DE3542569A1 - Process for the preparation of cathodic electrodeposition coating binders based on modified epoxy resins - Google Patents
Process for the preparation of cathodic electrodeposition coating binders based on modified epoxy resinsInfo
- Publication number
- DE3542569A1 DE3542569A1 DE19853542569 DE3542569A DE3542569A1 DE 3542569 A1 DE3542569 A1 DE 3542569A1 DE 19853542569 DE19853542569 DE 19853542569 DE 3542569 A DE3542569 A DE 3542569A DE 3542569 A1 DE3542569 A1 DE 3542569A1
- Authority
- DE
- Germany
- Prior art keywords
- epoxy resins
- modified epoxy
- reaction
- preparation
- compounds
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000011230 binding agent Substances 0.000 title claims abstract description 12
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 6
- 238000000576 coating method Methods 0.000 title abstract description 5
- 238000002360 preparation method Methods 0.000 title abstract 2
- 239000011248 coating agent Substances 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000003822 epoxy resin Substances 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 10
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003973 paint Substances 0.000 claims abstract description 5
- 238000004132 cross linking Methods 0.000 claims abstract description 4
- 230000008030 elimination Effects 0.000 claims abstract description 4
- 238000003379 elimination reaction Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 230000005588 protonation Effects 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 238000013459 approach Methods 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- -1 enamels Substances 0.000 abstract description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 abstract description 3
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- 239000002966 varnish Substances 0.000 abstract description 2
- 210000003298 dental enamel Anatomy 0.000 abstract 1
- 150000002118 epoxides Chemical class 0.000 abstract 1
- 239000004922 lacquer Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 5
- OIVLITBTBDPEFK-UHFFFAOYSA-N 5,6-dihydrouracil Chemical compound O=C1CCNC(=O)N1 OIVLITBTBDPEFK-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 206010035148 Plague Diseases 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000003940 butylamines Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 201000006747 infectious mononucleosis Diseases 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- NYIODHFKZFKMSU-UHFFFAOYSA-N n,n-bis(methylamino)ethanamine Chemical compound CCN(NC)NC NYIODHFKZFKMSU-UHFFFAOYSA-N 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000002924 oxiranes Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
- C08G18/643—Reaction products of epoxy resins with at least equivalent amounts of amines
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
- C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
Abstract
Description
Verfahren zur Herstellung von KETL-Bindemitteln auf BasisProcess for the production of KETL binders based on
von modifizierten Epoxidharzen Verfahren zur Herstellung von KETL-Bindemitteln auf Basis von modifizierten Epoxidharzen Die Erfindung betrifft ein Verfahren zur Herstellung von selbstvernetzenden wasserverdünnbaren Bindemitteln für Lacke, welche nach dem Elektrotauchlackierverfahren an der Kathode abgeschieden werden können (K-ETL-Bindemittel) auf der Basis von modifizierten Epoxidharzen.of modified epoxy resins Method of manufacture of KETL binders based on modified epoxy resins The invention relates to a process for the production of self-crosslinking water-thinnable binders for paints that are deposited on the cathode after the electrodeposition process (K-ETL binders) based on modified epoxy resins.
Die wesentliche Modifizierungsreaktion erfolgt gemäß der vorliegenden-Erfindung durch Umsetsung von Bydroxylgruppen aufweisenden Epoxidharzen bzw. und vorzugsweise von Hydroxylgruppen aufweisenden Epoxid-Amin-Addukten mit Verbindungen der allgemeinen Formel NCO - R3 - NH - CO - N(R2) - CH2 - CH2 - CO - OR1 wobei die Indizes die im Anspruch angegebene Bedeutung haben und einer nachfolgenden Kondensationsphase, wobei angenommen wird, daß in dieser Phase unter Abspaltung des Alkohols R1-OH Ringschluß unter Ausbildung eines Dihydrourazils erfolgt (siehe beiliegendes Formelschema).The essential modification reaction occurs in accordance with the present invention by reacting epoxy resins containing hydroxyl groups or and preferably of hydroxyl-containing epoxy-amine adducts with compounds of the general Formula NCO - R3 - NH - CO - N (R2) - CH2 - CH2 - CO - OR1 where the indices are the im Claim have given meaning and a subsequent condensation phase, it is assumed that in this phase with elimination of the alcohol R1-OH ring closure takes place with the formation of a dihydrouracil (see attached formula scheme).
