DE1669104A1 - Process for the production of stoving enamels - Google Patents
Process for the production of stoving enamelsInfo
- Publication number
- DE1669104A1 DE1669104A1 DE19671669104 DE1669104A DE1669104A1 DE 1669104 A1 DE1669104 A1 DE 1669104A1 DE 19671669104 DE19671669104 DE 19671669104 DE 1669104 A DE1669104 A DE 1669104A DE 1669104 A1 DE1669104 A1 DE 1669104A1
- Authority
- DE
- Germany
- Prior art keywords
- terephthalic acid
- acid
- mixture
- high molecular
- molecular weight
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
-
- 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
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Landscapes
- 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)
- Sustainable Development (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
Patentanmeldung Verfahren zur Herstellung von Einbrennlacken Patent application Process for the production of stoving enamels
Für die Herstellung von Stanzlacken, welche nach dem ßandlackierverfahren (Coil-Coating) auf Metallbändern aufgetragen und im Ofen bei hohen Temperaturen getrocknet werden, haben sich Kombinationen von nichttrocknenden OH-Gruppen-haltigen Polyesterharzen auf Isophthalsäurebasis mit Hexamethoxymethylmelamin bewährt. BeSchichtungen auf dieser Basis besitzen bei ausgezeichneter Stanzfähigkeit eine sehr hohe Oberflächenhärte und geringe Fleckempfindlichkeit. Als Katalysator für die Vernetzung ist bisher ein Zusatz von etwa 1% p-Toluolsulfonsäure oder einer anderen starken Säure notwendig (Journ. of Paint Technology, Vol. 38, No. 501, Oct. 1966, S.600-609, Paint and Varnish Production nug. 1965, S. 59-62; Official Digest Jan. 1963, S. 56-68; Werbeschriften der American Cyanamid Corp. Cyzac 1476-8, I526, Cymel 300 und J1Ol). Da der Säurekatalysator bei der Ofentrocknung aus dem Film nicht entvreicht, wird hierdurch eine Minderung des Korrosionsschutzes und c-er Gilbungsbestandigkeit bedingt.Combinations of non-drying, OH-group-containing polyester resins based on isophthalic acid with hexamethoxymethylmelamine have proven to be effective for the production of punching varnishes, which are applied to metal strips using the coil coating process and are dried in the oven at high temperatures. Coatings on this basis have excellent punchability, very high surface hardness and low stain sensitivity. As a catalyst for crosslinking, an addition of about 1% p-toluenesulfonic acid or another strong acid has hitherto been necessary (Journ. Of Paint Technology, Vol. 38, No. 501, Oct. 1966, pp.600-609, Paint and Varnish Production n ug. 1965, pp. 59-62; Official Digest Jan. 1963, pp. 56-68; commercials from American Cyanamid Corp. Cyzac 1476-8, I526, Cymel 300 and J 1 Ol). Since the acid catalyst does not escape from the film during oven drying, this leads to a reduction in the protection against corrosion and resistance to yellowing.
