CA2008194C - Composition for cationic electrodeposition coating - Google Patents
Composition for cationic electrodeposition coatingInfo
- Publication number
- CA2008194C CA2008194C CA002008194A CA2008194A CA2008194C CA 2008194 C CA2008194 C CA 2008194C CA 002008194 A CA002008194 A CA 002008194A CA 2008194 A CA2008194 A CA 2008194A CA 2008194 C CA2008194 C CA 2008194C
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- compound
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- resin
- cationic
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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
- C09D5/4473—Mixture of polymers
-
- 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
- C09D5/4488—Cathodic paints
- C09D5/4492—Cathodic paints containing special additives, e.g. grinding agents
Abstract
An improved composition for cationic electrodeposition coating contains a water dispersion of a cationic aqueous resin and inner-crosslinked micro-resin particles, The micro-resin particles comprise an inner-crosslinked addition polymer of an active hydrogen-containing compound with an active double bond-containing compound having cationic groups. The composition is superior in preventing corrosion at the edge portions of articles to be coated.
Description
,~.
The present invention relates to a composition for cationic electrodeposition coating superior in preventing the edge portion of articles to be coated from corrosion (hereinafter referred to as edge-corrosion prevention).
Cationic electrodeposition coating is a process for coating a cathode article to be coated by passing direct current through a cationic water dispersion prepared by neutralizing a resin having basic groups with an organic acid and diluting with water, this process being widely used in industry at present.
Various compositions for cationic electrodeposition coating are therefore being devised.
However, the conventional compositions do not satisfy the recent requirements for the prevention of automobile corrosion, that is, requirements for a high-level edge-covering performance ( in turn, edge-corrosion preventive performance). If a sufficient corrosion resistance is thought to have been given to articles to be coated by cationically electro-depositing the articles in a film thickness of 15 to 25~-, the thickness of a film formed on the edge is only O to 3 ~ (this film thickness is affected by an edge angle). As a result, corrosion begins from the edge earlier than from other portions, and the retention of corrosion resistance of the coated articles as a whole becomes a problem.
The fact is, therefore, that there must be taken labor-requiring measures other than cationic electrodeposition coating, for ~08 ~ 9 4 ,., example, the edge is bent inwards at the time of cutting, processing before coating so as to be in a secret place, or it is additionally coated with other materials after cationic electro-deposition coating.
The present inventors have made an intensive study on .
an improvement in the edge-corrosion preventive power of cationic electrodeposition paints, and as a result, have found that, by adding a water dispersion of inner-crosslinked micro-resin particles of 0.05 to 3 ~ in particle size synthesized from an active hydrogen-containing compound and an active double bond-containing compound to the hitherto known cationic electro-deposition paints, excellent edge-corrosion resistance is obtained with the same appearance and corrosion resistance as ever being maintained. The present inventors thus completed the present invention.
The present invention provides a composition for cationic electrodeposition coating characterized in that said composition contains a water dispersion of a cationic aqueous resin and inner-crosslinked micro-resin particles, said inner-crosslinked micro-resin particles comprising an inner-crosslinked addition polymer of an active hydrogen-containing compound (A) with an active double bond-containing compound (B) and having cationic groups.
The cationic aqueous resin of the present invention may B ~ ---2--~n~
be any of the conventionally known ones. For example, there are mentioned amino group-containing resins such as amine-modified epoxy resins ~Japanese Patent Publication No. 4978/1979, Japanese Patent Kokai (Laid-open) No. 93024/1979, Japanese Patent Publication No. 47143/1978, Japanese Patent Kokai (Laid-open) No. 8673/1978, No. 80436/1980 and No. 206442/1984~, amine-modified polyurethane-polyol resins CJapanese Patent Kokai (Laid-open) No. 15449/1979 and No. 115476/1980~ and amine-modified polybutadiene resins ~
Japanese Patent Kokai (Laid-open) No. 16048/1978, No. 142444/1978 and No. 90273/1985~, sulfonium group-containing resins, phosphonium group-containing resins, etc.
The foregoing cationic aqueous resin is made water-dispersible or water-soluble before use by neutralizing it with an acid. The acid usable may be any of mineral acids and organic acids, and for example it includes nitric acid, lactic acid, formic acid, acetic acid, propionic acid, butyric acid, hydrochloric acid, phosphoric acid and sulfuric acid.
The aqueous coating composition is a dispersion consisting mainly of water, but it may contain solvents other than water such as hydrocarbons, alcohols, esters, ethers and ketones.
The amount of these solvents is not important, but it is 0.1 to 40 wt.%, preferably 0.5 to 25 wt.% based on the solid resin.
In producing the composition for cationic electro-deposition coating of the present invention, the cationic aqueous 2~08194 ,.".
resin may be blended, if necessary, with the known curing agents such as melamine resins, blocked polyisocyanate compounds and trans-esterification curing agents.
To the composition for cationic electrodeposition coating of the present invention may be added a curing catalyst.
Such a curing catalyst includes the organic acid salts of cobalt, manganese, iron, zinc, lead, calcium and zirconium, manganese dioxide and organotin compounds. The foregoing organic acid salts and manganese dioxide are used as a curing catalyst for oxidation polymerization, and the organotin compounds such as dibutyltin oxide, dibutyltin laurate, etc. are used as a catalyst for decomposing blocked isocyanate.
The amount of the curing catalyst added is 0.005 to 2.0 wt.%, preferably 0.05 to 1.0 wt.%, calculated as metal, of the solid resin.
To the composition for cationic electrodeposition coating of the present invention may further be added pigments such as extender pigments (e.g. aluminum silicate, precipitated barium sulfate, kaolin, precipitated calcium carbonate), color pigments ( e.g. titanium oxide, carbon black, zinc white, iron oxide, manganese dioxide) and anti-corrosive pigments (e.g. strontium chromate, lead chromate, basic lead silicate, aluminum phospho-molybdate). These pigments, however, are not limitative.
To the composition for cationic eletrodeposition coating 20081~4 .,, of the present invention may further be added other additives.
Specific examples of the additives include surface active agents, organic solvents (e.g. alcohols, ketones, ethers), flow-controlling agents, ultraviolet ray absorbers, etc.
The composition for cationic electrodeposition coating of the present invention may be applied by the coating methods such as dip coating, spray coating, etc., but electrodeposition coating is preferred. Electrodeposition coating conditions for the composition of the present invention resembles the commonly used ones. Applied voltage may be varied over a wide range. It may be as low as, for example, l volt, but typically, it is in a range of 50 to 500 volts. Current density is usually l.O to 15 ampere/feet2, but it decreases during electro-deposition coating, which means that insulating film is formed during electrodeposition coating.
In electrodeposition coating, the coating composition can be applied not only to various electroconductive supports, particularly metals such as steel, aluminum, copper, magnesium, etc., but also to metallized plastics, electroconductive carbon coatings, etc.
The inner-crosslinked micro-resin particles used in the present invention are produced from a compound (A) having at least two active hydrogens per molecule and a compound (B) having at least two active double bonds per molecule.
20~194 .,,,=
The particle size of the micro-resin particles is preferably 0.05 to 3/~. The particle size exceeding 3~l is not preferred because a stable water dispersion is not obtained, and also because defects appear in the baked coating film.
When the particle size is less than 0.05~, an effect to control the flow on the edge portions at the time of baking is so little that sufficient edge-corrosion resistance is not obtained.
Further, it is necessary for at least one of two these compounds to contain amino groups in an amount of 0.3 to 3.0 milligram equivalents per gram of the inner-crosslinked micro-resin particles, because a cationic property must be given to the micro-resin particles produced from these compounds in order to stably disperse the micro-resin particles in water.
This amino group may be contained in either all or one of these compounds.
As described above, the compound (A) contains at least two active hydrogens per molecule, and this active hydrogen refers to one contained in a primary or secondary amino group, a thiol group or an active methylene group. This compound (A) includes compounds containing two or more of the foregoing groups per molecule and the commonly known paint resins such as polyepoxy resins, acrylic resins, polybutadiene resins, polyester resins, polyurethane resins, polyamide resins, etc. all of which have been modified with two or more molecules of a compound ~UU~1~4 ~, containing at least one of the foregoing groups per molecule or one or more molecules of a compound containing two or more of the foregoing groups per molecule.
As described above, the compound (B) contains at least two active double bonds per molecule, and this active double bond refers to an ~ ethylenic double bond adjacent to a carbonyl group. This compound (B) includes compounds containing two or more foregoing double bonds per molecule and the foregoing commonly known paint resins modified with two or more molecules of a compound containing one foregoing double bond per molecule or one or more molecules of a compound containing two or more foregoing double bonds per molecule.
