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EP0000941B1 - Low-volatility, curable, unsaturated polyester resins with good lamination properties - Google Patents

Low-volatility, curable, unsaturated polyester resins with good lamination properties Download PDF

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Publication number
EP0000941B1
EP0000941B1 EP78100727A EP78100727A EP0000941B1 EP 0000941 B1 EP0000941 B1 EP 0000941B1 EP 78100727 A EP78100727 A EP 78100727A EP 78100727 A EP78100727 A EP 78100727A EP 0000941 B1 EP0000941 B1 EP 0000941B1
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EP
European Patent Office
Prior art keywords
acid
unsaturated
polyester resins
paraffin
unsaturated polyester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
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EP78100727A
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German (de)
French (fr)
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EP0000941A1 (en
Inventor
Walter Gramlich
Wolfgang Dr. Koser
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BASF SE
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BASF SE
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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
    • 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
    • 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
    • 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 optionally further structural components and auxiliaries which contain paraffin mixtures to reduce monomer evaporation and to improve the ability to be laminated.
  • Molding and molding compounds made from unsaturated polyester resins usually contain, apart from unsaturated polyesters and monomeric vinyl compounds copolymerizable therewith, polymerization initiators and inhibitors, and often powdery 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.
  • DE-OS 1 956376 it is proposed to apply a wax-like substance, its dispersion or solution in a thin layer to a paint 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 quantities 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.
  • 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, however, 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 relatively easily from one another. The better the substrate is hardened, the worse the adhesion.
  • DE-AS 1 156 230 describes curable molding compositions which contain unsaturated polyesters, polymerizable compounds, customary auxiliaries and a mixture of waxes. This mixture contains waxes with a melting point above 75 ° C and those with a melting point below 75 ° C. None of the waxes mentioned in the description melt below 50 ° C. The overlaminability of unsaturated polyester resins cannot be improved with such wax mixtures.
  • the laminability of 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 Addition of liquid alkanes or their mixtures to waxy substances can be improved.
  • 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 ethylenically un did not or only to a minor extent evaporate saturated monomers during processing without impairing overlaminability.
  • 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.
  • the low-evaporation, easily over-aminable, curable, unsaturated polyester resins according to the invention are prepared 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.
  • Suitable polyhydric, in particular dihydric, optionally unsaturated alcohols are the customary, in particular acyclic, cyclic groups and also alkanediols and oxalkanediols containing both types of groups, such as Ethylene glycol, propylene glycol 1,2, propanediol 1,3, butylene glycol 1,3, 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-bismethylolcyclohexane,, vinyl glycol,. Trimethylolpropane monoallyl ether or 1,4-butenediol.
  • one-, three- or higher-hydric alcohols such as ethylhexanol, fatty alcohols, benzyl alcohols, 1,2-di (allyl l oxy) propanol (-3), glycerol, pentaerythritol or trimethylol propane, are co-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.
  • Suitable carboxylic acids or their derivatives are dibasic olefinically unsaturated, preferably, a, ⁇ -olefinically unsaturated carboxylic acids, e.g. Maleic acid, fumaric acid, iltaconic 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, a-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-1,2,3-methylene chloride, tetrachlorophthalic acid, 3,6-endomethylene-1,2,3-methylene chloride, , be condensed, 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 optionally crystallizable unsaturated polyesters can be used for the process according to the invention.
  • 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.
  • 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.
  • Suitable reinforcing agents are inorganic or organic fibers or flat structures, optionally woven therefrom, e.g. 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 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 ⁇ -keto amides such as ethyl 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 and polyvinyl acetate 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).
  • the individual components (a) to (d) can be mixed and the paraffin mixtures mixed in using conventional mixing units, for example with an agitator or a roller mill.
  • Unsaturated polyester resins produced in this way can be cured with polymerization initiators, such as peroxides, azo compounds, etc., possibly in the presence of polymerization 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 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 B is produced analogously to the specifications of polyester resin A, but the starting components maleic acid, o-phthalic acid and 1,2-propylene glycol 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 and 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 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, whose softening range was between 32 ° C 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.
  • the comparative tests a, b, d and e which are not produced according to the invention have good layer adhesion, but high styrene evaporation and the comparison tests c and f have low styrene evaporation and poor layer adhesion.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Description

Die Erfindung betrifft verdunstungsarme, in Gegenwart üblicher Pöiymerisationsinitiatoren 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 optionally further structural components and auxiliaries which contain paraffin mixtures to reduce monomer evaporation and to improve the ability to be laminated.