Diese Annahme wird durch die Literatur, z. B. durch einen Aufsatz von K. Norsch, ß-Ureidocarbonsäuren und Dihydrourazile, Nonatsh. Chem. 64, 333 - 340 (1934) gestützt.This assumption is supported by the literature, e.g. B. through an essay by K. Norsch, ß-Ureidocarbonsäuren und Dihydrourazile, Nonatsh. Chem. 64, 333 - 340 (1934).
Es hat sich gezeigt, daß durch diese Modifikation, im Vergleich zu anderen Verfahren, eine wesentliche Verbesserung der Haftungseigenschaften von Folgeschichten auf der ausgehärteten KETL-Grundierung erzielt wird.It has been shown that by this modification, compared to other processes, a significant improvement in the adhesion properties of subsequent layers is achieved on the cured KETL primer.
Insbesonders wird die Haftung von Unterbodenbeschichtungen auf PVC-Basis, wie sie bei Kraftfahrzeugen zum Schutz gegen Steinschlagschäden aufgebracht werden, verbessert.In particular, the adhesion of underbody coatings based on PVC, how they are applied to motor vehicles to protect against stone chip damage, improved.
Überdies werden dabei Bindemittel erhalten, welche bereits bei Einbrenntemperaturen von 150 bis 1600C Pilme mit hervorragenden Beständigkeitseigenschaften ergeben. Durch das Fehlen von Estergruppen im Molekülgerüst sind überdies Verseifungsreaktionen ausgeschlossen.In addition, binders are obtained which are already at stoving temperatures from 150 to 1600C pilme with excellent resistance properties. The lack of ester groups in the molecular structure also leads to saponification reactions locked out.
Die vorliegende Erfindung betrifft demgemäß ein Verfahren zur Herstellung von selbstvernetzenden, nach Protonisierung wasserverdünnbaren Bindemitteln für Lacke, welche nach dem Elektrotauchlackierverfahren an der Kathode abgeschieden werden können, auf der Basis von modifizierten Epoxidharzen, welches dadurch gekennzeichnet ist, daß man die Hydroxylgruppen eines gegebenenfalls modifizierten Epoxidharzes mit einem Epoxidäquivalentgewicht zwischen 180 und 2000 vor der Umsetzung mit einer den Epoxidgruppen äquivalenten Menge eines Amins, oder die Hydroxylgruppen eines Adduktes aus den genannten Verbindungen mit einer Verbindung der allgemeinen Formel NCO - R3 - NH - CO - N(R2) - CH2 - CH2 - CO - OR wobei R1 einen Alkylrest mit 1 bis 12 C-Atomen, R2 einen Alkylrest oder einen tert. Aminoalkylrest mit 4 bis 8 C-Atomen und R3 einen gegebenenfalls alkylsubstituierten, aromatischen, aliphatischen oder cycloaliphatischen Kohlenwasserstoffrest bedeutet, bei 60 bis 700C bis zu einem NCO-Wert von praktisch 0 umsetzt und anschließend den Ansatz bei 80 bis 90iC 1 bis 3 Stunden unter Abspaltung des Alkohols R1 - OH weiterreagiert, wobei der Anteil an Verbindungen der angegebenen Formel bezogen auf 1000 Teile Bindemittel mindestens 0,3, vorzugsweise 0,6 bis 1,2 Mol beträgt.The present invention accordingly relates to a method of manufacture of self-crosslinking binders that can be thinned with water after protonation for Paints which are deposited on the cathode after the electrodeposition process can be based on modified epoxy resins, which is characterized is that the hydroxyl groups of an optionally modified epoxy resin with an epoxy equivalent weight between 180 and 2000 before reacting with a the amount of an amine equivalent to the epoxide groups, or the hydroxyl groups of one Adduct of the compounds mentioned with a compound of the general formula NCO - R3 - NH - CO - N (R2) - CH2 - CH2 - CO - OR where R1 is an alkyl radical with 1 up to 12 carbon atoms, R2 is an alkyl radical or a tert. Aminoalkyl radical with 4 to 8 C atoms and R3 an optionally alkyl-substituted, aromatic, aliphatic or cycloaliphatic hydrocarbon radical means at 60 to 700C up to one NCO value of practically 0 and then the approach at 80 to 90iC 1 to The reaction continued for 3 hours with elimination of the alcohol R1 - OH, the proportion of compounds of the formula given based on 1000 parts of binder at least 0.3, preferably 0.6 to 1.2 mol.