Modification referred to herein is to bond the foregoing compounds to the resins by the commonly known reactions described below. At this time, it is necessary that at least two active hydrogens or active double bonds remain in one molecule of the composition after modification.
Examples of the reaction of the foregoing compounds with the resins will be shown below :
(a) Reaction of an amine compound having one or more primary amino and secondary amino groups in the molecule with epoxy groups in the resin.
(b) Amidation reaction of the above amine compound with carboxyl groups in the polyester resin.
~U~94 (c) Urethane reaction or biuret reaction of the above amine compound and/or an amine compound having one or more primary amino or secondary amino groups and one or more hydroxyl groups ln the molecule with isocyanate groups in the resin.
(d) Method comprising reacting an epoxy group with a ketimine compound derived from a ketone and an amine having one or more secondary amines and at least one primary amino group in the molecule, and hydrolyzing the resulting product to separate the ketone, whereby the primary amino group is regenerated ~refer to Japanese Patent Kokai (Laid-open) No. 129270/1984~.
(e) Reaction of mercapto groups in a polymercapto compound with epoxy groups in the resin.
(f) Esterification and ester-exchange reaction of hydroxyl groups in the foregoing resin with the foregoing active methylene group-containing compound ~refer to Japanese Patent Kokai (Laid-open) No. 83568/1982~.
(g) Esterification or ester-exchange reaction of the foregoing active double bond-containing compound with hydroxyl groups in the foregoing resin, or etherification of said active double bond-containing compound with epoxy groups in the foregoing resin ~refer to Japanese Patent Koaki (Laid-open) No. 83568/1982~.
In introducing an amino group in order to give the cationic property, when the active hydrogen in the compound (A) has its origin in the amino group of the compound (A), this amino ,."., group gives the cationic property. In cases other than the one described above, the cationic property is obtained by bonding an amino group-containing compound to the compounds lA) and (B) by all the known chemical reactions so that these active hydrogen and active double bond may not be lost by the reaction.
As the compound containing a primary or secondary amino group, there are mentioned primary alkylamines (e.g. monomethyl-amine, monoethylamine, monobutylamine, monopropylamine), primary alkanolamines (e.g. monoethanolamine, monopropanolamine, mono-butanolamine), secondary alkylamines (e.g. dimethylamine, diethylamine, dibutylamine), secondary alkylalkanolamines (e.g.
diethanolamine, dipropanolamine, methylethanolamine, ethyl-ethanolamine, methylpropanolamine), diamines having one primary amino group and one secondary amino group in the molecule (e.g.
monomethylaminoethylamine, monoethylaminoethylamine, monomethyl-aminopropylamine, monoethylaminopropylamine), primary diamines ( e.g. ethylenediamine, 1,4-butanediamine, 1,6-hexanediamine, phenylenediamine, piperazine), polyamines (e.g. diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylene-hexamine), polyamidepolyamines which are a condensation product of the foregoing di- or polyamine with an organic dicarboxylic acid (e.g. adipic acid, azelaic acid, maleic acid) and ketimine compounds obtained by the reaction of a polyamine having one secondary amino group and one or more primary amino groups in the ~nsl~
molecule with a ketone, said polyamine including monomethyl-aminoethylamine, monoethylaminopropylamine, diethylenetriamine, dibutylenetriamine, etc. belonging to the foregoing amine compounds, and said ketone including methyl ethyl ketone, methyl isobutyl ketone, cyclohexane, etc.
As the foregoing compound containing a thiol group, there are mentioned for example those which are produced by reacting glycol, polyesterpolyol, polyetherpolyol or polyamine with a monomercaptomonocarboxylic acid or its lower alkyl ester represented by the formula, R'OOC - R - SH (in which R represents a divalent organic residue such as a C1-C20 alkylene which may be substituted, and R' represents a C1-C4 alkyl group such as methyl and ethyl).
Examples of polyesterpolyol include for example polymerized polyesters obtained by reacting ethylene glycol, propylene glycol, neopentyl glycol or cyclohexanedimethanol with an organic dicarboxylic acid (e.g. terephthalic acid, hexahydro-phthalic acid, adipic acid, azelaic acid) or its anhydride.
Examples of polyetherpolyol include for example poly(oxytetramethylene)glycol, poly(oxyethylene)glycol, poly(oxy-propylene)glycol, etc.
Examples of polyamine include for example the foregoing di- or polyamines and polyamidepolyamines, etc.
Examples of the monomercaptomonocarboxylic acid include ."...,~
mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercapto-propionic acid, etc.
As examples of the foregoing active methylene group-containing compound, there are mentioned for example malonic acid, monomethyl malonate, monoethyl malonate, monobutyl malonate, dimethyl malonate, diethyl malonate, succinic acid, monoethyl succinate, dibutyl succinate, cyanoacetamide, cyanoacetic acid, ethyl cyanoacetate, methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate, etc.
As examples of the ~,~-ethylenic unsaturated carbonyl compound used in the present invention, there are mentioned for example acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, cinnamic acid and ester compounds of these acids with methanol, ethanol, propanol, butanol, allyl alcohol, ethylene glycol, propylene glycol, trimethylolpropane, penta-erythritol, phenol, 4,4-diphenolpropane, etc.
Production of inner-crosslinked spherical micro-resin particles :
The inner-crosslinked micro-resin particles used in the present invention is obtained by mixing the active hydrogen-containing compound (A), the active double bond-containing compound (B) and if necessary a solvent (e.g. water, alcohol, ester, ether, ketone) and an organic acid (e.g. formic acid, acetic acid, lactic acid, propionic acid), thoroughly mixing the resulting mixture at a temperature of room temperature ~ B ~ 4 ., .
to 150 C with stirring, adding water or an aqueous solution of the above organic acid or a water dispersion of a cationically electrodepositable aqueous resin which is an essential component to the present invention, and then stirring the resulting mixture at a temperature of room temperature to 95 C to carry out addition polymerization. When the compunds (A) and (B) are kept for a long time in a state wherein they are mixed and heated, addition polymerization naturally takes place to the full to produce gelled products. Consequently, at a point when the addition polymeri-zation does not begin at all or has begun only partly, water or an aqueous solution of the organic acid or a water dispersion of a cationically electrodepositable aqueous resin is added to disperse the compounds (A) and (B) in fine particles, and then the addition polymerization is allowed to proceed to the full to produce inner-crosslinked micro-resin particles.
In the present invention, the inner-crosslinked micro-resin particles are added in an amount of preferably 0.1 to 40 parts by weight based on 100 parts by weight of the solid matter of the foregoing cationically electrodepositable water-dispersible resin. When the amount is less than 0.1 part by weight, a satisfactory edge-corrosion preventive performance is not obtained. When the amount exceeds 40 parts by weight, the micro-resin particles, because of their crosslinked structure, do not melt by joule heat during electrodeposition coating, so _ that electrical resistance of film referred to in this field is not obtained uniformly. The coating film obtained, therefore, has many defects and is non-uniform in quality, and also a sufficient throwing powder is not obtained.
The present invention will be illustrated in more detail with reference to the following specific examples, but it is not limited thereto. Unless otherwise stated, all the parts and percents (%) in the examples are by weight.
Production examples for active hydrogen-containing compound (A) :
Production example l To a 3-liter four-necked flask equipped with a thermometer, a reflux condenser and a stirrer were added 950 parts of a bisphenol A-type epoxy resin having an epoxy equivalent of 475 and 588 parts of propylene glycol methyl ether, and the mixture was heated to llO C with stirring and dissolved.
After cooling the mixture to 80 C, 422 parts of a diketimine compound prepzred from 2 moles of me~hyl ethyl ketone and l mole of diethylenetriamine was adGeG. After ~;eeping the mixture at a temperature of 80 C for ' hours, 12 parts of ac:etic acid anc 180 parts of pure water were added, and reaction was carried out at a temperature of 80 C for l hour to obtain Compound A-l containing two primary amino groups per molecule.
Production example 2 To the same 3-liter four-necked flask as used in ,~
Production example l was added 1100 parts of a methyl ethyl ketone solution of an acrylpolyol resin having a number average molecular weight of 2200 and comprising methyl methacrylate and 2-hydroxyethyl methacrylate in a weight ratio of l:l, and then stirring was started. In said solution, the solid resin content was 75% and the hydroxyl equivalent was 216 mg KOH per gram of the solid resin. Subsequently, 452 parts of malonic acid monoester and 3 parts of dimethylbenzylamine were added, and reaction was carried out at a temperature of 165 C for 3 hours to obtain Compound A-2 having an acid value of 25.