Es wurde nun gefunden, daß man auf den Zusatz der Säurekatalysatoren verzichten kann, wenn man Polyesterharze auf der Basis von Terephthalsäure einsetzt. ^ Is Rohstoffe sind zum Beispiel Dimethylterephthalat und Ä'thylenglykol geeignet, jedoch haben sich besonders hochmolekulare Terephthalsäureester von Glykolen, vor allem Äthylenglykol bewährt, die bei der Fabrikation von Fasern und Folien als Abfall in beachtlichen Mengen anfallen. Diese hochmolekularen Ester werden zunächst in an sich bekannter V/eise, vgl. englisches Patent IOI6 596 mit zwei-bis vierwertigen Alkoholen, vorzugsweise einem Gemisch solcher zwei- und dreiwertiger "lkoholejdie mindestens drei C-Atome enthalten, wieIt has now been found that one can rely on the addition of the acid catalysts can do without using polyester resins based on terephthalic acid. ^ Is raw materials are for example Dimethyl terephthalate and ethylene glycol are suitable, but have Particularly high molecular weight terephthalic acid esters of glycols, especially ethylene glycol, have proven useful in the manufacture of Substantial quantities of fibers and foils are produced as waste. These high molecular weight esters are initially known per se V / eise, see English patent IOI6 596 with two- to four-valued Alcohols, preferably a mixture of such di- and trihydric ones "Alcohols that contain at least three carbon atoms, such as
909844/1666 - 2 -909844/1666 - 2 -
BAD ORIGINALBATH ORIGINAL
Propandiol -1,2 oder -1,3* 2,2-Dimethylpropandiol-l,3,die verschiedenen Butan->Pentan- oder Hexandiole, Glycerin, Trimethyloläthan oder -propan, Pentaerythrit oder Diglycerin, durch Umesterung aufgeschlossen und dann mit aliphatischen gesättigten oder olefinisch ungesättigten Dicarbonsäuren, wie Bernstein-, Adipin-, Azelain-, Sebacin-, Malein-, Fumar-, Itacon-, Mesacon- oder Citraconsäure verestert. Auch Isophthalsäure oder Phthalsäure können als Dicarbonsäure verwendet werden, sofern sie zu weniger als 50$, vorzugsweise zu weniger als 20 Äquivalentprozent, bezogen ^Uf die Äquivalentmenge an Terephthalsäureeinheiten,verwendet werden.Propanediol -1,2 or -1,3 * 2,2-Dimethylpropanediol-1,3, the various butane> pentane or hexanediols, glycerine, Trimethylolethane or propane, pentaerythritol or diglycerin, broken down by transesterification and then with aliphatic saturated or olefinically unsaturated dicarboxylic acids, such as Esterified succinic, adipic, azelaic, sebacic, maleic, fumaric, itaconic, mesaconic or citraconic acid. Also isophthalic acid or phthalic acid can be used as the dicarboxylic acid provided it is less than $ 50, preferably less than 20 equivalent percent, based on ^ Uf the equivalent amount on terephthalic acid units.
In den Gemischen der zwei- und dreiwertigen Alkohole sind diese Verbindungen vorteilhaft in einer solchen Menge enthalten, da3 das Äquivalentverhältnis zwischen 1:3 und 3:1 liegt. Soweit sie existieren, können auch die Anhydride verwendet werden. Zur Förderung der Benetzung der Pigmente und des Verlaufes baut man zweckmäi3ig noch eine oder mehrere nicht trocknenden Fettsäuren, wie Capryl-, Cap""' , Laurin-, Pelargon-, Isononan- oder Isooctansäure in einer Menge bis zu 30 Gewichtsprozent in das Harz ein, wobei die Prozentangabe auf das gesamte Harz bezogen ist. Vorzugsweise beträgt die Menge 5-25 Gewichtsprozent.In the mixtures of dihydric and trihydric alcohols, these compounds are advantageously contained in such an amount da3 the equivalent ratio between 1: 3 and 3: 1 lies. If they exist, the anhydrides can also be used. To promote the wetting of the pigments and during the course of the process, one or more non-drying fatty acids such as caprylic, cap "" ', lauric, Pelargonic, isononanoic or isooctanoic acid in an amount up to at 30 percent by weight in the resin, the percentage being based on the entire resin. Preferably the amount is 5-25 percent by weight.
Als Hexaalkoxyalkylmelamin kommt vor allem das Hexaalkoxymelamin in Frage. Es sind jedoch auch die Äther anderer niederer aliphatischer Alkohole, z.B. des Äthanols oder Butanols geeignet.As a hexaalkoxyalkylmelamine, the hexaalkoxymelamine is particularly suitable. However, it is also the ethers of others lower aliphatic alcohols, e.g. ethanol or butanol.
