CA2095570A1 - Polyfunctional epoxide compounds - Google Patents
Polyfunctional epoxide compoundsInfo
- Publication number
- CA2095570A1 CA2095570A1 CA 2095570 CA2095570A CA2095570A1 CA 2095570 A1 CA2095570 A1 CA 2095570A1 CA 2095570 CA2095570 CA 2095570 CA 2095570 A CA2095570 A CA 2095570A CA 2095570 A1 CA2095570 A1 CA 2095570A1
- Authority
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- Canada
- Prior art keywords
- compounds
- polyfunctional
- weight
- carbon atoms
- epoxide
- 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.)
- Abandoned
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1444—Monoalcohols
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/64—Amino alcohols
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Abstract
BASF Aktiengesellschaft 900175 O.Z. 0062/02119 Abstract of the Disclosure:
Polyfunctional epoxide compounds obtainable by reacting (A) polyfunctional aromatic amines, in which the amino groups carry more than two glycidyl groups per molecule, with quantities of (B) b1) an alkylphenol in which the alkyl radicals contain 1 to 12 carbon atoms, b2) a primary or secondary aliphatic amine in which the alkyl radicals contain 1 to 10 carbon atoms, or b3) an aliphatic C1-C20-alcohol or a mixture of two or more components (b1) to (b3), such that the reaction product carries on average two epox-ide groups per molecule can be reacted to form synthetic resins from which it is possible to prepare dispersions suitable for cathodic elec-trodeposition coating.
Polyfunctional epoxide compounds obtainable by reacting (A) polyfunctional aromatic amines, in which the amino groups carry more than two glycidyl groups per molecule, with quantities of (B) b1) an alkylphenol in which the alkyl radicals contain 1 to 12 carbon atoms, b2) a primary or secondary aliphatic amine in which the alkyl radicals contain 1 to 10 carbon atoms, or b3) an aliphatic C1-C20-alcohol or a mixture of two or more components (b1) to (b3), such that the reaction product carries on average two epox-ide groups per molecule can be reacted to form synthetic resins from which it is possible to prepare dispersions suitable for cathodic elec-trodeposition coating.
Description
sAsF Lacke + Farben AG gO0175 O.Z. 006~/02119 203~7~
Polyfunctional epoxide compounds l'he present invention relates to novel polyfunctional epox-ide compounds obtainable by reacting A) polyfunctional aromatic amines, in which the amino groups carry more than two glycidyl groups per molecule, with quantities of B) b1) an alkylphenol in which the alkyl radicals contain 1 to 12 carbon atoms, b2) a primary or secondary aliphatic amine in which the alkyl radicals contain 1 to 10 carbon atoms, or b3) an aliphatic C1-C20-alcohol or mixtures of two or more of components (bl) to ~b3), such that the reaction products carry on average two epoxide groups per molecu]e.
The invention also relat2s to the production of the poly-functional epoxide compounds. The invention also relates to synthetic resins which can be prepared from the novel epox-ide compounds, and to the preparation of these synthetic resins and to their use for heat-curable coating composi-tions. Finally the invention relates to electrodepositionbinder systems containing the abovementioned synthetic res-ins, to dispersions prepared from these resins, to a process for electrodeposition using these dispersions, and to ar-ticles coated using this process.
Coatings on metallic components in the automobile industry, which are applied by cathodic electrodeposition and are then heat-cured, are subject to a number of requirements. For instance, they should offer, inter alia, good protection ~0 against corrosion. They should in addition be sufficiently elastic to prevent the impact of stones leading directly to chipping of the coating.
sASF Lac~e + Farben AG 900175 O.Z. 0062/02119 2 20~a37~
lrhe coatings proposed in DE-A-35 42 168 contain as binders a polyaddition~polycondensation product carrying groups con-taining basic nitrogen. Such a product is prepared by react-ing an addition product built up Erom a secondary amine and polyepoxide compounds with a specific polyamide. In coating, this binder results in good protection against corrosion and is sufficiently elastic at ambient temperature to give ef-fectlve stone-chip protection. At lower temperatures, how-ever, the embrittlement of the coating results in inade~uate protection against stone-chipping.
It is therefore an object of the present invention to pro-vide binders for electrodeposition coating which give good protection against corrosion and which remain elastic at low temperatures so as to be insensitive to stone-chipping.
We have found that this object is achieved by the polyEunc-tional epoxide compounds defined above.
We have also found a process for their preparation, syn-thetic resins containing these epoxide compounds, and a pro-cess for preparing these synthetic resins. We have addition-ally found binder systems which are suitable for electrode-position coating and which contain these synthetic resins, dispersions prepared from these binder systems, a process for electrodeposition coating using these dispersions, and articles coated by this process.
The following text describes particularly advantageous em-bodiments for the application of the polyfunctional epoxide compounds in electrodeposition coating.
Component A
The compounds suitable as component (A) are derived from polyfunctional aromatic amines which generally carry 2 amino groups per molecule. Suitable compounds for this purpose are therefore 9,10-diaminoanthracene, 2,2-bis-(4-aminophenyl)propane, ~0 4,4'-diaminobenzophenone, 1,2-bis-(4-aminophenyl)ethane, sASF Lacke + Farbe~ AG 900175 O.Z. 0062/02119 3 2095~70 bis-(2 aminonaphthyl~methane and 1,5-diaminonaphthalene, and preferably 4,4'-diaminodiphenylmethane.