Production example 3 To the same 3-liter four-necked flask as used in Production example 1 were added 950 parts of a bisphenol F-type epoxy resin having an epoxy equivalent of 950 and 407 parts of ethylene glycol butyl ether, and the mixture was dissolved at a temperature of 110 C with stirring. After cooling the mixture to 60 C, 105 parts of diethanolamine was added, and reaction was carried out at a temperature of 120 C for 2 hours. Thereafter, 462 parts of mercaptobenzoic acid was added, and reaction was carried out at a temperature of 170 C for 5 hours to obtain Compound A-3 having an acid value of 1.5.
Production example 4 To the same 3-liter four-necked flask as used in Production example l were added 1100 parts of a polyesterpolyol 20~8~ 9 4 resin having a hydroxyl value of 215 mg KOH/g (Nippolan 1100i a product of Nippon Polyurethane Co., Ltd.) and 472 parts of methyl isobutyl ketone, and the mixture was dissolved at a temperature of 70 C with stirring.
Separately from this, 340 parts of methyl isobutyl ketone and 348 parts of 2,4-tolylenediisocyanate were added to a similar 2-liter four-necked flask, and 376 parts of a methyl isobutyl ketone solution (solid content, 91.5%) of a ketimine compound prepared from l mole of monomethylaminopropylamine and l mole of methyl isobutyl ketone was added dropwise at a temperature of 25 to 30 C over 60 minutes with stirring to prepare a semi-blocked isocyanate compound. This compound was gradually added to the above polyesterpolyol resin solution, and reaction was carried out O
at a temperature of 70 C for 3 hours to obtain Compound A-4.
Production examples for active double bond-containing compound (B) :
Production example 5 To the same 3-liter four-necked flask as used in Production example l were added 1000 parts of an epoxidized polybutadiene resin having an oxirane oxygen content of 6.5% and a number average molecular weight of 1800 (E-1800-6.5; a product of Nisseki Kagaku Co., Ltd.), 377 parts of ethylene glycol butyl ether and 131 parts of methylethanolamine, and reaction was carried out at a temperature of 170 C for 6 hours in a nitrogen gas stream. After cooling the reaction solution to 120 C, * Trade Mark B ~ -15--... .
81.4 parts of acrylic acid, 8.8 parts of hydroquinone and 27.1 parts of ethylene glycol ethyl ether were added, and reaction was carried out at a temperature of 120 C for 4 hours to obtain an active double bond-containing compound B-1.
Production example 6 To a l-liter four-necked flask similar to that used in Production example l were added 196 parts of maleic acid anhydride and 232 parts of 2-hydroxyethyl acrylate, and then 0.9 part of triethylamine was added at a temperature of 65 C. Reaction was carried out at the same temperature for l hour to prepare a compound having an acid value of 260 mg KOH/g.
To an another 3-liter four-necked flask were added 1200 parts of a novolak-type epoxy resin having an epoxy equivalent of 180, 514 parts of ethylene glycol butyl ether and 490 parts of diethanolamine, and reaction was carried out at a temperature of o 90 C for 1.5 hours. Thereafter, 428 parts of the above compound prepared from maleic acid anhydride and 2-hydroxyethyl acrylate and 2 parts of hydroquinone were added, and reaction was carried out at a temperature of 120 C for 3 hours to obtain Compound B-2 having an acid value of 0.5.
Production example 7 514 Parts of toluene was added to the same 3-liter four-necked flask as used in Production example l and refluxed at a ~temperature of about 110 C. Separately from this, 200 parts of 2 o o ~ ~ ~ 4 n-butyl acrylate, 400 parts of methyl methacrylate, 400 parts of 2-hydroxyethyl methacrylate and 50 parts of di-tert-butyl peroxide were added to an another flask and mixed with stirring.
The resulting mixture was added dropwise to the above flask over 3 hours under reflux of toluene. Thereafter, reaction was continued at a temperature of 115 C for 2 hours, followed by cooling to 80 C.
Subsequently, 294 parts of maleic acid anhydride and 10 parts of tributylamine were added, and reaction was carried out at a temperature of 100 C for 4 hours to obtain a reaction product having an acid value of 130 mg KOH/g. Thereafter, 426 parts of glycidyl methacrylate was added and reaction was carried out at a temperature of 120 C for 4 hours to obtain Compound B-3 having an acid value of 3.5 mg KOH/g.
Production examples for inner-crosslinked micro-resin particles :
Production example 8 To the same 3-liter four-necked flask as used in Production example 1 were added 1067 parts of Compound B-l, 300 parts of a modified aliphatic polyamine having an amine value of 345 mg KOH/g (Adeka Hardener EH-266, a product of Asahi Denka Co., Ltd.) and 325 parts of isopropanolamine, and the contents of forO30 minutes the flask were mixed at a temperature of 60 C~with stirring.
During this period, 2500 parts of pure water and 15 * Trade Mark --17--B t 20~8194 ,.. ..
parts of acetic acid were added to a 4-liter stainless steel cylindrical container and kept at a temperature of 60 C while stirring with a disper. To this aqueous acetic acid solution was gradually added 621 parts of the above resin mixture over 20 minutes. Thereafter, stirring was continued at a temperature of 60 C for 3 hours to obtain a water dispersion H of inner-crosslinked micro-resin particles.
The solid content of this water dispersion was 20%, and the base value was 1.7 mg equivalent/g. On measuring the particle size on a particle size-measuring instrument (LP 3000/
3100; a product of Otsuka Denshi Co., Ltd.) according to the laser scattering method, the particle size was 0.1 ~. The content of insoluble matter of the water dispersion was measured by adding THF to the dispersion and centrifuging, and as a result, the content was found to be 95% of the total solid content (herein-after referred to as gel ratio).
Production example 9 To the same 3-liter four-necked flask as used in Production example 1 were added 1428 parts of Compound A-l, 666 parts of Compound B-l and 406 parts of ethylene glycol butyl ether, o and the contents of the flask were mixed at a temperature of S0 C
for l hour, after which 13.8 parts of formic acid was added.
After mixing for 10 minutes, 833 parts of the resulting resin mixture was gradually added to 2500 parts of pure water over 20 ", .
minutes in the same manner as in Production example 8, and stirring was continued at a temperature of 60 C for 3 hours to obtain a water dispersion I of inner-crosslinked micro-resin particles. The solid content of the water dispersion was 20%, the base value was 2.9 mg equivalent/g, the particle size was 0.3~-, and the gel ratio was 88%.
Production example lO
To a 5-liter four-necked flask similar to that used in Production example l were added 400 parts of Compound A-2, 500 parts of Compound B-2, 330 parts of ethylene glycol ethyl ether and 19.2 parts of acetic acid, and the contents of the flask were mixed at a temperature of 60 C for 2 hours with stirring.
Thereafter, 1950 parts of pure water was gradually added, and stirring was continued at a temperature of 80 C for 3 hours to obtain a water dispersion J of inner-crosslinked micro-resin particles having a particle size of 0.2~l. The solid content of this water dispersion was 25%, the gel ratio thereof was 80%, and the base value was 1.0 mg equivalent/g.
Production example 11 To the same 3-liter four-necked flask as used in Production example 1 were added 1265 parts of Compound A-3, 667 parts of Compound B-3, 568 parts of isopropanol and 19.3 parts of formic acid, and the contents of the flask were mixed at a tempe-rature of 80 C for 1 hour with stirring. Thereafter, in the same manner as in Production example 8, 840 parts of the resulting resin mixture was added over 20 minutes to 2500 parts of pure water kept at a temperature of 60 C in a 4-liter stainless steel container, and the mixture was kept at the same temperature for 3 hours to obtain a water dispersion K of inner-crosslinked micro-resin particles. The solid content of the water dispersion was 20%, the particle size was 1.1/~, and the base value was 0.4 mg equivalent/g. The gel ratio of the water dispersion was 85%.
Production example 12 To a 5-liter four-necked flask similar to that used in Production example l were added 1470 parts of Compound A-4, 102 parts of trimethylolpropane triacrylate and 123 parts of ethylene glycol ethyl ether, and the contents of the flask were mixed at a temperature of 50 C for l hour with stirring. Thereafter, a mixture of 2673 parts of pure water and 40 parts of lactic acid was gradually added over 30 minutes, after which stirring was continued at a temperature of 70 C for 4 hours to obtain a water dispersion L of inner-crosslinked micro-resin particles.
The solid content of the water dispersion was 25%, the particle size was 0.8/l" and the base value was 2.2 mg equivalent/g.
The gel ratio of the water dispersion was 98%.