909844/ 1666909844/1666
BAD ORfGfNAtBAD ORfGfNAt
300 g Polyethylenterephthalat, 100 g 2,2-Dimethylpropandiol-1,3 und 80 g Trimethylolpropan werden bei 220-2500CJmit oder'1 ^*1 ohne Zusatz von Umesterungskatalysatoren umgeestert, bis die Masse in ."lkohol klar löslich ist. Dann wird auf l80°C gekühlt und 110 g Maleinsäureanhydrid sowie 50 g Isononansäure zugegeben und bei 2000C verestert, bis die Säurezahl = 10-15 beträgt. Das Harz wird dann in einem Gemisch von Äthylenglykolmonoäthylather und aromatischen Kohlenwasserstoffen (Solvesso 150) (Gev/ichtsverhältnis 2:l)gelöst und dann filtriert.300 g of polyethylene, 100 g of 2,2-dimethyl-1,3 and 80 g of trimethylol propane are esterified at 220-250 0 CJmit or '1 ^ * 1 without the addition of transesterification catalysts, until the mass in. "Lkohol clear soluble. Then is cooled to l80 ° C and 110 g of maleic anhydride and 50 g of isononanoic acid were added and esterified at 200 0 C, is until the acid value = 10-15. the resin is then in a mixture of Äthylenglykolmonoäthylather and aromatic hydrocarbons (Solvesso 150) (Gev / light ratio 2: 1) dissolved and then filtered.
Zur Herstellung des Lackes wird das Harz mit Hexamethoxymethylmelamin im Gewichtsverhältnis 85:15(jeweils gerechnet ρ Is Trocken substanz)kombiniert und mit Titandioxyd im Gewichtsverhältnis 1:1,(jeweils gerechnet als Peststoffe) pigmentiert und der Lack 15 Minuten lang bei 170-l80°C eingebrannt. Die erhaltenen Filme sind rein weiß, einwandfrei stanzfähig, haben Pendelhärte von I6O-I8O nach König(s. "Farbe und Lack" Band £2 (1953) Seite 435), und sind fleckbeständig gegen Jod, Schuhkrem, Lippenstift,Senf usw.To produce the varnish, the resin is mixed with hexamethoxymethylmelamine in a weight ratio of 85:15 (calculated in each case ρ Is dry substance) combined and pigmented with titanium dioxide in a weight ratio of 1: 1 (each calculated as pesticides) and the varnish Baked for 15 minutes at 170-180 ° C. The films obtained are pure white, perfectly punchable, have a pendulum hardness of I6O-I8O according to König (see "Color and Lacquer" Volume £ 2 (1953) page 435), and are stain resistant to iodine, shoe polish, lipstick, mustard, etc.
Ersetzt man in dem Beispiel die Terephthalsäure durch Isophthalsäure, so ist ein Zusatz von er. 1% Toluolsulfosäure zu dem Lack notwendig, um eine Lackierung mit vergleichbaren Eigenschaften zu erzielen.If terephthalic acid is replaced by isophthalic acid in the example, then there is an addition of er. 1% toluenesulphonic acid is required for the paint in order to achieve a paint finish with comparable properties.
432 g Polyalkylenterephthalat, I56 £ Neopentylglykol und 121 g Trimethylolpropui werden bei 220-250° mit oder ohne Zusatz von Katal; c-.toren umgeestert, bis das Recktionsprodukt in Kthylalkoliol löslich ist. Nach Kühlung auf 1-.jO°C vrerden £20 g Maleincäuro^nh· dric und 60g Isononansäure zugegeben und bei 2000C verestern, bis eine Säurezciil von 30-35 erreicht is*~. Das H--ν ζ v.rirs 'ir-nn in einem Gemisch von Äthylenglykolmor.oaV.hylather ur.: aromatischen Kohlenwasserstoffen gelöst -Ui-' f ilti-ic-:·:·.432 g of polyalkylene terephthalate, I56 £ neopentyl glycol and 121 g of trimethylolpropui are at 220-250 ° with or without the addition of catal; c-.toren transesterified until the reaction product is soluble in ethyl alcohol. After cooling to 1-.jO ° C vrerden £ 20 g Maleincäuro ^ NH · dric 60g and isononanoic acid are added and esterified at 200 0 C, until an Säurezciil of 30-35 is * ~. The H - ν ζ v. r ir s ' ir-nn in a mixture of ethylene glycol mor.oaV.hylather ur. : aromatic hydrocarbons dissolved -Ui- 'f ilti-ic-: ·: ·.