Die modifizierende Komponente gemäß der allgemeinen Formel NCO - R3 - NH - CO - N(R2) - CH2 - CH2 - CO - OR1, wobei die Indizes R1 bis R3 die im Patentanspruch angegebene Bedeutung haben, wird durch Addition eines Acrylsäureesters an ein primäres Amin und Umsetzung dieses Adduktes mit äquimolaren Mengen eines Diisocyanats erhalten (siehe Formelschema).The modifying component according to the general formula NCO - R3 - NH - CO - N (R2) - CH2 - CH2 - CO - OR1, where the indices R1 to R3 are those in the claim Have given meaning, is by addition of an acrylic acid ester to a primary Obtained amine and reaction of this adduct with equimolar amounts of a diisocyanate (see formula scheme).
Als Ausgangsmaterialien für diese Komponente dienen als Amine primäre Alkylamine mit 4 bis 8 Kohlenstoffatomen, wie die isomeren Butylamine und deren höheren Homologe sowie primär-tertiäre Alkylendiamine, wie N,N-Dimethylaminoethylamin oder N,N-Diethylaminopropylamin. Als Acrylsäureester sind die Ester mit Alkoholen mit 1 bis 12 Kohlenstoffatomen geeignet. Die erhaltenen ß-Aminocarbonsäureester werden weiter mit aromatischen, aliphatischen oder cycloaliphatischen Diisocyanaten, wie Toluylendiisocyanat, Hexamethylendiisocyanat oder Isophorondiisocyanat reagiert.The starting materials for this component are primary amines Alkylamines with 4 to 8 carbon atoms, such as the isomeric butylamines and their higher homologues and primary-tertiary alkylenediamines, such as N, N-dimethylaminoethylamine or N, N-diethylaminopropylamine. As acrylic acid esters, the esters are with alcohols with 1 to 12 carbon atoms are suitable. The ß-aminocarboxylic acid esters obtained continue with aromatic, aliphatic or cycloaliphatic diisocyanates, reacts like tolylene diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate.
Die Herstellung dieser Komponente erfolgt in erster Stufe durch Umsetzung des im Reaktionsgefäß vorgelegten Amins bei 30 bis 400C unter Kühlen durch gleichmäßige Zugabe des Acrylates innerhalb 30 bis 60 Minuten. Die Reaktion wird bei 75-C während weiterer 1 bis 2 Stunden vervollständigt. In der 2. Stufe wird das Diisocyanat, gegebenenfalls zusammen mit isocyanatinerten Lösungsmitteln vorgelegt und die in der ersten Stufe hergestellte Aminkomponente unter Kühlen bei 20 bis 300C während 30 bis 45 Minuten zugegeben. Nach diesem Zeitraum ist die Halbblockierung üblicherweise abgeschlossen.The production of this component takes place in the first stage by conversion of the amine presented in the reaction vessel at 30 to 40 ° C. with cooling by uniform Addition of the acrylate within 30 to 60 minutes. The reaction is carried out at 75-C completed another 1 to 2 hours. In the 2nd stage, the diisocyanate, optionally presented together with isocyanate solvents and the in the amine component produced in the first stage with cooling at 20 to 300C during Added for 30 to 45 minutes. After this period, the half-block is usually closed.
Die Umsetzung mit dem Epoxidharz bzw. vorzugsweise mit dem Epoxid-Amin-Addukt erfolgt bei 60 bis 700C bis zu einem NCO-Wert von praktisch 0. Soferne die Reaktion mit den Hydroxylgruppen eines Epoxidharzes erfolgt, erfolgt die Herstellung des Aminadduktes im Anschluß an diese Reaktion.The reaction with the epoxy resin or preferably with the epoxy-amine adduct takes place at 60 to 700C up to an NCO value of practically 0. Unless the reaction occurs takes place with the hydroxyl groups of an epoxy resin, the production takes place Amine adduct following this reaction.
