts by weight and percentages by weight.
Ungesättigtes Polyesterharz:Unsaturated polyester resin:
Polyesterharz A ist eine mit 0,01 % Hydrochinon stabilisierte 66 %ige styrolische Lösung eines ungesättigten Polyesters mit einer Säurezahl von 50, der durch Schmelzkondensation bei 190 bis 210°C in Gegenwart einer Inertgasatmosphäre aus Maleinsäure, o-Phthalsäure und Propylenglykol-1,2 im Molverhältnis 1 : 2 : 3 hergestellt wurde. Der Isomerisierungsgrad Maleinsäure - Fumarsäure betrug 95 %.Polyester resin A is a 66% styrenic solution of an unsaturated polyester with an acid number of 50, stabilized with 0.01% hydroquinone, which by melt condensation at 190 to 210 ° C in the presence of an inert gas atmosphere of maleic acid, o-phthalic acid and 1,2-propylene glycol was produced in a molar ratio of 1: 2: 3. The degree of isomerization of maleic acid - fumaric acid was 95%.
Polyesterharz 3 wird analog den Angaben des Polyesterharzes A hergestellt, wobei jedoch zur Herstellung des ungesättigten Polyesters die Ausgangskomponenten Maleinsäure, o-Phthalsäure und Propylenglykol-1,2 im Molverhältnis 1 : 0,5 : 1,5 kondensiert werden. Der Isomerisierungsgrad betrug 95 %.Polyester resin 3 is produced analogously to the specifications of polyester resin A, but the starting components maleic acid, o-phthalic acid and propylene glycol-1,2 are condensed in a molar ratio of 1: 0.5: 1.5 to produce the unsaturated polyester. The degree of isomerization was 95%.
Polyesterharz C wird analog den Angaben des Polyesterharzes A hergestellt, wobei jedoch zur Herstellung des ungesättigten Polyesters die Ausgangskomponenten Maleinsäure, Isophthalsäure, Neopentylglycol im Molverhältnis 1 : 1 : 2 kondensiert wirden. Der Isomerisierungsgrad betrug 90Polyester resin C is produced analogously to the specifications of polyester resin A, but the starting components maleic acid, isophthalic acid, neopentyl glycol are condensed in a molar ratio of 1: 1: 2 to produce the unsaturated polyester. The degree of isomerization was 90
Polyesterharz D wird analog den Angaben des Polyesterharzes A hergestellt, wobei jedoch zur Herstellung des ungesättigten Polyesters die Ausgangskomponenten Maleinsäure, Tetrahydrophthalsäure, Phthalsäure Diäthylenglycol, Propylenglycol im Molverhältnis 1 : 0,5 : 0,5 : 1,0 : 1,0 kondensiert werden. Der Isomerisierungsgrad betrug 95 %.Polyester resin D is produced analogously to the specifications of polyester resin A, but the starting components maleic acid, tetrahydrophthalic acid, phthalic acid, diethylene glycol, propylene glycol are condensed in a molar ratio of 1: 0.5: 0.5: 1.0: 1.0 to produce the unsaturated polyester. The degree of isomerization was 95%.
Polyesterharz E wird analog den Angaben des Polyesterharzes A hergestellt, wobei jedoch zur Herstellung des ungesättigten Polyesters die Ausgangskomponenten Maleinsäure, Isophthalsäure, Diäthylenglycol, Propylenglycol im Molverhältnis 1 : 1 : 1 : 1 kondensiert werden. Der Isomierisierungsgrad betrug 95 %.Polyester resin E is produced analogously to the specifications for polyester resin A, but the starting components maleic acid, isophthalic acid, diethylene glycol, propylene glycol are condensed in a molar ratio of 1: 1: 1: 1 to produce the unsaturated polyester. The degree of isomerization was 95%.
Messung der Monomerverdunstung:Measurement of monomer evaporation:
In einer planen Schale mit niedrigem Rand (z.B. 25 x 25 x 0,3 cm) wird Polyesterharz verteilt, daß eine gleichmäßig 2 mm dicke Schicht entsteht. Zur Bestimmung der Monomerverdunstung wird der Gewichtsverlust innerhalb einer Stunde bei 23 + 1°C ermittelt.Polyester resin is distributed in a flat bowl with a low rim (e.g. 25 x 25 x 0.3 cm) so that a uniform 2 mm thick layer is created. To determine the monomer evaporation, the weight loss is determined within one hour at 23 + 1 ° C.
Prüfung der Uberlaminierbarkeit:Examination of overlaminability:
Praxisnaher Test:Practical test:
Eine 3 mm dicke glasfaserverstärkte ungesättigte Polyesterharzschicht, bestehend aus 3 Lagen Glasfasermatte, wird unter Verwendung von 1 % Methyläthylketonperoxid (50 %ig in Dimethylphthalat) und 0,2 bis 0,5 % 1 %iger Kobaltoctoatlösung in Styrol ( 1 % Kobaltgehalt) bei einer Raumtemperatur von 23 + 1°C gehärtet.A 3 mm thick glass fiber reinforced unsaturated polyester resin layer consisting of 3 layers of glass fiber mat is made using 1% methyl ethyl ketone peroxide (50% in dimethyl phthalate) and 0.2 to 0.5% 1% cobalt octoate solution in styrene (1% cobalt content) Room temperature hardened from 23 + 1 ° C.