These polyfunctional aromatic compounds are reacted with an epihalohydrin by a known method (cE. eg. EP-A-0 lS5 238~ to give products carrying more than 2, preferably 3 to 4 and paLticularly preferably on average 3.5 to 4 glycidyl groups per rrlolecule. 5Ome of these products are also commercially available.
Component B
Component (A) is reacted with compounds which are reactive toward epoxide groups. Suitable examples are:
bl) Alkylphenols, in which the alkyl radicals contain 1 to 12 carbon atoms.
PreEerence is given to monoalkylphenols containing 4 to 12 carbon atoms in the alkyl radical. 4-Nonylphenol and 4-dodecylphenol are particularly preferred.
b~) Primary or secondary aliphatic amines in which the alkyl radicals contain 1 to 10 carbon atoms.
It is preferred to use secondary amines. The alkyl radi-cals preferably contain 3 to 6 carbons. Diiso-propyla-mine, di-n-propylamine, di-n-butylamine, dipentylamine and dihexylamine are particularly preferred.
b3) Aliphatic Cl-C20-alcohols.
Methanol, ethanol, iso-propanol, n-propanol, iso-butanol and n-butanol are preferred.
It is also possible to employ mixtures of components (bl) to (b-,) as component (B).
Components (A) and (B) are mixed and expediently heated to from 100 to 160"C. It is often advantageous here to carry out the reaction in a polar solvent such as ethylene gIycol monobutyl ether or propylene glycol monophenyl ether, the BASF ~acke + Farbe~ AG 900175 O.Z. 0062J02119 2~9~7a solvent generally making up from 5 to 30% by weight of the mixture. In the presence of component (B) there is only a minor degree of reaction between component (A) and one of the hydroxyl-containing solvents mentioned.
The reactio~ of (A) and (B) is advantageously carried out in the presence of a catalyst, such as a tertiary amine and preferably an aliphatic tertiary amine, such as tributyla-mine or diethylhe~ylamine. Depending on the number oE
glycidyl groups in (A), the quantities of (B) are chosen such that the reaction product carries on average two epox-ide groups per molecule.
Component C
~5 The polyfunctional epoxide compounds prepared from compo-nents (A) and (B) can be reacted to give synthetic resins.
This is effected by reaction with component (C), which com-prises the following individual compounds:
cl) Polyalkylene oxides having an average molecular weight from 200 to 2000.
These are preferably polymers of ethylene oxide, 1,2-propylene oxide, 1,3-propylene oxide or tetrahydro-furan. Both homopolymers and copolymers of these compounds can be used. Polytetrahydrofuran having an av-erage molecular weight from 300 to 1000 is particularly preferred.
C!) Polyalkylene oxides having terminal amino groups and an average molecular weight from 200 to 2000.
These compounds are also derived from cyclic ethers such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene ox-ide and tetrahydrofuran, the terminal groups being con-verted to amino groups after polymerization by a known method. Poly(tetrahydrofuran)diamines having an average molecular weight from 250 bis 750 are particularly pre-ferred.
BA~F hacke ~ Farben AG 900175 O.Z. 0062/02119 5 2 ~ 9 ~ ~ 7 0 C3 ) Aliphatic amino-alcohols having a total of 2 to 12 car-bons.
Suitable compounds are those containing primary and sec-ondary amino groups, such as ethanolamine or methyletha-nolamine, but it is also possible to employ compounds with tertiary amino groups, such as dimethylamino-propanol or triethanolamine.
c~) Bisphenols.
Suitable bisphenols are compounds such as 4,4'-dihydroxybenzophenone, 4,4'-dihydroxyphenyl sulfone, 1,1-bis(4--hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)isobutane, 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane, Bis(4-hydroxynaphthyl)methane, 1,5-dihydroxynaphthalene or preferably 2,2-bis(4-hydroxyphenyl)propane ( Bi sphenol A).
It is also possible to use mixtures of components (c1) to (C4 ) . A further possibility is to react various components (C) in succession with polyfunctional epoxide compounds com-prising (A) and (B). The function of component (C) is to link the polyfunctional epoxide compounds to form a syn-thetic resin.
The epoxides prepared from components (A) and (B) can be reacted directly to give the synthetic resins. For this pur-pose it is usual first to neutralize the amine catalyst -when present - with an acid. Component (C) is then added, a catalyst such as triphenylphosphine may be added, as is the case when using bisphenols, and the mixture is heated to about 100 to 160C, until all the epoxide groups have reacted. It has proven advantageous to carry out this reaction in a solvent, since the mixture becomes more vis-cous during the reaction. Suitable solvents in this case are ethylene glycol monobutyl ether or propylene glycol mono-phenyl ether.
BASF Lack0 ~ Farben AG 900175 O.Z. 0062/02119 2~9~0 The resulting synthetic resins form a constituent of binder systems which can be used for electrodeposition coating.
These binder systems contain from 50 to 95% by weight, pre-ferably 50 to 75~ by weight, of the synthetic resins. They also comprise a crosslinking agent D in amounts from 5 to 50, and preferably 25 to 50~ by weight.