Das Reaktionsprodukt wird anschließend auf 80 bis 900C erwärmt und bei dieser Temperatur 1 bis 3 Stunden gehalten. Da während dieser Reaktions&eit eine zunehmende Rückflußdestillation des Alkohols R1 - OH auftritt wird angenommen, daß in dieser Stufe ein Ringschluß zum Dihydrourazil eintritt. Nach dieser Zeit ist üblicherweise des bei der Bildung der Dihydrourazilgruppe gebildete Alkohol R1-OH abgespalten, was sich durch Bestimmung des Festkörpergehaltes oder gaschromatische Untersuchungen verfolgen läßt.The reaction product is then heated to 80 to 90 ° C. and held at this temperature for 1 to 3 hours. Since during this reaction & eit an increasing reflux distillation of the alcohol R1 - OH occurs is assumed that in this stage a ring closure to the dihydrourazil occurs. After this time is usually the alcohol formed in the formation of the dihydrouracil group R1-OH split off, which can be determined by determining the solids content or by gas chromatography Investigations.
Als Epoxidharze werden die handelsüblichen Diepoxidharze eingesetzt, wie sie durch Umsetzung von (Methyl)epichlorhydrin mit Bisphenolen, Phenolnovolaken,-Glykolen oder Dicarbonsäuren erhalten werden. Bevorzugt werden Diepoxidharze auf Basis von Bisphenol A mit Epoxidäquivalentgewichten von 180 bis etwa 2000 verwendet.Commercially available diepoxy resins are used as epoxy resins, as they do by reacting (methyl) epichlorohydrin with bisphenols, phenol novolaks, glycols or dicarboxylic acids can be obtained. Preference is given to diepoxy resins based on Bisphenol A with epoxy equivalent weights from 180 to about 2000 is used.
Für die Herstellung der Epoxid-Amin-Addukte werden die Epoxidharze in bekannter Weise mit aliphatischen, Aminen umgesetzt. Insbesonders kommen dabei Alkylamine, wie Diethylamin oder Diethylaminopropylamin bzw.Alkanolamine, wie Diethanolamin und dessen Homologe in Betracht.The epoxy resins are used for the production of the epoxy-amine adducts reacted in a known manner with aliphatic amines. Especially come with it Alkylamines such as diethylamine or diethylaminopropylamine or alkanolamines such as diethanolamine and its homologues into consideration.
Außerdem können, wie bekannt, auch primäre Mono- oder Diamine oder prim.-tert. Diamine zum Einsatz kommen.In addition, as is known, primary mono- or diamines or primary-tert. Diamines are used.
Die Epoxidharze bzw. die Epoxid-Amin-Addukte können gegebenenfalls auch zusätzlich nach anderen bekannten Verfahren, z. B. Umsetzung mit Monocarboxylverbindungen oder anderen Monoisocyanatverbindungen modifiziert werden.The epoxy resins or the epoxy-amine adducts can optionally also in addition by other known methods, e.g. B. Reaction with monocarboxyl compounds or other monoisocyanate compounds.
Die Verarbeitung der erfindungsgemäß hergestellten Produkte erfolgt in der üblichen Weise. Die Menge der zur Protonisierung notwendigen Säure beträgt etwa 25 bis 60 mMol pro 100 g Pestharz. Die Methoden zur Herstellung von KET-Lacken sowie deren Verarbeitung nach dem Elektrotauchlack-Lackierverfahren sind dem Pachmann bekannt und bedürfen keiner weiteren Erläuterung. Soferne die erfindungsgemäß hergestellten Produkte über eine entsprechende Menge freier Hydroxylgruppen verfügen, kann die Einbrenntemperatur bei Zusatz von Cobaltsalsen, vorsugsweise Cobaltoctoat bis auf 1400C (Einbrennzeit 20 Minuten) gesenkt werden. Im allgemeinen werden praxisgerechte Ergebnisse bei 170 bis 1900C erzielt.The products manufactured according to the invention are processed in the usual way. The amount of acid necessary for protonation is about 25 to 60 millimoles per 100 grams of plague resin. The methods of making KET varnishes as well as their processing according to the electrodeposition coating process are the Pachmann known and do not require any further explanation. Provided that they are produced according to the invention Products have a corresponding amount of free hydroxyl groups, the Stoving temperature when adding cobalt salsen, preferably cobalt octoate up to 1400C (burn-in time 20 minutes). In general, they are practical Results obtained at 170 to 1900C.