Nach genau 24 Stunden wird 1/3 der oberen Laminatfläche mit Folie abgedeckt (Ansatzpunkt für spätere Reißprobe) und eine gleiche 3 mm starke glasfaserverstärkte ungesättigte Polyesterharzschicht überlaminiert. Nach weiteren 24 Stunden wird von Hand das obere Laminat vom unteren abgezogen.After exactly 24 hours, 1/3 of the upper laminate surface is covered with film (starting point for a later tear test) and an identical 3 mm thick glass fiber reinforced unsaturated polyester resin layer is overlaminated. After another 24 hours, the top laminate is peeled off from the bottom by hand.
Die Polyesterharze A und B wurden mit Paraffinen versetzt, deren Erweichungsbereich zwischen 32° und 96°C lag.The polyester resins A and B were mixed with paraffins, the softening range of which was between 32 ° and 96 ° C.
Die verwendeten Paraffine und die zugesetzten Mengen in Gewichtsprozent, bezogen auf das Gewicht an Polyesterharz, sind in der folgenden Tabelle zusammengefaßt.The paraffins used and the amounts added in percent by weight, based on the weight of polyester resin, are summarized in the following table.
Wie aus der Tabelle zu entnehmen ist, weisen die nicht erfindungsgemäß hergestellten Vergleichsbeispiele a, b, d und e eine gute Lagenhaftung, jedoch große Styrolverdunstung und die Vergleichsbeispiele c und f eine geringe Styrolverdunstung und schlechte Lagenhaftung auf.
Claims (3)
wie sie üblicherweise bei ungesättigten Polyesterharzen Anwendung finden, dadurch gekennzeichnet, daß die Polyesterharze als wachsartige Stoffe eine Paraffinmischung enthalten, die im wesentlichen besteht aus mindestens einem Paraffin mit einem Schmelzpunkt zwischen 25°C und 50°C und mindestens einem Paraffin mit einem Schmelzpunkt zwischen 510C und 100°C.1. Low-evaporation, containing easily overlaminatable in the presence of polymerization initiators curable unsaturated polyester resins
as they are usually used in unsaturated polyester resins, characterized in that the polyester resins contain as wax-like substances a paraffin mixture which essentially consists of at least one paraffin with a melting point between 25 ° C and 50 ° C and at least one paraffin with a melting point between 51 0 C and 1 0 0 ° C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2738805 | 1977-08-29 | ||
| DE19772738805 DE2738805A1 (en) | 1977-08-29 | 1977-08-29 | LOW EVAPORATION, EASILY OVERLAMINABLE, HARDABLE, UNSATATURATED POLYESTER RESINS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000941A1 true EP0000941A1 (en) | 1979-03-07 |
| EP0000941B1 EP0000941B1 (en) | 1980-07-23 |
Family
ID=6017531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100727A Expired EP0000941B1 (en) | 1977-08-29 | 1978-08-23 | Low-volatility, curable, unsaturated polyester resins with good lamination properties |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0000941B1 (en) |
| DE (2) | DE2738805A1 (en) |
| DK (1) | DK378278A (en) |
| NO (1) | NO782921L (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2475562A1 (en) * | 1980-02-11 | 1981-08-14 | Inst Chemii Przemyslowej | Reducing monomer volatility of unsatd. polyester resins - by addn. of a reaction prod. of an epoxy cpd. with a mono:carboxylic acid |
| EP0422455A2 (en) * | 1989-10-09 | 1991-04-17 | BASF Aktiengesellschaft | Low volatile polyester resins |
| EP0473531A2 (en) * | 1990-08-16 | 1992-03-04 | Keld Jakobsen | Wear-proof paint |
| WO1993011193A1 (en) * | 1991-11-25 | 1993-06-10 | The Dow Chemical Company | Low vaporizable ethylenically unsaturated monomer emission vinyl ester and polyester resin compositions |
| US5378743A (en) * | 1989-11-08 | 1995-01-03 | The Dow Chemical Company | Stable low styrene emission vinyl ester and unsaturated polyester resin composition |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1113351A (en) * | 1953-10-09 | 1956-03-28 | American Cyanamid Co | Improvements relating to resinous polyester compositions |
| DE1156230B (en) * | 1961-01-02 | 1963-10-24 | Jaeger Fabrik Chem Ernst | Process for producing molded parts or coatings from polyester molding compounds which contain waxes |