Crosslinking agent D
~0 The crosslinking agents D, which are known per se, are compounds which are able to efEect crosslinking by various types of reaction. The following classes of compound are preferred in this context:
dl) amidation crosslinkers, d2) transamination crosslinkers, d3) transesterification crosslinkers and d4) blocked polyisocyanates.
dl) Amidation crosslinkers are those organic compounds which react with primary and/or secondary amino groups in the synthetic resin to form amide lin]cs, this reaction only taking place under stoving conditions. Examples of these are resins containing at least two carboalkoxymethyl groups and having an average molecular weight from 200 to 10,000, whose structure is described in DE-A-31 45 714.
d~`) Transamination crosslinkers are organic compounds which likewise react with primary and/or secondary amino groups in the synthetic resin under stoving conditions, with elimination of amine, so that crosslinking agent and synthetic resin are linked by these groups. Examples are Mannich bases which are built up from phenols, form-aldehyde and secondary amines. Particular preference is given to those compounds which are built up from polyal-kylene oxide diglycidyl ethers with phenols such as bis-phenol A, and are then reacted with dialkylamines such as dimethylamine, diethylamine, or piperidine and with-formaldehyde or formaldehyde-donor compounds.
BASF Lacke ~ Fa~ben AG 900175 O. æ . 0062/0211g 7 2~9~57Q
d-~ Transesterification crosslinkers can undergo transes-terification reactions with synthetic resins containing hydroxyl groups. Examples are resins comprising acrylic acid esters, or resins containing malonic ester groups, S which are described in DE-A-37 35 601.
d,1) Polyisocyanates are particularly preferred. Examples of these compounds are tolylene diisocyanate, 4,~'-diphenylmethane diisocyanate, isophorone diiso-cyanate and trimerized hexamethylene diisocyanate. These isocyanates are preferably employed in blocked form.
Customary blocking agents are amines such as dibutyla-mine, which react to give urea compounds, alcohols such as methanol, ethanol or polyhydric alcohols such as polyoxyalkylene glycols, which form urethane groups, and ketoximes such as methyl ethyl ketoxime, which likewise react bY addition to an isocyanate group.
The binders according to the invention are dispersible in water after partial or complete neutrali2ation. Acids suit-able for the neutralization are preferably carboxylic acids such as formic acid, acetic acid, propionic acid or lactic acid, but also include inorganic acids such as phosphoric acid. The neutrali~ation of the synthetic resin and the crosslinking agent can be carried out separately, but is preferably carried out in unison after prior mixing. The re-sulting dispersions can be diluted with water, possibly af-ter removing organic solvent, to a desired solids content.
For preparing electrodeposition baths the binders accordlng to the invention can be admixed with further binders, pig-ments and auxiliaries and additives conventional in electro-deposition coating, such as fillers, corrosion inhibitors, dispersion auxiliaries, antifoams and/or solvents.
Electrodeposition coating is carried out by a conventional procedure.
BASF Lacke ~ Farben AG 900175 O.Z. 006~02119 209~70 The binders according to the invention afford, after ca-thodic deposition and heat-curing, a good protection against corrosion on metallic components. They also have - even at ]ow temperatures - only a slight sensitivity toward stone-chipping.
The po:Lyfunctional epoxide compounds according to the inven-tion are of interest as components of epoxy resins. Novel binders prepared therefrom find application as heat-curable coatings.
Examples 1.1 Preparation of a polyfunctional epoxide compound ac-cording to the invention 3.08 kg of a polyglycidyl ether based on 4,4'-diaminodiphenylmethane (epoxide equivalent weight 7'7; average number of epoxide groups per mole-cule 3.8) in 760 g of ethylene glycol monobutyl ether were mixed with 1100 g (5 mol) of 4-nonylphenol and 3.35 g of diethylhexylamine and heated at 130C until the epoxide equivalent weight was 385.
1.2 Preparation of a synthetic resin ~ according to the invention After addition of 6.35 g of concentrated formic acid to the reaction mixture obtained in 1.1, 513 g (2.25 mol) of bisphenol A and 1.10 g of triphenyl phosphine in 110 g of ethylene glycol monobutyl ether were added. The temperature was maintained at 130C until the epoxide equivalent weight was 650. At 70C 300 g of polytetrahydrofurandiamine having an average mo-lecular weight of 600 and 165 g (1.58 mol) of dimethylaminopropanol were added. The mixture was maintained at this temperature until no further epox-ide groups could be detected.
The resin solution at a solids content of 85~ by weight had a viscosity of 4400 mPas at 75C.
sAsF Lacke ~ Fa~ben ~G 900175 O.Z. 0062/02119 2~95570 1.3 Preparation of a com~arative synthetic resin Rc (ac-cording to DE-A-35 42 168) 3.06 kg (3.15 mol) of a diglycidyl ether based on S bisphenol A and eplchlorohydrin (epoxide eq~livalent weight 485) in 570 g of toluene and 534 g of iso-butanol are mixed at 65"C with 135 g (1.8 mol) of me-thylethanolamine. When the mixture had reached an epoxide equivalent weight of 835, 656 g of a solution of a condensation product and 140 g of toluene were added, and the mixture was heated for 2 h at 80C.
The condensation product was prepared by reacting 290 g (2.5 mol) of hexamethylenediamine, 218 g (0.39 mol) of dimerized fatty acid and 70 g (0.25 mol) of linseed oil fatty acid at 195C, distilling off the water oE reaction. After addition of 242 g of toluene this solution had a solids content of 70% by weight and an amine nurnber of 350 mg/g.