Form- und Preßmassen aus ungesättigten Polyesterharzen enthalten üblicherweise, außer ungesättigten Polyestern und damit copolymerisierbaren monomeren Vinylverbinddungen, 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, apart from unsaturated polyesters and monomeric vinyl compounds copolymerizable therewith, polymerization initiators and inhibitors, and often powdery 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 Wickerverfahren, Mono- merenverluste 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.By the addition of essential for the application-technical usability volatile, olefinically unsaturated monomers such as styrene, occur in the processing of unsaturated curable polyester molding compositions necessarily in all processing techniques, for example during hand, spray or Wicker method, mono - merenverluste as soon as the unsaturated , curable 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 DE-PS 948 816 ist bekannt, daß Zusätze von wachsartigen 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 DE-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 DE-OS 1 956376 wird vorgeschlagen, 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 DE-OS 1 956376 it is proposed to apply a wax-like substance, its dispersion or solution in a thin layer to a paint 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 quantities 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 lacquer film with the solution containing the barrier layer, too high a pressure, too high a temperature and too great a solubility of the process components are avoided, 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 jedoach 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 voneiander 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. Paraffins have the disadvantage, however, 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 relatively easily from one another. The better the substrate is hardened, the worse the adhesion.

In der DE-AS 1 156 230 sind härtbare Formmassen beschrieben, die ungesättigte Polyester, polymerisierbare Verbindungen, übliche Hilfsstoffe, sowie eine Mischung von Wachsen enthalten. Diese Mischung enthält Wachse mit einem Schmelzpunkt über 75°C und solche mit einem Schmelzpunkt unter 75°C. Von den in der Beschreibung genannten Wachsen schmilzt keines unter 50°C. Mit derartigen Wachsgemischen läßt sich die Überlaminierbarkeit von ungesättigten Polyesterharzen nicht verbessern.DE-AS 1 156 230 describes curable molding compositions which contain unsaturated polyesters, polymerizable compounds, customary auxiliaries and a mixture of waxes. This mixture contains waxes with a melting point above 75 ° C and those with a melting point below 75 ° C. None of the waxes mentioned in the description melt below 50 ° C. The overlaminability of unsaturated polyester resins cannot be improved with such wax mixtures.

Die Überlaminierbarkeit von ungesättigten Polyesterharzen kann nach Angaben der DE--OS 25 54 930 und 27 05 966 durch den Zusatz von Wasser-in-ÖI oder ÖI-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 DE-OS 25 54 930 and 27 05 966, the laminability of 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 Addition of liquid alkanes or their mixtures to waxy substances can be improved. 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 äthylenisch ungesättigten Monomerln 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 ethylenically un did not or only to a minor extent evaporate saturated monomers during processing without impairing overlaminability.

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 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) üblichen Aufbaukomponenten und Hilfsstoffen, die dadurch gekennzeichnet sind, daß sie als wachsartige Stoffe eine Paraffinmischung enthalten, die besteht aus 0,01 bis 0,5 Gew.% mindestens eines Paraffins mit einem Schmelzpunkt zwischen 25°C und 50°C und mindestens 0,01 bis 0,5 Gew.% eines Paraffins mit einem Schmelzpunkt zwischen 51 und 100°C, wobei sich die Prozentangaben auf des Gesamtgewicht der Komponenten a) und b) beziehen.
The present invention thus relates to curable, unsaturated polyester resins
  • a) at least one ethylenically unsaturated copolymerizable polyester,
  • b) at least one ethylenically unsaturated copolymerizable monomeric compound,
  • c) a waxy substance, and optionally
  • d) usual structural components and auxiliaries, which are characterized in that they contain, as waxy substances, a paraffin mixture which consists of 0.01 to 0.5% by weight of at least one paraffin with a melting point between 25 ° C. and 50 ° C. and at least 0.01 to 0.5% by weight of a paraffin with a melting point between 51 and 100 ° C., the percentages relating to the total weight of components a) and b).