Production example 13 To the same 3-liter four-necked flask as used in Production example l were added 1250 parts of Compound B-2 and " ,=, lO0 parts of trimethylolpropane trimercaptopropionate, and the contents of the flask were mixed at a temperature of 80 C for 2 hours. Thereafter, 614 parts of the resulting resin mixture was gradually added over 20 minutes to a mixture, kept at a temperature of 70 C, of 1877 parts of pure water and 9 parts of acetic acid. Stirring was then continued at a temperature of 60 C for 3 hours to obtain a water dispersion M of inner-crosslinked mincro-resin particles. The solid content of the water dispersion was 20%, the particle size was 0.5~, and the base value was 2.0 mg equivalent/g. The gel ratio of the water dispersion was 90%.
Production example 14 To the same 3-liter four-necked flask as used in Production example l were added 1333 parts of Compound B-3 and 259 parts of ethylene glycol butyl ether, and 100 parts of triethylenetetramine was added at a temperature of 60 C with stirring. Stirring was then continued at a temperature of 60 C for further 30 minutes. In the same manner as in Production example 8, 769 parts of the resulting resin mixture was added over 15 minutes to a mixture, kept at a temperature of 55 C, of 1718 parts of pure water and 12.6 parts of formic acid, and stirring was continued at a temperature of 35 C for 3 hours to obtain a water dispersion N of inner-crosslinked micro-resin particles. The solid content of the water dispersion was 18%, ~8~ 9 4 the particle size was 1.7 ~, and the base value was 2.5 mg equivalent/g. The gel ratio of the water dispersion was 93%.
Production examples for cationic aqueous resin and its water dispersion :
Production example 15 1900 Grams of Epikote #1004*(epibis-epoxy resin; a product of Shell Co.) was dissolved in 700 g of ethylene glycol ethyl ether in a clean 4-liter four-necked flask. After adding 200 g of diethanolamine, the resulting mixture was kept at a temperature of 60 C to 65 C for l hour, heated to 120 C and then kept at the same temperature for l hour. Subsequently, after cooling the mixture to 80 C, 500 g of a blocked isocyanate-type curing agent (EH-117-20; a product of Asahi Denka Co., Ltd.) was added. The resulting mixture was thoroughly mixed while keeping it at a temperature of 80 C to 85 C for l hour to obtain a cationic aqueous resin. Thereafter, 45 g of the above resin, 45 g of ethylene glycol ethyl ether, 135 g of titanium oxide, 7 g of carbon black and 300 g of glass beads were put in a l-liter mayonnaise bottole and finely pulverized on a quick mill to obtain a pigment dispersion. 540 Grams of the above aqueous resin, 232 g of the pigment dispersion and 8.5 g of formic acid were added to a 4-liter stainless steel vat and thoroughly mixed together with 2179.5 g of deionized water while gradually adding the deionized water and stirring with a disper. Thus, a cationic water * Trade Mark --22--B ~ -200819~
dispersion O having a solid content of 20% was obtained.
Production example 16 45 Grams of the above cationic aqueous resin, 45 g of ethyl cellosolve, 120 g of titanium oxide, 7 g of carbon black, 35 g of basic lead silicate and 300 g of glass beads were put in a l-liter mayonnaise bottle and finely pulverized on a quick mill to obtain a pigment dispersion.
Thereafter, 540 g of the above cationic resin, 252 g of the pigment dispersion and 8.5 g of formic acid were added to a 4-liter stainless steel vat and thoroughly mixed together with 2259.5 g of deionized water while gradually adding the deionized water and stirring with a disper. Thus, a cationic water dispersion P having a solid content of 20% was obtained.
Examples 1 to 9 and Comparative examples l and 2 The inner-crosslinked micro-resin particles H to N and the water dispersions O and P of the cationic aqueous resin were mixed in the prescribed proportions to prepare cationic electrodeposition paints. Dull steel plate treated with zinc phosphate and the edge of a cutter knife (a product of Co.) were subjected to cationic electrodeposition coating.
The appearance and the results of the salt spray test are shown in Table 1.
200819~
a) ~ ,-- o ~ ~ N P~ ~ ¦ O O
O ~ O ~ ~1 a) z c~
QJ
~ E O ~ ao o E ~ ~ O ~ I o o . o O X O ~ O ~'1 t' Z
U~
Z ~ O O ~
O ~
o o ~ o O
~ oo [_ Pl H ~ ~ ~ ~
~I O
o ~
~ O
a) .,, E ~ Ln U~ O 1~ ~ o O ~
E O ~'1 0 ~1S t~l X
(~ ~ O H ~1 0 0 0 ~ ~
E-~ o ~ o (~
r~ c7 O X U~ O O ~ O
O
O ~ ~ O O ~
O
U~
O ~: ~ O O ~
~ O
o z ~ a o a) *
O 0 4 0 0~~ O aJ ~~1 ~
h ~ 1 u~ V u~ *
~) u.-~ ~.) ~uj ~: a) o r ~ *
~I) Ul E ~ ~ ~ ~ u~
UJ r F 4(a ~1 0 a u~ o u~ r oc, a) F F I O ~ G~ l u~ O I
O O h S- ~,1F. F I
J C ~ ~ ~- E E ~ a)-~
~,, Note :
*l Weight ratio (%) of the solid content of micro-resin particle to that of cationic electrodeposition paint.
*2 The flat portion of the test plate is cross-cut and salt spray-tested for 960 hours according to JIS Z 2371, and the width (mm) of rust formed from the cut portion is measured.
*3 The edge of the foregoing cutter knife is coated so that the film thickness on the flat portion is 20 ~, and baked as determined to make a test plate. The knife is set in a salt spray tester so that the edge turns up and salt spray-tested for 168 hours according to JIS Z 2371, and the number of rusts at the edge portion is counted.
According to the present invention, cationic electro-deposition films having excellent edge-corrosion resistance are obtained with the same good appearance and corrosion resistance as ever being maintained.
The present invention relates to a composition for cationic electrodeposition coating superior in preventing the edge portion of articles to be coated from corrosion (hereinafter referred to as edge-corrosion prevention).
Cationic electrodeposition coating is a process for coating a cathode article to be coated by passing direct current through a cationic water dispersion prepared by neutralizing a resin having basic groups with an organic acid and diluting with water, this process being widely used in industry at present.
Various compositions for cationic electrodeposition coating are therefore being devised.
However, the conventional compositions do not satisfy the recent requirements for the prevention of automobile corrosion, that is, requirements for a high-level edge-covering performance ( in turn, edge-corrosion preventive performance). If a sufficient corrosion resistance is thought to have been given to articles to be coated by cationically electro-depositing the articles in a film thickness of 15 to 25~-, the thickness of a film formed on the edge is only O to 3 ~ (this film thickness is affected by an edge angle). As a result, corrosion begins from the edge earlier than from other portions, and the retention of corrosion resistance of the coated articles as a whole becomes a problem.
The fact is, therefore, that there must be taken labor-requiring measures other than cationic electrodeposition coating, for ~08 ~ 9 4 ,., example, the edge is bent inwards at the time of cutting, processing before coating so as to be in a secret place, or it is additionally coated with other materials after cationic electro-deposition coating.
The present inventors have made an intensive study on .
an improvement in the edge-corrosion preventive power of cationic electrodeposition paints, and as a result, have found that, by adding a water dispersion of inner-crosslinked micro-resin particles of 0.05 to 3 ~ in particle size synthesized from an active hydrogen-containing compound and an active double bond-containing compound to the hitherto known cationic electro-deposition paints, excellent edge-corrosion resistance is obtained with the same appearance and corrosion resistance as ever being maintained. The present inventors thus completed the present invention.
The present invention provides a composition for cationic electrodeposition coating characterized in that said composition contains a water dispersion of a cationic aqueous resin and inner-crosslinked micro-resin particles, said inner-crosslinked micro-resin particles comprising an inner-crosslinked addition polymer of an active hydrogen-containing compound (A) with an active double bond-containing compound (B) and having cationic groups.
The cationic aqueous resin of the present invention may B ~ ---2--~n~
be any of the conventionally known ones. For example, there are mentioned amino group-containing resins such as amine-modified epoxy resins ~Japanese Patent Publication No. 4978/1979, Japanese Patent Kokai (Laid-open) No. 93024/1979, Japanese Patent Publication No. 47143/1978, Japanese Patent Kokai (Laid-open) No. 8673/1978, No. 80436/1980 and No. 206442/1984~, amine-modified polyurethane-polyol resins CJapanese Patent Kokai (Laid-open) No. 15449/1979 and No. 115476/1980~ and amine-modified polybutadiene resins ~
Japanese Patent Kokai (Laid-open) No. 16048/1978, No. 142444/1978 and No. 90273/1985~, sulfonium group-containing resins, phosphonium group-containing resins, etc.