2. Preparation of crosslinking agents 2.1 Crosslinking agent D1 (according to Example 1 of EP-A-304 834) 425 g of polyoxypropylene glycol having an average molecular weight of 425 at 60C were added to 696 g (4 mol) of toluylene diisocyanate`(80% by weight of the 2,4- and 20 ~ by weight of the 2,6-isomer) and 2.8 g of dibutyltin dilaurate as catalyst. 522 g (6 mol) of methyl ethyl ketoximP were then added to the mixture which was maintained at 60C until no further free isocyanate groùps could be detected.
2.2 Crosslinking agent D2 5.04 kg (10 rnol) of trimerized hexamethylene diiso-cyanate in 3.80 kg of methyl isobutyl ketone were reacted at 70C with 3.88 kg (30 mol) of dibutylamine until no further free isocyanate groups could be de-tected.
B~SF ~acke ~ Farben AG 900175O.Z. 0062/02119 209~370 3. Preparation of dispersions 3.1 Preparation of dispersions of R
3.1.1 Example 1 780 g of R were mixed with 340 g of Dl and neutral-ized with 19.5 g of acetic acid. The organic solvents were removed by azeotropic distillation and the dis-persion was adjusted to a solids content of 35% by weight with water.
3.1.2 Example 2 Procedure as for 3.1.1; 780 g of R, 485 g of D2 3.2 Preparation of a dispersion of Rc (Comparative exam-ple) ~0 Procedure as for 3.1; 695 g of Rc; 298 g of D2; neu-tralization with 16 g of acetic acid 4. Preparation of a pigment paste 580 g of diglycidyl ether based on bisphenol and epichlorohydrin (epoxide equivalent weight 485) and 145 g of a similar diglycidyl ether having an epoxide equivalent weight of 188 were added at 100C to 452 g (3.9 mol) of hexamethylenediamine. After 30 minutes the excess diamine was stripped off at 200C and 30 mbar. Then 57.6 g (0.2 mol) of stearic acid and 173 g (0.3 mol) of dimeric fatty acid in 115 g of xylene were added. The water of reaction which formed was removed by azeotropic distillation at 175C. After addition of 58 g of ethylene glycol monobutyl ether and 322 g of isobutanol the reaction solution had a solids content of 7Q% by weight and a viscosity of 2240 mPas at 75 C. 110 g of this resin solution were milled in a ball mill with 36 g of ethylene glycol monobutyl ether, 3 g of acetic acid, 170 g of tita-nlum diox~:e, ~ g of lead sili~aee, 4.5 g ^f carbon .
sASF Lacke + Farben AG 900175 O.Z. 9062/02119 20g3~70 black and 170 g oE water to a particle size of below 7 ~Im.
5. Electrodeposition coating and measurement data 19~2 g of dispersion and 69~ g of pigmerlt paste were mixed and adjusted to a solids content of 20% by weight with water.
At ambient temperature, coatings were applied by de-position at 250 to 500 V in conventional manner to phosphatized metal panels connected as cathode, and the coatings were cured for 20 minutes at a panel temperature of 165C.
Stone chip test ~in accordance with DIN 55 995, Method A) At -20C a coated metal sample panel was struck with 5 blows of a hammer at different points. The parameters measured were:
1. The area of coating chipped off, in mm2 2. The number of blows which exposed the panel.
This nu~ber is an indirect measurement of how deeply the coating is damaged by stone-chipping, and how often cor-rosion sites can form on a panel attacked in this way.
Chipping [mm~] Number of blows _____ which exp sed the Example 1 6 2 (as in 3.1.1) 35 Example 2 5 1 (as in 3.1.2) _ _ _ Comparative exam- 10 5 (as in 3.2) _ _ ~ASF Lacke ~ ~a~en ~G 900175 O.Z. 0062/02119 ~2 2 ~ 9 ~ ~ 7 0 We claim:
l. A polyfunctional epoxide compound which can be obtained by reacting A) a polyfunctional aromatic amine, in which the amino ~roups carry more than two glycidyl groups per mol-ecule, with ~1antities of B) b1) an alkylphenol in which the alkyl radicals con-tain 1 to 12 carbon atoms, b2) a primary or secondary aliphatic amine in which the alkyl radicals contain 1 to 10 carbon atoms, or b3) an aliphatic Cl-C20-alcohol or a mixture of two or more of components (b1) to (b3), such that the reaction product carries on average two epoxide groups per molecule~
2. A polyfunctional epoxide compound as claimed in claim 1, in which component (A) is N,N,N',N'-tetra-glycidyl-4,4'-diaminodiphenylmethane.
3. A process for the preparation of a polyfunctional epox-ide cornpound as claimed in claim l, which cornprises reacting A) a polyfunctional aromatic amine, in which the amino groups carry more than two glycidyl groups per mol-ecule, with c~uantities of B) b1) an alkylphenol in which the alkyl radicals con-tain 1 to 12 carbon atoms,
Polyfunctional epoxide compounds l'he present invention relates to novel polyfunctional epox-ide compounds obtainable by reacting A) polyfunctional aromatic amines, in which the amino groups carry more than two glycidyl groups per molecule, with quantities of B) b1) an alkylphenol in which the alkyl radicals contain 1 to 12 carbon atoms, b2) a primary or secondary aliphatic amine in which the alkyl radicals contain 1 to 10 carbon atoms, or b3) an aliphatic C1-C20-alcohol or mixtures of two or more of components (bl) to ~b3), such that the reaction products carry on average two epoxide groups per molecu]e.