Das folgende Beispiel erläutert die Erfindung, ohne sie in ihrem Umfang zu beschränken. Alle Angaben in Teilen oder Prozenten beziehen sich, soferne nichts anderes angegeben ist, auf Gewichtseinheiten.The following example illustrates the invention without it in its scope to restrict. All data in parts or percentages relate unless nothing otherwise stated, based on weight units.
In einem mit Rührer, Rückflußkühler, Thermometer und Zugabegefäß ausgestatteten Reaktionsgefäß werden 130 Tle Diethylaminopropylamin langsam mit 128 Tlen n-Butylacrylat versetzt, wobei die Temperatur des Ansatzes durch Kühlung und Regulierung der Zugabegeschwindigkeit zwischen 30 und maximal 40eC gehalten wird. Nach Abklingen der exothermen Reaktion wird der Ansatz auf 750C erwärmt und 2 Stunden bei dieser Temperatur gehalten.In one equipped with a stirrer, reflux condenser, thermometer and addition vessel 130 parts of diethylaminopropylamine are slowly mixed with 128 parts of n-butyl acrylate in the reaction vessel offset, the temperature of the batch by cooling and regulating the rate of addition is kept between 30 and a maximum of 40eC. After the exothermic reaction has subsided the batch is heated to 750C and kept at this temperature for 2 hours.
In einem weiteren gleichartig ausgestatteten Reaktionsgefäß werden 174 Tle Toluylendiisocyanat (handelsübliches Isomerengemisch) in 185 Tlen Xylol gelöst und unter Kühlung bei maximal 250C innerhalb einer Stunde mit 258 Tlen des in der oben beschriebenen Weise hergestellten Vorproduktes zum Monoisocyanatvorprodukt umgesetzt.In another similarly equipped reaction vessel 174 parts of toluylene diisocyanate (commercial mixture of isomers) in 185 parts of xylene dissolved and with cooling at a maximum of 250C within one hour with 258 Tlen des precursor prepared in the manner described above to the monoisocyanate precursor implemented.
In einem weiteren mit Rührer, Thermometer, Rückflußkühler und Zugagegefäß ausgestatteten Reaktionsgefäß werden 1900 Tle eines Epoxidharzes auf Basis von Bisphenol A (EG 475) in 814 Tlen Diethylenglykoldimethylether gelöst und bei 650C mit 1234 Tlen des Monoisocyanatvorproduktes bis zu einem Isocyanatwert von praktisch 0 reagiert. Nach Zugabe von 129 Tlen Propylenglykolmonomethylether, 105 Tlen Diethanolamin und 195 Tlen Diethylaminopropylamin wird der Ansatz bei 65 bis 70-C-bis zur Umsetzung aller Epoxidgruppen reagiert. Dann wird die Temperatur auf 90-C erhöht und so lange gehalten, bis ein konstant bleibender Festkörpergehalt erreicht ist.In another with a stirrer, thermometer, reflux condenser and addition vessel equipped reaction vessel are 1900 parts of an epoxy resin based on bisphenol A (EG 475) dissolved in 814 parts of diethylene glycol dimethyl ether and at 650C with 1234 Part of the monoisocyanate precursor reacts to an isocyanate value of practically zero. After adding 129 parts of propylene glycol monomethyl ether, 105 parts of diethanolamine and 195 parts of diethylaminopropylamine are used at 65 to 70 ° C. until the reaction of all epoxy groups reacts. Then the temperature is increased to 90-C and so long held until a constant solids content is reached.
Nach dem Abkühlen wird das Produkt mit 50 Nillimol Ameisensäure () Rj versetzt und durch Verdünnen mit deionisiertem Wasser ein stabiler Klarlack hergestellt.After cooling, the product is treated with 50 nillimoles of formic acid () Rj is added and a stable clear coat is produced by diluting it with deionized water.
Das Produkt enthält 0,65 Mol Dihydrourazilgruppen pro 1000 g Bindemittel (Pestharz).The product contains 0.65 mol of dihydrouracil groups per 1000 g of binder (Plague resin).