| GB1007449A (en) * | 1961-07-27 | 1965-10-13 | British Titan Products | Titanium dioxide pigment |
| DE1592956A1 (en) * | 1966-06-27 | 1971-02-11 | Du Pont | Process for the production of coated titanium dioxide pigments |
| DE2554930A1 (en) * | 1975-12-06 | 1977-06-16 | Basf Ag | Unsaturated polyester moulding compsn. - with low monomer evaporation, contains oil-in-water or water-in-oil emulsifier |
| DE2948334A1 (en) * | 1978-11-30 | 1980-06-19 | Du Pont | LIGHT-RESISTANT TITANIUM DIOXIDE PIGMENT COMPOSITION |
| DE2223524C2 (en) * | 1972-05-13 | 1987-01-02 | Kronos Titan-Gmbh, 5090 Leverkusen, De |
-
1977
- 1977-08-29 DE DE19772738805 patent/DE2738805A1/en active Pending
-
1978
- 1978-08-23 EP EP78100727A patent/EP0000941B1/en not_active Expired
- 1978-08-23 DE DE7878100727T patent/DE2860076D1/en not_active Expired
- 1978-08-28 NO NO782921A patent/NO782921L/en unknown
- 1978-08-28 DK DK378278A patent/DK378278A/en unknown
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1113351A (en) * | 1953-10-09 | 1956-03-28 | American Cyanamid Co | Improvements relating to resinous polyester compositions |
| DE1156230B (en) * | 1961-01-02 | 1963-10-24 | Jaeger Fabrik Chem Ernst | Process for producing molded parts or coatings from polyester molding compounds which contain waxes |
| GB1007449A (en) * | 1961-07-27 | 1965-10-13 | British Titan Products | Titanium dioxide pigment |
| DE1592956A1 (en) * | 1966-06-27 | 1971-02-11 | Du Pont | Process for the production of coated titanium dioxide pigments |
| DE2223524C2 (en) * | 1972-05-13 | 1987-01-02 | Kronos Titan-Gmbh, 5090 Leverkusen, De | |
| DE2554930A1 (en) * | 1975-12-06 | 1977-06-16 | Basf Ag | Unsaturated polyester moulding compsn. - with low monomer evaporation, contains oil-in-water or water-in-oil emulsifier |
| DE2948334A1 (en) * | 1978-11-30 | 1980-06-19 | Du Pont | LIGHT-RESISTANT TITANIUM DIOXIDE PIGMENT COMPOSITION |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2475562A1 (en) * | 1980-02-11 | 1981-08-14 | Inst Chemii Przemyslowej | Reducing monomer volatility of unsatd. polyester resins - by addn. of a reaction prod. of an epoxy cpd. with a mono:carboxylic acid |
| EP0422455A2 (en) * | 1989-10-09 | 1991-04-17 | BASF Aktiengesellschaft | Low volatile polyester resins |
| EP0422455A3 (en) * | 1989-10-09 | 1992-05-20 | Basf Aktiengesellschaft | Low volatile polyester resins |
| US5132343A (en) * | 1989-10-09 | 1992-07-21 | Basf Aktiengesellschaft | Low-evaporation polyester resins |
| US5378743A (en) * | 1989-11-08 | 1995-01-03 | The Dow Chemical Company | Stable low styrene emission vinyl ester and unsaturated polyester resin composition |
| EP0473531A2 (en) * | 1990-08-16 | 1992-03-04 | Keld Jakobsen | Wear-proof paint |
| EP0473531A3 (en) * | 1990-08-16 | 1992-12-09 | Keld Jakobsen | Wear-proof paint |
| WO1993011193A1 (en) * | 1991-11-25 | 1993-06-10 | The Dow Chemical Company | Low vaporizable ethylenically unsaturated monomer emission vinyl ester and polyester resin compositions |
| US5286554A (en) * | 1991-11-25 | 1994-02-15 | The Dow Chemical Company | Substrate materials saturated with low vaporizable ethylenically unsaturated monomer emission vinyl ester and polyester resin compositions |
| US5340856A (en) * | 1991-11-25 | 1994-08-23 | The Dow Chemical Company | Curable vinyl ester comprising monomer ceresin wax and drying oil and epoxidized drying oil as secondary adhesion promoters and a curing agent |
| US5380775A (en) * | 1991-11-25 | 1995-01-10 | The Dow Chemical Company | Vinyl ester and polyester resins containing monomer, ceresin wax, drying oil and epoxidized drying oil |
| US5412010A (en) * | 1991-11-25 | 1995-05-02 | The Dow Chemical Company | Monomer supression additive containing ethylenically unsaturated monomer, ceresin wax, drying oil and epoxidized drying oil |
Also Published As
| Publication number | Publication date |
|---|---|
| NO782921L (en) | 1979-03-01 |
| DK378278A (en) | 1979-03-01 |
| EP0000941B1 (en) | 1980-07-23 |
| DE2738805A1 (en) | 1979-03-08 |
| DE2860076D1 (en) | 1980-11-13 |
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