The invention also relat2s to the production of the poly-functional epoxide compounds. The invention also relates to synthetic resins which can be prepared from the novel epox-ide compounds, and to the preparation of these synthetic resins and to their use for heat-curable coating composi-tions. Finally the invention relates to electrodepositionbinder systems containing the abovementioned synthetic res-ins, to dispersions prepared from these resins, to a process for electrodeposition using these dispersions, and to ar-ticles coated using this process.
Coatings on metallic components in the automobile industry, which are applied by cathodic electrodeposition and are then heat-cured, are subject to a number of requirements. For instance, they should offer, inter alia, good protection ~0 against corrosion. They should in addition be sufficiently elastic to prevent the impact of stones leading directly to chipping of the coating.
sASF Lac~e + Farben AG 900175 O.Z. 0062/02119 2 20~a37~
lrhe coatings proposed in DE-A-35 42 168 contain as binders a polyaddition~polycondensation product carrying groups con-taining basic nitrogen. Such a product is prepared by react-ing an addition product built up Erom a secondary amine and polyepoxide compounds with a specific polyamide. In coating, this binder results in good protection against corrosion and is sufficiently elastic at ambient temperature to give ef-fectlve stone-chip protection. At lower temperatures, how-ever, the embrittlement of the coating results in inade~uate protection against stone-chipping.
It is therefore an object of the present invention to pro-vide binders for electrodeposition coating which give good protection against corrosion and which remain elastic at low temperatures so as to be insensitive to stone-chipping.
We have found that this object is achieved by the polyEunc-tional epoxide compounds defined above.
We have also found a process for their preparation, syn-thetic resins containing these epoxide compounds, and a pro-cess for preparing these synthetic resins. We have addition-ally found binder systems which are suitable for electrode-position coating and which contain these synthetic resins, dispersions prepared from these binder systems, a process for electrodeposition coating using these dispersions, and articles coated by this process.
The following text describes particularly advantageous em-bodiments for the application of the polyfunctional epoxide compounds in electrodeposition coating.
Component A
The compounds suitable as component (A) are derived from polyfunctional aromatic amines which generally carry 2 amino groups per molecule. Suitable compounds for this purpose are therefore 9,10-diaminoanthracene, 2,2-bis-(4-aminophenyl)propane, ~0 4,4'-diaminobenzophenone, 1,2-bis-(4-aminophenyl)ethane, sASF Lacke + Farbe~ AG 900175 O.Z. 0062/02119 3 2095~70 bis-(2 aminonaphthyl~methane and 1,5-diaminonaphthalene, and preferably 4,4'-diaminodiphenylmethane.
These polyfunctional aromatic compounds are reacted with an epihalohydrin by a known method (cE. eg. EP-A-0 lS5 238~ to give products carrying more than 2, preferably 3 to 4 and paLticularly preferably on average 3.5 to 4 glycidyl groups per rrlolecule. 5Ome of these products are also commercially available.
Component B
Component (A) is reacted with compounds which are reactive toward epoxide groups. Suitable examples are:
bl) Alkylphenols, in which the alkyl radicals contain 1 to 12 carbon atoms.
PreEerence is given to monoalkylphenols containing 4 to 12 carbon atoms in the alkyl radical. 4-Nonylphenol and 4-dodecylphenol are particularly preferred.
b~) Primary or secondary aliphatic amines in which the alkyl radicals contain 1 to 10 carbon atoms.
It is preferred to use secondary amines. The alkyl radi-cals preferably contain 3 to 6 carbons. Diiso-propyla-mine, di-n-propylamine, di-n-butylamine, dipentylamine and dihexylamine are particularly preferred.
b3) Aliphatic Cl-C20-alcohols.
Methanol, ethanol, iso-propanol, n-propanol, iso-butanol and n-butanol are preferred.
It is also possible to employ mixtures of components (bl) to (b-,) as component (B).
Components (A) and (B) are mixed and expediently heated to from 100 to 160"C. It is often advantageous here to carry out the reaction in a polar solvent such as ethylene gIycol monobutyl ether or propylene glycol monophenyl ether, the BASF ~acke + Farbe~ AG 900175 O.Z. 0062J02119 2~9~7a solvent generally making up from 5 to 30% by weight of the mixture. In the presence of component (B) there is only a minor degree of reaction between component (A) and one of the hydroxyl-containing solvents mentioned.
The reactio~ of (A) and (B) is advantageously carried out in the presence of a catalyst, such as a tertiary amine and preferably an aliphatic tertiary amine, such as tributyla-mine or diethylhe~ylamine. Depending on the number oE
glycidyl groups in (A), the quantities of (B) are chosen such that the reaction product carries on average two epox-ide groups per molecule.
Component C
~5 The polyfunctional epoxide compounds prepared from compo-nents (A) and (B) can be reacted to give synthetic resins.
This is effected by reaction with component (C), which com-prises the following individual compounds:
cl) Polyalkylene oxides having an average molecular weight from 200 to 2000.