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 ver- 'dunstungsarmen, gut überiaminierbaren, 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 low-evaporation, easily over-aminable, curable, unsaturated polyester resins according to the invention are prepared 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.
For the starting components a) to d) which can be used to prepare the low-evaporation, low-evaporation, readily overlaminatable and curable in the presence of customary polymerization initiators:
  • 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-Bismethylolcyclohexan, , Vinylglykol, . Trimethylolpropanmonoallyläther oder Butendiol-1,4.Suitable polyhydric, in particular dihydric, optionally unsaturated alcohols are the customary, in particular acyclic, cyclic groups and also alkanediols and oxalkanediols containing both types of groups, such as Ethylene glycol, propylene glycol 1,2, propanediol 1,3, butylene glycol 1,3, 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-bismethylolcyclohexane,, 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-(allyll oxy-) propanol (-3), Glycerin, Pentaerythrit oder Trimethylolpropan, in untergeordneten Mengen mitverwendet werden. Die mehrwertigen, insbesondere zweiwertigen Alkohole werden im allgemeinen in stöchiometrischen oder annähernd stöchiometrischen Mengen mit mehrbasischen, insbesondere zweibasischen Carbonsäuren bzw. deren kondensierbaren Derivaten umgesetzt.Further, one-, three- or higher-hydric alcohols, such as ethylhexanol, fatty alcohols, benzyl alcohols, 1,2-di (allyl l oxy) propanol (-3), glycerol, pentaerythritol or trimethylol propane, are co-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, a,ß-olefinisch ungesättigte Carbonsäuren, wei z.B. Maleinsäure, Fumarsäure, Iltaconsaüre, 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 Carbonsaüren oder -derivate, wie z.B. Bernsteinsäure, Glutarsäure, a-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, a, β-olefinically unsaturated carboxylic acids, e.g. Maleic acid, fumaric acid, iltaconic 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, a-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-1,2,3-methylene chloride, tetrachlorophthalic acid, 3,6-endomethylene-1,2,3-methylene chloride, , be condensed, 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. Amorphous and optionally crystallizable unsaturated polyesters can be used for the process according to the invention.

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 bi 70, vorzugsweise 15 bis 50 Gewichtsprozent, bezogen auf die Komponente a) bis c) an ungesättigten Polyestern a).

  • b) Als copolymerisierbare äthylenisch 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, Athylhexyacrylat, Hydroxypropylacrylat, Dicyclopentadienylacrylat, Butandioldiacrylat und (Meth)-acryl- säureamide, Allylester, wie z.B. Diallylphthalat und Vinylester, wie z.B. Äthylhexansäurevinylester, Vinylpivalat und andere.
With regard to the composition of unsaturated polyesters, reference is also made, for example, to the book by HV 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) Suitable copolymerizable ethylenically 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 For example, methyl methacrylate, butyl acrylate, ethylhexyacrylate, hydroxypropyl acrylate, dicyclopentadienyl acrylate, butanediol diacrylate and (meth) acrylic acid amides, allyl esters, such as diallyl phthalate and vinyl esters, such as, for example, ethylhexanoic acid vinyl acetate and others, vinylpivalate.

Desgleichen eignen sich Gemische der genannten äthylenisch ungesättigten Monomeren. Bevorzugt geeignet als Komponente (b) sind Styrol, Vinyltoluol, a-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.

  • 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.
Mixtures of the ethylenically unsaturated monomers mentioned are likewise suitable. Styrene, vinyl toluene, a-methylstyrene and diallyl phthalate are particularly suitable as component (b). Component b) is generally present in the polyester resins in an amount of 5 to 60, preferably 10 to 45 percent by weight, based on the mixture of components a) + b).
  • c) Wax-like substances falling under point c) which can be used for the paraffin mixture are, 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.

  • 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.
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, ceresin and the like, can also be used.
  • d) Examples of suitable structural components and auxiliaries in accordance with point d, such as are usually used in unsaturated polyester resins: thickeners, inhibitors, fillers, reinforcing agents and, if appropriate, inert solvents, polymerization accelerators, shrinkage-reducing additives and others conventionally used in the processing of polyester resins Auxiliaries.

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.-Butyl- brenzkatechin, 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.Suitable reinforcing agents are inorganic or organic fibers or flat structures, optionally woven therefrom, e.g. 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 ungesättigten Polyesterharze können vorbeschleunigt sein. Als Poiymerisationsbeschleuniger kommen beispielsweise Schwermetallsalze wie Kobaltund Vanadinsalze, tertiäre aromatische Amine, 1,3-Diketonverbindungen wie Acetylaceton, ß-Ketoester, wie Acetessigsäureäthylester und ß-Ketoamide wie Acetessigsäurediäthylamid und Kombinationer, dieser Verbindungen in Frage.The unsaturated polyester resins 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-keto amides such as ethyl 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 and polyvinyl acetate 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).

Das Vermischen der Einzelkomponenten (a) bis (d) und das Zumischen der Paraffingemische kann unter Verwendung üblicher Mischaggregate erfolgen, beispielsweise mit einem Rührewerk oder einem Walzenstuhl. Derartig hergestellte ungesättigte Polyesterharze lassen sich mit Polymerisationsinitiatoren, wie Peroxide, Azoverbindungen u.a., evtl. in Gegenwart von Polymerisationsbeschleunigern oder Cobeschleunigern bzw. Promotoren oder durch Bestrahlung, beispielsweise mit Licht, durch UV-Strahlung oder beschleunigte Elektronenstrahlen evtl. in Gegenwart von Lichtinitiatoren und Sensibilisatoren härten.The individual components (a) to (d) can be mixed and the paraffin mixtures mixed in using conventional mixing units, for example with an agitator or a roller mill. Unsaturated polyester resins produced in this way can be cured with polymerization initiators, such as peroxides, azo compounds, etc., possibly in the presence of polymerization 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 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 Polyester: harze 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 polyesters.