The foregoing cationic aqueous resin is made water-dispersible or water-soluble before use by neutralizing it with an acid. The acid usable may be any of mineral acids and organic acids, and for example it includes nitric acid, lactic acid, formic acid, acetic acid, propionic acid, butyric acid, hydrochloric acid, phosphoric acid and sulfuric acid.
The aqueous coating composition is a dispersion consisting mainly of water, but it may contain solvents other than water such as hydrocarbons, alcohols, esters, ethers and ketones.
The amount of these solvents is not important, but it is 0.1 to 40 wt.%, preferably 0.5 to 25 wt.% based on the solid resin.
In producing the composition for cationic electro-deposition coating of the present invention, the cationic aqueous 2~08194 ,.".
resin may be blended, if necessary, with the known curing agents such as melamine resins, blocked polyisocyanate compounds and trans-esterification curing agents.
To the composition for cationic electrodeposition coating of the present invention may be added a curing catalyst.
Such a curing catalyst includes the organic acid salts of cobalt, manganese, iron, zinc, lead, calcium and zirconium, manganese dioxide and organotin compounds. The foregoing organic acid salts and manganese dioxide are used as a curing catalyst for oxidation polymerization, and the organotin compounds such as dibutyltin oxide, dibutyltin laurate, etc. are used as a catalyst for decomposing blocked isocyanate.
The amount of the curing catalyst added is 0.005 to 2.0 wt.%, preferably 0.05 to 1.0 wt.%, calculated as metal, of the solid resin.
To the composition for cationic electrodeposition coating of the present invention may further be added pigments such as extender pigments (e.g. aluminum silicate, precipitated barium sulfate, kaolin, precipitated calcium carbonate), color pigments ( e.g. titanium oxide, carbon black, zinc white, iron oxide, manganese dioxide) and anti-corrosive pigments (e.g. strontium chromate, lead chromate, basic lead silicate, aluminum phospho-molybdate). These pigments, however, are not limitative.
To the composition for cationic eletrodeposition coating 20081~4 .,, of the present invention may further be added other additives.
Specific examples of the additives include surface active agents, organic solvents (e.g. alcohols, ketones, ethers), flow-controlling agents, ultraviolet ray absorbers, etc.
The composition for cationic electrodeposition coating of the present invention may be applied by the coating methods such as dip coating, spray coating, etc., but electrodeposition coating is preferred. Electrodeposition coating conditions for the composition of the present invention resembles the commonly used ones. Applied voltage may be varied over a wide range. It may be as low as, for example, l volt, but typically, it is in a range of 50 to 500 volts. Current density is usually l.O to 15 ampere/feet2, but it decreases during electro-deposition coating, which means that insulating film is formed during electrodeposition coating.
In electrodeposition coating, the coating composition can be applied not only to various electroconductive supports, particularly metals such as steel, aluminum, copper, magnesium, etc., but also to metallized plastics, electroconductive carbon coatings, etc.
The inner-crosslinked micro-resin particles used in the present invention are produced from a compound (A) having at least two active hydrogens per molecule and a compound (B) having at least two active double bonds per molecule.
20~194 .,,,=
The particle size of the micro-resin particles is preferably 0.05 to 3/~. The particle size exceeding 3~l is not preferred because a stable water dispersion is not obtained, and also because defects appear in the baked coating film.
When the particle size is less than 0.05~, an effect to control the flow on the edge portions at the time of baking is so little that sufficient edge-corrosion resistance is not obtained.
Further, it is necessary for at least one of two these compounds to contain amino groups in an amount of 0.3 to 3.0 milligram equivalents per gram of the inner-crosslinked micro-resin particles, because a cationic property must be given to the micro-resin particles produced from these compounds in order to stably disperse the micro-resin particles in water.
This amino group may be contained in either all or one of these compounds.
As described above, the compound (A) contains at least two active hydrogens per molecule, and this active hydrogen refers to one contained in a primary or secondary amino group, a thiol group or an active methylene group. This compound (A) includes compounds containing two or more of the foregoing groups per molecule and the commonly known paint resins such as polyepoxy resins, acrylic resins, polybutadiene resins, polyester resins, polyurethane resins, polyamide resins, etc. all of which have been modified with two or more molecules of a compound ~UU~1~4 ~, containing at least one of the foregoing groups per molecule or one or more molecules of a compound containing two or more of the foregoing groups per molecule.
As described above, the compound (B) contains at least two active double bonds per molecule, and this active double bond refers to an ~ ethylenic double bond adjacent to a carbonyl group. This compound (B) includes compounds containing two or more foregoing double bonds per molecule and the foregoing commonly known paint resins modified with two or more molecules of a compound containing one foregoing double bond per molecule or one or more molecules of a compound containing two or more foregoing double bonds per molecule.
Modification referred to herein is to bond the foregoing compounds to the resins by the commonly known reactions described below. At this time, it is necessary that at least two active hydrogens or active double bonds remain in one molecule of the composition after modification.
Examples of the reaction of the foregoing compounds with the resins will be shown below :
(a) Reaction of an amine compound having one or more primary amino and secondary amino groups in the molecule with epoxy groups in the resin.
(b) Amidation reaction of the above amine compound with carboxyl groups in the polyester resin.
~U~94 (c) Urethane reaction or biuret reaction of the above amine compound and/or an amine compound having one or more primary amino or secondary amino groups and one or more hydroxyl groups ln the molecule with isocyanate groups in the resin.
(d) Method comprising reacting an epoxy group with a ketimine compound derived from a ketone and an amine having one or more secondary amines and at least one primary amino group in the molecule, and hydrolyzing the resulting product to separate the ketone, whereby the primary amino group is regenerated ~refer to Japanese Patent Kokai (Laid-open) No. 129270/1984~.
(e) Reaction of mercapto groups in a polymercapto compound with epoxy groups in the resin.
(f) Esterification and ester-exchange reaction of hydroxyl groups in the foregoing resin with the foregoing active methylene group-containing compound ~refer to Japanese Patent Kokai (Laid-open) No. 83568/1982~.
(g) Esterification or ester-exchange reaction of the foregoing active double bond-containing compound with hydroxyl groups in the foregoing resin, or etherification of said active double bond-containing compound with epoxy groups in the foregoing resin ~refer to Japanese Patent Koaki (Laid-open) No. 83568/1982~.
In introducing an amino group in order to give the cationic property, when the active hydrogen in the compound (A) has its origin in the amino group of the compound (A), this amino ,."., group gives the cationic property. In cases other than the one described above, the cationic property is obtained by bonding an amino group-containing compound to the compounds lA) and (B) by all the known chemical reactions so that these active hydrogen and active double bond may not be lost by the reaction.
As the compound containing a primary or secondary amino group, there are mentioned primary alkylamines (e.g. monomethyl-amine, monoethylamine, monobutylamine, monopropylamine), primary alkanolamines (e.g. monoethanolamine, monopropanolamine, mono-butanolamine), secondary alkylamines (e.g. dimethylamine, diethylamine, dibutylamine), secondary alkylalkanolamines (e.g.
diethanolamine, dipropanolamine, methylethanolamine, ethyl-ethanolamine, methylpropanolamine), diamines having one primary amino group and one secondary amino group in the molecule (e.g.
monomethylaminoethylamine, monoethylaminoethylamine, monomethyl-aminopropylamine, monoethylaminopropylamine), primary diamines ( e.g. ethylenediamine, 1,4-butanediamine, 1,6-hexanediamine, phenylenediamine, piperazine), polyamines (e.g. diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylene-hexamine), polyamidepolyamines which are a condensation product of the foregoing di- or polyamine with an organic dicarboxylic acid (e.g. adipic acid, azelaic acid, maleic acid) and ketimine compounds obtained by the reaction of a polyamine having one secondary amino group and one or more primary amino groups in the ~nsl~
molecule with a ketone, said polyamine including monomethyl-aminoethylamine, monoethylaminopropylamine, diethylenetriamine, dibutylenetriamine, etc. belonging to the foregoing amine compounds, and said ketone including methyl ethyl ketone, methyl isobutyl ketone, cyclohexane, etc.
As the foregoing compound containing a thiol group, there are mentioned for example those which are produced by reacting glycol, polyesterpolyol, polyetherpolyol or polyamine with a monomercaptomonocarboxylic acid or its lower alkyl ester represented by the formula, R'OOC - R - SH (in which R represents a divalent organic residue such as a C1-C20 alkylene which may be substituted, and R' represents a C1-C4 alkyl group such as methyl and ethyl).