These are preferably polymers of ethylene oxide, 1,2-propylene oxide, 1,3-propylene oxide or tetrahydro-furan. Both homopolymers and copolymers of these compounds can be used. Polytetrahydrofuran having an av-erage molecular weight from 300 to 1000 is particularly preferred.
C!) Polyalkylene oxides having terminal amino groups and an average molecular weight from 200 to 2000.
These compounds are also derived from cyclic ethers such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene ox-ide and tetrahydrofuran, the terminal groups being con-verted to amino groups after polymerization by a known method. Poly(tetrahydrofuran)diamines having an average molecular weight from 250 bis 750 are particularly pre-ferred.
BA~F hacke ~ Farben AG 900175 O.Z. 0062/02119 5 2 ~ 9 ~ ~ 7 0 C3 ) Aliphatic amino-alcohols having a total of 2 to 12 car-bons.
Suitable compounds are those containing primary and sec-ondary amino groups, such as ethanolamine or methyletha-nolamine, but it is also possible to employ compounds with tertiary amino groups, such as dimethylamino-propanol or triethanolamine.
c~) Bisphenols.
Suitable bisphenols are compounds such as 4,4'-dihydroxybenzophenone, 4,4'-dihydroxyphenyl sulfone, 1,1-bis(4--hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)isobutane, 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane, Bis(4-hydroxynaphthyl)methane, 1,5-dihydroxynaphthalene or preferably 2,2-bis(4-hydroxyphenyl)propane ( Bi sphenol A).
It is also possible to use mixtures of components (c1) to (C4 ) . A further possibility is to react various components (C) in succession with polyfunctional epoxide compounds com-prising (A) and (B). The function of component (C) is to link the polyfunctional epoxide compounds to form a syn-thetic resin.
The epoxides prepared from components (A) and (B) can be reacted directly to give the synthetic resins. For this pur-pose it is usual first to neutralize the amine catalyst -when present - with an acid. Component (C) is then added, a catalyst such as triphenylphosphine may be added, as is the case when using bisphenols, and the mixture is heated to about 100 to 160C, until all the epoxide groups have reacted. It has proven advantageous to carry out this reaction in a solvent, since the mixture becomes more vis-cous during the reaction. Suitable solvents in this case are ethylene glycol monobutyl ether or propylene glycol mono-phenyl ether.
BASF Lack0 ~ Farben AG 900175 O.Z. 0062/02119 2~9~0 The resulting synthetic resins form a constituent of binder systems which can be used for electrodeposition coating.
These binder systems contain from 50 to 95% by weight, pre-ferably 50 to 75~ by weight, of the synthetic resins. They also comprise a crosslinking agent D in amounts from 5 to 50, and preferably 25 to 50~ by weight.
Crosslinking agent D
~0 The crosslinking agents D, which are known per se, are compounds which are able to efEect crosslinking by various types of reaction. The following classes of compound are preferred in this context:
dl) amidation crosslinkers, d2) transamination crosslinkers, d3) transesterification crosslinkers and d4) blocked polyisocyanates.
dl) Amidation crosslinkers are those organic compounds which react with primary and/or secondary amino groups in the synthetic resin to form amide lin]cs, this reaction only taking place under stoving conditions. Examples of these are resins containing at least two carboalkoxymethyl groups and having an average molecular weight from 200 to 10,000, whose structure is described in DE-A-31 45 714.
d~`) Transamination crosslinkers are organic compounds which likewise react with primary and/or secondary amino groups in the synthetic resin under stoving conditions, with elimination of amine, so that crosslinking agent and synthetic resin are linked by these groups. Examples are Mannich bases which are built up from phenols, form-aldehyde and secondary amines. Particular preference is given to those compounds which are built up from polyal-kylene oxide diglycidyl ethers with phenols such as bis-phenol A, and are then reacted with dialkylamines such as dimethylamine, diethylamine, or piperidine and with-formaldehyde or formaldehyde-donor compounds.
BASF Lacke ~ Fa~ben AG 900175 O. æ . 0062/0211g 7 2~9~57Q
d-~ Transesterification crosslinkers can undergo transes-terification reactions with synthetic resins containing hydroxyl groups. Examples are resins comprising acrylic acid esters, or resins containing malonic ester groups, S which are described in DE-A-37 35 601.
d,1) Polyisocyanates are particularly preferred. Examples of these compounds are tolylene diisocyanate, 4,~'-diphenylmethane diisocyanate, isophorone diiso-cyanate and trimerized hexamethylene diisocyanate. These isocyanates are preferably employed in blocked form.
Customary blocking agents are amines such as dibutyla-mine, which react to give urea compounds, alcohols such as methanol, ethanol or polyhydric alcohols such as polyoxyalkylene glycols, which form urethane groups, and ketoximes such as methyl ethyl ketoxime, which likewise react bY addition to an isocyanate group.
The binders according to the invention are dispersible in water after partial or complete neutrali2ation. Acids suit-able for the neutralization are preferably carboxylic acids such as formic acid, acetic acid, propionic acid or lactic acid, but also include inorganic acids such as phosphoric acid. The neutrali~ation of the synthetic resin and the crosslinking agent can be carried out separately, but is preferably carried out in unison after prior mixing. The re-sulting dispersions can be diluted with water, possibly af-ter removing organic solvent, to a desired solids content.