9098A4/166b
BAD ORIGINAL9098A4 / 166b
BATH ORIGINAL
260 g Terephthalsäuredimethylester, 68 g Äthylenglykol 100 g Neopentylglykol und 80,5 g Trimetir./lolpropan werden bei 180-200°C umgeestert und nach Zugabe von 110 g Maleinsäureanhydrid und 50 g Isononansäure bei 2000C verestert, bir. die Säurezahl 10 - 15 beträgt. Oes Harz wird dann im gleichen Lösungsmittel wie nach Beispiel 2 gelöst.260 g of dimethyl terephthalate, 68 g ethylene glycol 100 g of neopentyl glycol and 80.5 g Trimetir./lolpropan are transesterified at 180-200 ° C and esterified by adding 110 g of maleic anhydride and 50 g of isononanoic acid at 200 0 C, bir. the acid number is 10-15. The resin is then dissolved in the same solvent as in Example 2.
Die mechanischen Eigenschaften der erfindüngsgemäß erhaltenen Produkte wurden un Lackmustern mit einer Schichtdicke von 20-25 /U ermittelt. Die Pendelhärte nach König betrug I6O-I8O sec, J ie Erichsentiefung 7-8 mm, Schlagtiefung nach Niessen 70-80 cm (2 kg), Glanz nach Lange 95-98, Bleistifthärte J> - 4 H.The mechanical properties obtained according to the invention Products were determined in paint samples with a layer thickness of 20-25 / U. The pendulum hardness according to König Was 160-180 sec, J ie Erichsen depression 7-8 mm, impact depression according to Niessen 70-80 cm (2 kg), gloss according to Lange 95-98, pencil hardness J> - 4 H.
9 0 9 8 4 Λ/1666
BAD ORIGINAL9 0 9 8 4 Λ / 1666
BATH ORIGINAL
Claims (1)
Dr. LQ/GbJuly 7, 1967
Dr. LQ / Gb
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEC0042822 | 1967-07-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
DE1669104A1 true DE1669104A1 (en) | 1969-10-30 |
Family
ID=7025112
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19671669104 Pending DE1669104A1 (en) | 1967-07-08 | 1967-07-08 | Process for the production of stoving enamels |
Country Status (2)
Country | Link |
---|---|
DE (1) | DE1669104A1 (en) |
FR (1) | FR1579681A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0103251A2 (en) * | 1982-09-10 | 1984-03-21 | Hannes Dr. Fischer | Binding agents for stoving lacquers |
EP0150476A2 (en) * | 1984-01-18 | 1985-08-07 | Hüls Troisdorf Aktiengesellschaft | Coating composition |
EP0558906A1 (en) * | 1992-01-23 | 1993-09-08 | The Sherwin-Williams Company | Non-aqueous coating compositions from polyethylene terephthalate |
-
1967
- 1967-07-08 DE DE19671669104 patent/DE1669104A1/en active Pending
-
1968
- 1968-07-05 FR FR1579681D patent/FR1579681A/fr not_active Expired
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0103251A2 (en) * | 1982-09-10 | 1984-03-21 | Hannes Dr. Fischer | Binding agents for stoving lacquers |
EP0103251A3 (en) * | 1982-09-10 | 1986-07-30 | Hannes Dr. Fischer | Binding agents for stoving lacquers |
EP0150476A2 (en) * | 1984-01-18 | 1985-08-07 | Hüls Troisdorf Aktiengesellschaft | Coating composition |
EP0150476A3 (en) * | 1984-01-18 | 1985-08-21 | Dynamit Nobel Aktiengesellschaft | Coating composition |
EP0558906A1 (en) * | 1992-01-23 | 1993-09-08 | The Sherwin-Williams Company | Non-aqueous coating compositions from polyethylene terephthalate |
Also Published As
Publication number | Publication date |
---|---|
FR1579681A (en) | 1969-08-29 |
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