Examples of polyesterpolyol include for example polymerized polyesters obtained by reacting ethylene glycol, propylene glycol, neopentyl glycol or cyclohexanedimethanol with an organic dicarboxylic acid (e.g. terephthalic acid, hexahydro-phthalic acid, adipic acid, azelaic acid) or its anhydride.
Examples of polyetherpolyol include for example poly(oxytetramethylene)glycol, poly(oxyethylene)glycol, poly(oxy-propylene)glycol, etc.
Examples of polyamine include for example the foregoing di- or polyamines and polyamidepolyamines, etc.
Examples of the monomercaptomonocarboxylic acid include ."...,~
mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercapto-propionic acid, etc.
As examples of the foregoing active methylene group-containing compound, there are mentioned for example malonic acid, monomethyl malonate, monoethyl malonate, monobutyl malonate, dimethyl malonate, diethyl malonate, succinic acid, monoethyl succinate, dibutyl succinate, cyanoacetamide, cyanoacetic acid, ethyl cyanoacetate, methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate, etc.
As examples of the ~,~-ethylenic unsaturated carbonyl compound used in the present invention, there are mentioned for example acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, cinnamic acid and ester compounds of these acids with methanol, ethanol, propanol, butanol, allyl alcohol, ethylene glycol, propylene glycol, trimethylolpropane, penta-erythritol, phenol, 4,4-diphenolpropane, etc.
Production of inner-crosslinked spherical micro-resin particles :
The inner-crosslinked micro-resin particles used in the present invention is obtained by mixing the active hydrogen-containing compound (A), the active double bond-containing compound (B) and if necessary a solvent (e.g. water, alcohol, ester, ether, ketone) and an organic acid (e.g. formic acid, acetic acid, lactic acid, propionic acid), thoroughly mixing the resulting mixture at a temperature of room temperature ~ B ~ 4 ., .
to 150 C with stirring, adding water or an aqueous solution of the above organic acid or a water dispersion of a cationically electrodepositable aqueous resin which is an essential component to the present invention, and then stirring the resulting mixture at a temperature of room temperature to 95 C to carry out addition polymerization. When the compunds (A) and (B) are kept for a long time in a state wherein they are mixed and heated, addition polymerization naturally takes place to the full to produce gelled products. Consequently, at a point when the addition polymeri-zation does not begin at all or has begun only partly, water or an aqueous solution of the organic acid or a water dispersion of a cationically electrodepositable aqueous resin is added to disperse the compounds (A) and (B) in fine particles, and then the addition polymerization is allowed to proceed to the full to produce inner-crosslinked micro-resin particles.
In the present invention, the inner-crosslinked micro-resin particles are added in an amount of preferably 0.1 to 40 parts by weight based on 100 parts by weight of the solid matter of the foregoing cationically electrodepositable water-dispersible resin. When the amount is less than 0.1 part by weight, a satisfactory edge-corrosion preventive performance is not obtained. When the amount exceeds 40 parts by weight, the micro-resin particles, because of their crosslinked structure, do not melt by joule heat during electrodeposition coating, so _ that electrical resistance of film referred to in this field is not obtained uniformly. The coating film obtained, therefore, has many defects and is non-uniform in quality, and also a sufficient throwing powder is not obtained.
The present invention will be illustrated in more detail with reference to the following specific examples, but it is not limited thereto. Unless otherwise stated, all the parts and percents (%) in the examples are by weight.
Production examples for active hydrogen-containing compound (A) :
Production example l To a 3-liter four-necked flask equipped with a thermometer, a reflux condenser and a stirrer were added 950 parts of a bisphenol A-type epoxy resin having an epoxy equivalent of 475 and 588 parts of propylene glycol methyl ether, and the mixture was heated to llO C with stirring and dissolved.
After cooling the mixture to 80 C, 422 parts of a diketimine compound prepzred from 2 moles of me~hyl ethyl ketone and l mole of diethylenetriamine was adGeG. After ~;eeping the mixture at a temperature of 80 C for ' hours, 12 parts of ac:etic acid anc 180 parts of pure water were added, and reaction was carried out at a temperature of 80 C for l hour to obtain Compound A-l containing two primary amino groups per molecule.
Production example 2 To the same 3-liter four-necked flask as used in ,~
Production example l was added 1100 parts of a methyl ethyl ketone solution of an acrylpolyol resin having a number average molecular weight of 2200 and comprising methyl methacrylate and 2-hydroxyethyl methacrylate in a weight ratio of l:l, and then stirring was started. In said solution, the solid resin content was 75% and the hydroxyl equivalent was 216 mg KOH per gram of the solid resin. Subsequently, 452 parts of malonic acid monoester and 3 parts of dimethylbenzylamine were added, and reaction was carried out at a temperature of 165 C for 3 hours to obtain Compound A-2 having an acid value of 25.
Production example 3 To the same 3-liter four-necked flask as used in Production example 1 were added 950 parts of a bisphenol F-type epoxy resin having an epoxy equivalent of 950 and 407 parts of ethylene glycol butyl ether, and the mixture was dissolved at a temperature of 110 C with stirring. After cooling the mixture to 60 C, 105 parts of diethanolamine was added, and reaction was carried out at a temperature of 120 C for 2 hours. Thereafter, 462 parts of mercaptobenzoic acid was added, and reaction was carried out at a temperature of 170 C for 5 hours to obtain Compound A-3 having an acid value of 1.5.
Production example 4 To the same 3-liter four-necked flask as used in Production example l were added 1100 parts of a polyesterpolyol 20~8~ 9 4 resin having a hydroxyl value of 215 mg KOH/g (Nippolan 1100i a product of Nippon Polyurethane Co., Ltd.) and 472 parts of methyl isobutyl ketone, and the mixture was dissolved at a temperature of 70 C with stirring.
Separately from this, 340 parts of methyl isobutyl ketone and 348 parts of 2,4-tolylenediisocyanate were added to a similar 2-liter four-necked flask, and 376 parts of a methyl isobutyl ketone solution (solid content, 91.5%) of a ketimine compound prepared from l mole of monomethylaminopropylamine and l mole of methyl isobutyl ketone was added dropwise at a temperature of 25 to 30 C over 60 minutes with stirring to prepare a semi-blocked isocyanate compound. This compound was gradually added to the above polyesterpolyol resin solution, and reaction was carried out O
at a temperature of 70 C for 3 hours to obtain Compound A-4.
Production examples for active double bond-containing compound (B) :
Production example 5 To the same 3-liter four-necked flask as used in Production example l were added 1000 parts of an epoxidized polybutadiene resin having an oxirane oxygen content of 6.5% and a number average molecular weight of 1800 (E-1800-6.5; a product of Nisseki Kagaku Co., Ltd.), 377 parts of ethylene glycol butyl ether and 131 parts of methylethanolamine, and reaction was carried out at a temperature of 170 C for 6 hours in a nitrogen gas stream. After cooling the reaction solution to 120 C, * Trade Mark B ~ -15--... .
81.4 parts of acrylic acid, 8.8 parts of hydroquinone and 27.1 parts of ethylene glycol ethyl ether were added, and reaction was carried out at a temperature of 120 C for 4 hours to obtain an active double bond-containing compound B-1.
Production example 6 To a l-liter four-necked flask similar to that used in Production example l were added 196 parts of maleic acid anhydride and 232 parts of 2-hydroxyethyl acrylate, and then 0.9 part of triethylamine was added at a temperature of 65 C. Reaction was carried out at the same temperature for l hour to prepare a compound having an acid value of 260 mg KOH/g.
To an another 3-liter four-necked flask were added 1200 parts of a novolak-type epoxy resin having an epoxy equivalent of 180, 514 parts of ethylene glycol butyl ether and 490 parts of diethanolamine, and reaction was carried out at a temperature of o 90 C for 1.5 hours. Thereafter, 428 parts of the above compound prepared from maleic acid anhydride and 2-hydroxyethyl acrylate and 2 parts of hydroquinone were added, and reaction was carried out at a temperature of 120 C for 3 hours to obtain Compound B-2 having an acid value of 0.5.
Production example 7 514 Parts of toluene was added to the same 3-liter four-necked flask as used in Production example l and refluxed at a ~temperature of about 110 C. Separately from this, 200 parts of 2 o o ~ ~ ~ 4 n-butyl acrylate, 400 parts of methyl methacrylate, 400 parts of 2-hydroxyethyl methacrylate and 50 parts of di-tert-butyl peroxide were added to an another flask and mixed with stirring.
The resulting mixture was added dropwise to the above flask over 3 hours under reflux of toluene. Thereafter, reaction was continued at a temperature of 115 C for 2 hours, followed by cooling to 80 C.