For preparing electrodeposition baths the binders accordlng to the invention can be admixed with further binders, pig-ments and auxiliaries and additives conventional in electro-deposition coating, such as fillers, corrosion inhibitors, dispersion auxiliaries, antifoams and/or solvents.
Electrodeposition coating is carried out by a conventional procedure.
BASF Lacke ~ Farben AG 900175 O.Z. 006~02119 209~70 The binders according to the invention afford, after ca-thodic deposition and heat-curing, a good protection against corrosion on metallic components. They also have - even at ]ow temperatures - only a slight sensitivity toward stone-chipping.
The po:Lyfunctional epoxide compounds according to the inven-tion are of interest as components of epoxy resins. Novel binders prepared therefrom find application as heat-curable coatings.
Examples 1.1 Preparation of a polyfunctional epoxide compound ac-cording to the invention 3.08 kg of a polyglycidyl ether based on 4,4'-diaminodiphenylmethane (epoxide equivalent weight 7'7; average number of epoxide groups per mole-cule 3.8) in 760 g of ethylene glycol monobutyl ether were mixed with 1100 g (5 mol) of 4-nonylphenol and 3.35 g of diethylhexylamine and heated at 130C until the epoxide equivalent weight was 385.
1.2 Preparation of a synthetic resin ~ according to the invention After addition of 6.35 g of concentrated formic acid to the reaction mixture obtained in 1.1, 513 g (2.25 mol) of bisphenol A and 1.10 g of triphenyl phosphine in 110 g of ethylene glycol monobutyl ether were added. The temperature was maintained at 130C until the epoxide equivalent weight was 650. At 70C 300 g of polytetrahydrofurandiamine having an average mo-lecular weight of 600 and 165 g (1.58 mol) of dimethylaminopropanol were added. The mixture was maintained at this temperature until no further epox-ide groups could be detected.
The resin solution at a solids content of 85~ by weight had a viscosity of 4400 mPas at 75C.
sAsF Lacke ~ Fa~ben ~G 900175 O.Z. 0062/02119 2~95570 1.3 Preparation of a com~arative synthetic resin Rc (ac-cording to DE-A-35 42 168) 3.06 kg (3.15 mol) of a diglycidyl ether based on S bisphenol A and eplchlorohydrin (epoxide eq~livalent weight 485) in 570 g of toluene and 534 g of iso-butanol are mixed at 65"C with 135 g (1.8 mol) of me-thylethanolamine. When the mixture had reached an epoxide equivalent weight of 835, 656 g of a solution of a condensation product and 140 g of toluene were added, and the mixture was heated for 2 h at 80C.
The condensation product was prepared by reacting 290 g (2.5 mol) of hexamethylenediamine, 218 g (0.39 mol) of dimerized fatty acid and 70 g (0.25 mol) of linseed oil fatty acid at 195C, distilling off the water oE reaction. After addition of 242 g of toluene this solution had a solids content of 70% by weight and an amine nurnber of 350 mg/g.
2. Preparation of crosslinking agents 2.1 Crosslinking agent D1 (according to Example 1 of EP-A-304 834) 425 g of polyoxypropylene glycol having an average molecular weight of 425 at 60C were added to 696 g (4 mol) of toluylene diisocyanate`(80% by weight of the 2,4- and 20 ~ by weight of the 2,6-isomer) and 2.8 g of dibutyltin dilaurate as catalyst. 522 g (6 mol) of methyl ethyl ketoximP were then added to the mixture which was maintained at 60C until no further free isocyanate groùps could be detected.
2.2 Crosslinking agent D2 5.04 kg (10 rnol) of trimerized hexamethylene diiso-cyanate in 3.80 kg of methyl isobutyl ketone were reacted at 70C with 3.88 kg (30 mol) of dibutylamine until no further free isocyanate groups could be de-tected.
B~SF ~acke ~ Farben AG 900175O.Z. 0062/02119 209~370 3. Preparation of dispersions 3.1 Preparation of dispersions of R
3.1.1 Example 1 780 g of R were mixed with 340 g of Dl and neutral-ized with 19.5 g of acetic acid. The organic solvents were removed by azeotropic distillation and the dis-persion was adjusted to a solids content of 35% by weight with water.
3.1.2 Example 2 Procedure as for 3.1.1; 780 g of R, 485 g of D2 3.2 Preparation of a dispersion of Rc (Comparative exam-ple) ~0 Procedure as for 3.1; 695 g of Rc; 298 g of D2; neu-tralization with 16 g of acetic acid 4. Preparation of a pigment paste 580 g of diglycidyl ether based on bisphenol and epichlorohydrin (epoxide equivalent weight 485) and 145 g of a similar diglycidyl ether having an epoxide equivalent weight of 188 were added at 100C to 452 g (3.9 mol) of hexamethylenediamine. After 30 minutes the excess diamine was stripped off at 200C and 30 mbar. Then 57.6 g (0.2 mol) of stearic acid and 173 g (0.3 mol) of dimeric fatty acid in 115 g of xylene were added. The water of reaction which formed was removed by azeotropic distillation at 175C. After addition of 58 g of ethylene glycol monobutyl ether and 322 g of isobutanol the reaction solution had a solids content of 7Q% by weight and a viscosity of 2240 mPas at 75 C. 110 g of this resin solution were milled in a ball mill with 36 g of ethylene glycol monobutyl ether, 3 g of acetic acid, 170 g of tita-nlum diox~:e, ~ g of lead sili~aee, 4.5 g ^f carbon .
sASF Lacke + Farben AG 900175 O.Z. 9062/02119 20g3~70 black and 170 g oE water to a particle size of below 7 ~Im.