Die in den Beispielen angegebenen Teile und Prozente sind Gewichtsteile bzw. Gewichtsprdzente.The parts and percentages given in the examples are parts by weight or 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 B 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 B is produced analogously to the specifications of polyester resin A, but the starting components maleic acid, o-phthalic acid and 1,2-propylene glycol 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, Neopentylglykol im Molverhältnis 1 : 1 : 2 kondensiert werden. Der isomerisierungsgrad betrug 90 %.Polyester resin C is produced analogously to the specifications of polyester resin A, but the starting components maleic acid, isophthalic acid and 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.In a flat bowl with a low rim (e.g. 25 x 25 x 0.3 cm), polyester resin is distributed 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 Überlaminierbarkeit:Overlaminability test: 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.

Beispiele 1 bis 8 und Vergleichsversuche a bis fExamples 1 to 8 and comparative experiments a to f

Die Polyesterharze A und B wurden mit Paraffinen versetzt, deren Erweichungsbereich zwischen 32°C und 96°C lag.The polyester resins A and B were mixed with paraffins, whose softening range was between 32 ° C 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 Vergleichsversuche a, b, d und e eine gute Lagenhaftung, jedoch große Styrolverdunstung und die Vergleichsversuche c und f eine geringe Styrolverdunstung und schlechte Lagenhaftung auf.

Figure imgb0001
Figure imgb0002
 As can be seen from the table, the comparative tests a, b, d and e which are not produced according to the invention have good layer adhesion, but high styrene evaporation and the comparison tests c and f have low styrene evaporation and poor layer adhesion.
Figure imgb0001
Figure imgb0002

Claims (1)

  1. Curable unsaturated polyester resins containing
    a) at least one ethylenically unsaturated copolymerizable polyester,
    b) at least one ethylenically unsaturated copolymerizable monomeric compound
    c) waxy materials, with or without
    d) conventional components and auxiliaries, wherein the polyester resins contain, as waxy materials, a paraffin mixture consisting of 0.01 to 0.5 per cent by weight of at least one paraffin with a melting point of between 25°C and 50°C and 0.01 to 0.5 per cent by weight of a paraffin with a melting point of between 51 °C and 100°C, the percentages referring to the total weight of components a) and b).
EP78100727A 1977-08-29 1978-08-23 Low-volatility, curable, unsaturated polyester resins with good lamination properties Expired EP0000941B1 (en)

Applications Claiming Priority (2)

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DE2738805 1977-08-29
DE19772738805 DE2738805A1 (en) 1977-08-29 1977-08-29 LOW EVAPORATION, EASILY OVERLAMINABLE, HARDABLE, UNSATATURATED POLYESTER RESINS

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EP0000941A1 EP0000941A1 (en) 1979-03-07
EP0000941B1 true EP0000941B1 (en) 1980-07-23

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EP78100727A Expired EP0000941B1 (en) 1977-08-29 1978-08-23 Low-volatility, curable, unsaturated polyester resins with good lamination properties

Country Status (4)

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EP (1) EP0000941B1 (en)
DE (2) DE2738805A1 (en)
DK (1) DK378278A (en)
NO (1) NO782921L (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL125545B1 (en) * 1980-02-11 1983-05-31 Inst Chemii Przemyslowej Method of manufacture of unsaturated polyester resins of diminished monomer vaporization
DE3933656A1 (en) * 1989-10-09 1991-04-11 Basf Ag LOW EVAPORATIVE 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
DK195190D0 (en) * 1990-08-16 1990-08-16 Keld Jakobsen WEAR PAINT
US5206077A (en) * 1991-11-25 1993-04-27 The Dow Chemical Company Low vaporizable ethylenically unsaturated monomer emission vinyl ester and polyester resin compositions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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 Process for producing a coated titanium dioxide pigment

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE538294A (en) * 1953-10-09
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
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 Process for producing a coated titanium dioxide pigment
DE2948334A1 (en) * 1978-11-30 1980-06-19 Du Pont LIGHT-RESISTANT TITANIUM DIOXIDE PIGMENT COMPOSITION

Also Published As

Publication number Publication date
DE2860076D1 (en) 1980-11-13
DE2738805A1 (en) 1979-03-08
EP0000941A1 (en) 1979-03-07
NO782921L (en) 1979-03-01
DK378278A (en) 1979-03-01

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