Subsequently, 294 parts of maleic acid anhydride and 10 parts of tributylamine were added, and reaction was carried out at a temperature of 100 C for 4 hours to obtain a reaction product having an acid value of 130 mg KOH/g. Thereafter, 426 parts of glycidyl methacrylate was added and reaction was carried out at a temperature of 120 C for 4 hours to obtain Compound B-3 having an acid value of 3.5 mg KOH/g.
Production examples for inner-crosslinked micro-resin particles :
Production example 8 To the same 3-liter four-necked flask as used in Production example 1 were added 1067 parts of Compound B-l, 300 parts of a modified aliphatic polyamine having an amine value of 345 mg KOH/g (Adeka Hardener EH-266, a product of Asahi Denka Co., Ltd.) and 325 parts of isopropanolamine, and the contents of forO30 minutes the flask were mixed at a temperature of 60 C~with stirring.
During this period, 2500 parts of pure water and 15 * Trade Mark --17--B t 20~8194 ,.. ..
parts of acetic acid were added to a 4-liter stainless steel cylindrical container and kept at a temperature of 60 C while stirring with a disper. To this aqueous acetic acid solution was gradually added 621 parts of the above resin mixture over 20 minutes. Thereafter, stirring was continued at a temperature of 60 C for 3 hours to obtain a water dispersion H of inner-crosslinked micro-resin particles.
The solid content of this water dispersion was 20%, and the base value was 1.7 mg equivalent/g. On measuring the particle size on a particle size-measuring instrument (LP 3000/
3100; a product of Otsuka Denshi Co., Ltd.) according to the laser scattering method, the particle size was 0.1 ~. The content of insoluble matter of the water dispersion was measured by adding THF to the dispersion and centrifuging, and as a result, the content was found to be 95% of the total solid content (herein-after referred to as gel ratio).
Production example 9 To the same 3-liter four-necked flask as used in Production example 1 were added 1428 parts of Compound A-l, 666 parts of Compound B-l and 406 parts of ethylene glycol butyl ether, o and the contents of the flask were mixed at a temperature of S0 C
for l hour, after which 13.8 parts of formic acid was added.
After mixing for 10 minutes, 833 parts of the resulting resin mixture was gradually added to 2500 parts of pure water over 20 ", .
minutes in the same manner as in Production example 8, and stirring was continued at a temperature of 60 C for 3 hours to obtain a water dispersion I of inner-crosslinked micro-resin particles. The solid content of the water dispersion was 20%, the base value was 2.9 mg equivalent/g, the particle size was 0.3~-, and the gel ratio was 88%.
Production example lO
To a 5-liter four-necked flask similar to that used in Production example l were added 400 parts of Compound A-2, 500 parts of Compound B-2, 330 parts of ethylene glycol ethyl ether and 19.2 parts of acetic acid, and the contents of the flask were mixed at a temperature of 60 C for 2 hours with stirring.
Thereafter, 1950 parts of pure water was gradually added, and stirring was continued at a temperature of 80 C for 3 hours to obtain a water dispersion J of inner-crosslinked micro-resin particles having a particle size of 0.2~l. The solid content of this water dispersion was 25%, the gel ratio thereof was 80%, and the base value was 1.0 mg equivalent/g.
Production example 11 To the same 3-liter four-necked flask as used in Production example 1 were added 1265 parts of Compound A-3, 667 parts of Compound B-3, 568 parts of isopropanol and 19.3 parts of formic acid, and the contents of the flask were mixed at a tempe-rature of 80 C for 1 hour with stirring. Thereafter, in the same manner as in Production example 8, 840 parts of the resulting resin mixture was added over 20 minutes to 2500 parts of pure water kept at a temperature of 60 C in a 4-liter stainless steel container, and the mixture was kept at the same temperature for 3 hours to obtain a water dispersion K of inner-crosslinked micro-resin particles. The solid content of the water dispersion was 20%, the particle size was 1.1/~, and the base value was 0.4 mg equivalent/g. The gel ratio of the water dispersion was 85%.
Production example 12 To a 5-liter four-necked flask similar to that used in Production example l were added 1470 parts of Compound A-4, 102 parts of trimethylolpropane triacrylate and 123 parts of ethylene glycol ethyl ether, and the contents of the flask were mixed at a temperature of 50 C for l hour with stirring. Thereafter, a mixture of 2673 parts of pure water and 40 parts of lactic acid was gradually added over 30 minutes, after which stirring was continued at a temperature of 70 C for 4 hours to obtain a water dispersion L of inner-crosslinked micro-resin particles.
The solid content of the water dispersion was 25%, the particle size was 0.8/l" and the base value was 2.2 mg equivalent/g.
The gel ratio of the water dispersion was 98%.
Production example 13 To the same 3-liter four-necked flask as used in Production example l were added 1250 parts of Compound B-2 and " ,=, lO0 parts of trimethylolpropane trimercaptopropionate, and the contents of the flask were mixed at a temperature of 80 C for 2 hours. Thereafter, 614 parts of the resulting resin mixture was gradually added over 20 minutes to a mixture, kept at a temperature of 70 C, of 1877 parts of pure water and 9 parts of acetic acid. Stirring was then continued at a temperature of 60 C for 3 hours to obtain a water dispersion M of inner-crosslinked mincro-resin particles. The solid content of the water dispersion was 20%, the particle size was 0.5~, and the base value was 2.0 mg equivalent/g. The gel ratio of the water dispersion was 90%.
Production example 14 To the same 3-liter four-necked flask as used in Production example l were added 1333 parts of Compound B-3 and 259 parts of ethylene glycol butyl ether, and 100 parts of triethylenetetramine was added at a temperature of 60 C with stirring. Stirring was then continued at a temperature of 60 C for further 30 minutes. In the same manner as in Production example 8, 769 parts of the resulting resin mixture was added over 15 minutes to a mixture, kept at a temperature of 55 C, of 1718 parts of pure water and 12.6 parts of formic acid, and stirring was continued at a temperature of 35 C for 3 hours to obtain a water dispersion N of inner-crosslinked micro-resin particles. The solid content of the water dispersion was 18%, ~8~ 9 4 the particle size was 1.7 ~, and the base value was 2.5 mg equivalent/g. The gel ratio of the water dispersion was 93%.
Production examples for cationic aqueous resin and its water dispersion :
Production example 15 1900 Grams of Epikote #1004*(epibis-epoxy resin; a product of Shell Co.) was dissolved in 700 g of ethylene glycol ethyl ether in a clean 4-liter four-necked flask. After adding 200 g of diethanolamine, the resulting mixture was kept at a temperature of 60 C to 65 C for l hour, heated to 120 C and then kept at the same temperature for l hour. Subsequently, after cooling the mixture to 80 C, 500 g of a blocked isocyanate-type curing agent (EH-117-20; a product of Asahi Denka Co., Ltd.) was added. The resulting mixture was thoroughly mixed while keeping it at a temperature of 80 C to 85 C for l hour to obtain a cationic aqueous resin. Thereafter, 45 g of the above resin, 45 g of ethylene glycol ethyl ether, 135 g of titanium oxide, 7 g of carbon black and 300 g of glass beads were put in a l-liter mayonnaise bottole and finely pulverized on a quick mill to obtain a pigment dispersion. 540 Grams of the above aqueous resin, 232 g of the pigment dispersion and 8.5 g of formic acid were added to a 4-liter stainless steel vat and thoroughly mixed together with 2179.5 g of deionized water while gradually adding the deionized water and stirring with a disper. Thus, a cationic water * Trade Mark --22--B ~ -200819~
dispersion O having a solid content of 20% was obtained.
Production example 16 45 Grams of the above cationic aqueous resin, 45 g of ethyl cellosolve, 120 g of titanium oxide, 7 g of carbon black, 35 g of basic lead silicate and 300 g of glass beads were put in a l-liter mayonnaise bottle and finely pulverized on a quick mill to obtain a pigment dispersion.
Thereafter, 540 g of the above cationic resin, 252 g of the pigment dispersion and 8.5 g of formic acid were added to a 4-liter stainless steel vat and thoroughly mixed together with 2259.5 g of deionized water while gradually adding the deionized water and stirring with a disper. Thus, a cationic water dispersion P having a solid content of 20% was obtained.
Examples 1 to 9 and Comparative examples l and 2 The inner-crosslinked micro-resin particles H to N and the water dispersions O and P of the cationic aqueous resin were mixed in the prescribed proportions to prepare cationic electrodeposition paints. Dull steel plate treated with zinc phosphate and the edge of a cutter knife (a product of Co.) were subjected to cationic electrodeposition coating.