5. Electrodeposition coating and measurement data 19~2 g of dispersion and 69~ g of pigmerlt paste were mixed and adjusted to a solids content of 20% by weight with water.
At ambient temperature, coatings were applied by de-position at 250 to 500 V in conventional manner to phosphatized metal panels connected as cathode, and the coatings were cured for 20 minutes at a panel temperature of 165C.
Stone chip test ~in accordance with DIN 55 995, Method A) At -20C a coated metal sample panel was struck with 5 blows of a hammer at different points. The parameters measured were:
1. The area of coating chipped off, in mm2 2. The number of blows which exposed the panel.
This nu~ber is an indirect measurement of how deeply the coating is damaged by stone-chipping, and how often cor-rosion sites can form on a panel attacked in this way.
Chipping [mm~] Number of blows _____ which exp sed the Example 1 6 2 (as in 3.1.1) 35 Example 2 5 1 (as in 3.1.2) _ _ _ Comparative exam- 10 5 (as in 3.2) _ _ ~ASF Lacke ~ ~a~en ~G 900175 O.Z. 0062/02119 ~2 2 ~ 9 ~ ~ 7 0 We claim:
l. A polyfunctional epoxide compound which can be obtained by reacting A) a polyfunctional aromatic amine, in which the amino ~roups carry more than two glycidyl groups per mol-ecule, with ~1antities of B) b1) an alkylphenol in which the alkyl radicals con-tain 1 to 12 carbon atoms, b2) a primary or secondary aliphatic amine in which the alkyl radicals contain 1 to 10 carbon atoms, or b3) an aliphatic Cl-C20-alcohol or a mixture of two or more of components (b1) to (b3), such that the reaction product carries on average two epoxide groups per molecule~
2. A polyfunctional epoxide compound as claimed in claim 1, in which component (A) is N,N,N',N'-tetra-glycidyl-4,4'-diaminodiphenylmethane.
3. A process for the preparation of a polyfunctional epox-ide cornpound as claimed in claim l, which cornprises reacting A) a polyfunctional aromatic amine, in which the amino groups carry more than two glycidyl groups per mol-ecule, with c~uantities of B) b1) an alkylphenol in which the alkyl radicals con-tain 1 to 12 carbon atoms,
Claims (2)
1. 50 to 95% by weight of a synthetic resin as claimed in claim 4 and
2. 5 to 50% by weight of a crosslinking agent.
8. An aqueous dispersion which can be used directly for ca-thodic electrodeposition coating, comprising a binder system as claimed in claim 7.
9. A process for cathodic electrodeposition coating, which comprises using a dispersion as claimed in claim 8 in a conventional manner.
10. The use of an aqueous dispersion as claimed in claim 8 for cathodic electrodeposition coating.
11. An article coated by cathodic electrodeposition, obtain-able by the process as claimed in claim 9.
8. An aqueous dispersion which can be used directly for ca-thodic electrodeposition coating, comprising a binder system as claimed in claim 7.
9. A process for cathodic electrodeposition coating, which comprises using a dispersion as claimed in claim 8 in a conventional manner.
10. The use of an aqueous dispersion as claimed in claim 8 for cathodic electrodeposition coating.
11. An article coated by cathodic electrodeposition, obtain-able by the process as claimed in claim 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19924214964 DE4214964A1 (en) | 1992-05-06 | 1992-05-06 | Polyvalent epoxy compounds |
| DEP4214964.9 | 1992-05-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2095570A1 true CA2095570A1 (en) | 1993-11-07 |
Family
ID=6458298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2095570 Abandoned CA2095570A1 (en) | 1992-05-06 | 1993-05-05 | Polyfunctional epoxide compounds |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0568908A2 (en) |
| JP (1) | JPH06184273A (en) |
| BR (1) | BR9301759A (en) |
| CA (1) | CA2095570A1 (en) |
| DE (1) | DE4214964A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19622221A1 (en) * | 1996-06-03 | 1997-12-04 | Henkel Kgaa | Process for coating electrically conductive substrates |
| WO2000040634A2 (en) * | 1998-12-30 | 2000-07-13 | Hercules Incorporated | Modified epoxies for paper sizing |
| US10190228B2 (en) * | 2016-03-29 | 2019-01-29 | Rohm And Haas Electronic Materials Llc | Copper electroplating baths and electroplating methods capable of electroplating megasized photoresist defined features |
-
1992
- 1992-05-06 DE DE19924214964 patent/DE4214964A1/en not_active Withdrawn
-
1993
- 1993-04-26 JP JP9908193A patent/JPH06184273A/en active Pending
- 1993-04-28 EP EP19930106851 patent/EP0568908A2/en not_active Withdrawn
- 1993-05-05 BR BR9301759A patent/BR9301759A/en not_active Application Discontinuation
- 1993-05-05 CA CA 2095570 patent/CA2095570A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP0568908A2 (en) | 1993-11-10 |
| JPH06184273A (en) | 1994-07-05 |
| BR9301759A (en) | 1993-11-09 |
| DE4214964A1 (en) | 1993-11-11 |
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