FORMELSCHEMA
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT396884A AT380895B (en) | 1984-12-14 | 1984-12-14 | METHOD FOR PRODUCING KETL BINDERS BASED ON MODIFIED EPOXY RESINS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE3542569A1 true DE3542569A1 (en) | 1986-06-19 |
Family
ID=3557876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19853542569 Withdrawn DE3542569A1 (en) | 1984-12-14 | 1985-12-02 | Process for the preparation of cathodic electrodeposition coating binders based on modified epoxy resins |
Country Status (2)
| Country | Link |
|---|---|
| AT (1) | AT380895B (en) |
| DE (1) | DE3542569A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0292731A3 (en) * | 1987-05-18 | 1989-08-30 | Vianova Kunstharz Aktiengesellschaft | Cationic autocurable binder based on a urea modified epoxy resin and its preparation |
| EP0473548A3 (en) * | 1990-08-27 | 1992-10-21 | Ciba-Geigy Ag | Adducts from hydroxyl groups-containing epoxy resins and isocyanates and their use |
-
1984
- 1984-12-14 AT AT396884A patent/AT380895B/en not_active IP Right Cessation
-
1985
- 1985-12-02 DE DE19853542569 patent/DE3542569A1/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0292731A3 (en) * | 1987-05-18 | 1989-08-30 | Vianova Kunstharz Aktiengesellschaft | Cationic autocurable binder based on a urea modified epoxy resin and its preparation |
| EP0473548A3 (en) * | 1990-08-27 | 1992-10-21 | Ciba-Geigy Ag | Adducts from hydroxyl groups-containing epoxy resins and isocyanates and their use |
| US5272227A (en) * | 1990-08-27 | 1993-12-21 | Ciba-Geigy Corporation | Adducts of hydroxyl group containing epoxy resins and isocyanates and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| ATA396884A (en) | 1985-12-15 |
| AT380895B (en) | 1986-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE3644370A1 (en) | AMINOURETHANE, METHOD FOR THE PRODUCTION THEREOF FROM POLYAMINE AND THEIR USE | |
| EP0385293B1 (en) | Heat-curable coating composition for cathodic electrodeposition | |
| DE2707482A1 (en) | PROCESS FOR THE PRODUCTION OF BINDERS FOR ELECTRIC DIP PAINTING | |
| EP0288942A2 (en) | Process for the fabrication of cationic resins on the basis of epoxy resins modified by a phosphoric acid | |
| EP0093241B1 (en) | Self-cross-linking thermosetting binder | |
| EP0025555B1 (en) | Self-cross-linkable, heat-curable aqueous varnish-coating composition and its application to the cathodic electrodeposition on electro-conductive substrates | |
| EP0131038B1 (en) | Water dispersible binders for cationic electrophoretic lacquers and production method thereof | |
| EP0643111B1 (en) | Aqueous, solvent-free resin composition | |
| EP0227975B1 (en) | Method preparing self-crosslinking binders for cathodic electrocoating compositions | |
| CA1332993C (en) | Process for the preparation of pigment paste resins for cathodically depositable coating compositions | |
| DE3043479A1 (en) | METHOD FOR PRODUCING CATHODICALLY DEPOSITABLE BINDERS | |
| EP0249850A2 (en) | Self-cross-linking cationic varnish binders | |
| AT394372B (en) | METHOD FOR PRODUCING PIGMENT PASTE RESIN FOR CATHODICALLY DEPOSITABLE COATING COMPOSITIONS | |
| EP0030692B1 (en) | Process for the preparation of cathodically depositable binders | |
| EP0449072B1 (en) | Process for the preparation of cationic binders and their application | |
| EP0012963B1 (en) | Process for producing self-curing binding agents for cathodically electrodepositable enamels | |
| EP0010766B1 (en) | Heat-hardenable aqueous coating composition, application thereof to the electrodeposition and method for coating a conductive substrate by cathodic deposition | |
| EP0220440A1 (en) | Process for the preparation of self-curing cationic lacquer binders | |
| EP0292731B1 (en) | Cationic autocurable binder based on a urea modified epoxy resin and its preparation | |
| EP0305794A2 (en) | Process for the preparation of cationic paint binders | |
| EP0157102A1 (en) | Process for producing cathodically depositable paint binders | |
| EP0334284A2 (en) | Curing agents for synthetic resins, curable blends containing these and their use | |
| DE3542569A1 (en) | Process for the preparation of cathodic electrodeposition coating binders based on modified epoxy resins | |
| EP0267532A2 (en) | Method of making self-cross-linking cationic varnish binders | |
| EP0287052B1 (en) | Method of making self-cross-linking cationic paint binders containing biuret groups |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8139 | Disposal/non-payment of the annual fee |