The appearance and the results of the salt spray test are shown in Table 1.
200819~
a) ~ ,-- o ~ ~ N P~ ~ ¦ O O
O ~ O ~ ~1 a) z c~
QJ
~ E O ~ ao o E ~ ~ O ~ I o o . o O X O ~ O ~'1 t' Z
U~
Z ~ O O ~
O ~
o o ~ o O
~ oo [_ Pl H ~ ~ ~ ~
~I O
o ~
~ O
a) .,, E ~ Ln U~ O 1~ ~ o O ~
E O ~'1 0 ~1S t~l X
(~ ~ O H ~1 0 0 0 ~ ~
E-~ o ~ o (~
r~ c7 O X U~ O O ~ O
O
O ~ ~ O O ~
O
U~
O ~: ~ O O ~
~ O
o z ~ a o a) *
O 0 4 0 0~~ O aJ ~~1 ~
h ~ 1 u~ V u~ *
~) u.-~ ~.) ~uj ~: a) o r ~ *
~I) Ul E ~ ~ ~ ~ u~
UJ r F 4(a ~1 0 a u~ o u~ r oc, a) F F I O ~ G~ l u~ O I
O O h S- ~,1F. F I
J C ~ ~ ~- E E ~ a)-~
~,, Note :
*l Weight ratio (%) of the solid content of micro-resin particle to that of cationic electrodeposition paint.
*2 The flat portion of the test plate is cross-cut and salt spray-tested for 960 hours according to JIS Z 2371, and the width (mm) of rust formed from the cut portion is measured.
*3 The edge of the foregoing cutter knife is coated so that the film thickness on the flat portion is 20 ~, and baked as determined to make a test plate. The knife is set in a salt spray tester so that the edge turns up and salt spray-tested for 168 hours according to JIS Z 2371, and the number of rusts at the edge portion is counted.
According to the present invention, cationic electro-deposition films having excellent edge-corrosion resistance are obtained with the same good appearance and corrosion resistance as ever being maintained.
Claims (4)
1. A composition for cationic electrodeposition coating which contains an aqueous dispersion of a cationic aqueous resin and inner-crosslinked micro-resin particles, said inner-crosslinked micro-resin particles comprising an inner-crosslinked addition polymer of a compound (A) having at least two active hydrogens per molecule and a compound (B) having at least two active double bonds per molecule and having cationic groups contained in an amount of 0.3 to 3 milligram equivalents per gram of the inner-crosslinked micro-resin particles.
2. A composition according to Claim 1 wherein the compound (A) has at least two active hydrogen-containing groups in the molecule.
3. A composition according to Claim 1 wherein the compound (B) has at least two .alpha., .beta.-ethylenic double bonds adjacent to carbonyl group in the molecule.
4. A composition according to Claim 1 wherein the cationic groups contained in the inner-crosslinked micro-resin particles are amino groups contained in at least one of compound (A) and compound (B).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26488/89 | 1989-02-03 | ||
| JP1026488A JP2686635B2 (en) | 1989-02-03 | 1989-02-03 | Cationic electrodeposition coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2008194A1 CA2008194A1 (en) | 1990-08-03 |
| CA2008194C true CA2008194C (en) | 1999-06-01 |
Family
ID=12194889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002008194A Expired - Fee Related CA2008194C (en) | 1989-02-03 | 1990-01-19 | Composition for cationic electrodeposition coating |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5135969A (en) |
| EP (1) | EP0381347B1 (en) |
| JP (1) | JP2686635B2 (en) |
| CA (1) | CA2008194C (en) |
| DE (1) | DE69032299T2 (en) |
| ES (1) | ES2116266T3 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2793253B2 (en) * | 1989-05-18 | 1998-09-03 | 日産自動車株式会社 | Composite coating |
| DE3932816A1 (en) * | 1989-09-30 | 1991-04-11 | Hoechst Ag | USE OF CROSS-LINKED POLYMER MICROPARTICLES IN LACQUERS AS A FILLER REPLACEMENT AND / OR AS A CROSS-LINKING FILLER |
| KR960014106B1 (en) * | 1990-06-06 | 1996-10-14 | 바스프 락케+파르벤 악티엔게젤샤프트 | Process for coating electrically conductive substrates aqueous enamel and crosslinking agent containing blocked nco groups |
| DE4227030A1 (en) * | 1992-08-14 | 1994-02-17 | Basf Lacke & Farben | Polymers suitable as binders |
| WO2003072614A2 (en) * | 2002-02-28 | 2003-09-04 | Showa Denko K.K. | Thiol compound, photopolymerization initiator composition and photosensitive composition |
| TW200508286A (en) | 2003-03-25 | 2005-03-01 | Nippon Paint Co Ltd | Method of producing oil-in-water type emulsoid containing internally crosslinked fine resin particle, oil-in-water type emulsoid containing internally crosslinked fine resin particle, cation electrodeposition coating composition and substance coated |
| DE10335250B3 (en) * | 2003-08-01 | 2005-05-25 | Bayer Materialscience Ag | Polymer dispersions in polyester polyols |
| DE10357895A1 (en) * | 2003-12-11 | 2005-07-07 | Bayer Materialscience Ag | Polymer dispersions in polyester polyols |
| KR20070028301A (en) * | 2004-01-14 | 2007-03-12 | 닛본 페인트 가부시끼가이샤 | Cationic electrodeposition coating composition |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT351124B (en) * | 1977-11-03 | 1979-07-10 | Vianova Kunstharz Ag | PROCESS FOR THE MANUFACTURING OF CATIONIC BINDERS FOR WATER-DILUTABLE HEAT-TURNABLE COATING AGENTS |
| US4231907A (en) * | 1978-12-22 | 1980-11-04 | Grow Group Inc. | Cathodic electrodeposition compositions employing fatty acid derivatives |
| WO1982000148A1 (en) * | 1980-07-03 | 1982-01-21 | Australia Ltd Dulux | Dispersion process and product |
| DE3044447C2 (en) * | 1980-11-26 | 1982-12-09 | Basf Farben + Fasern Ag, 2000 Hamburg | Process for coating an electrically conductive substrate connected as a cathode and aqueous dispersion therefor |
| JPS5859266A (en) * | 1981-10-05 | 1983-04-08 | Nippon Paint Co Ltd | Water paint composition |
| JPS5840369A (en) * | 1981-09-02 | 1983-03-09 | Nippon Paint Co Ltd | Water paint composition |
| US4461870A (en) * | 1982-01-27 | 1984-07-24 | Nippon Paint Co., Ltd. | High solid coating composition containing novel microparticles of crosslinked copolymer including amphoionic groups |
| JPS60229968A (en) * | 1984-04-28 | 1985-11-15 | Nippon Oil Co Ltd | Cathode-deposition electrodeposition coating composition |
| JPS614761A (en) * | 1984-06-18 | 1986-01-10 | Nippon Paint Co Ltd | Fine resin particle containing crosslinking reaction promotor and method for using the same |
| JPH0786125B2 (en) * | 1985-10-09 | 1995-09-20 | 日本ペイント株式会社 | Reactive fine resin particles, method for producing the same, and cured composition |
| JPH0647658B2 (en) * | 1985-12-25 | 1994-06-22 | 日本ペイント株式会社 | Paint composition |
| JPH0759679B2 (en) * | 1986-02-25 | 1995-06-28 | 大日本塗料株式会社 | Cathode electrodeposition coating composition |
| JPS6341570A (en) * | 1986-08-06 | 1988-02-22 | Nippon Paint Co Ltd | Electrodeposition coating composition |
| AU590960B2 (en) * | 1986-09-04 | 1989-11-23 | Nippon Paint Co., Ltd. | Electrodeposition coating composition |
| CA1301393C (en) * | 1986-11-28 | 1992-05-19 | Yasuyuki Tsuchiya | Cationic micro gel particle dispersion and a coating composition therefrom |
-
1989
- 1989-02-03 JP JP1026488A patent/JP2686635B2/en not_active Expired - Fee Related
-
1990
- 1990-01-19 CA CA002008194A patent/CA2008194C/en not_active Expired - Fee Related
- 1990-01-22 ES ES90300629T patent/ES2116266T3/en not_active Expired - Lifetime
- 1990-01-22 DE DE69032299T patent/DE69032299T2/en not_active Expired - Fee Related
- 1990-01-22 EP EP90300629A patent/EP0381347B1/en not_active Expired - Lifetime
- 1990-01-23 US US07/468,667 patent/US5135969A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0381347B1 (en) | 1998-05-13 |
| EP0381347A1 (en) | 1990-08-08 |
| ES2116266T3 (en) | 1998-07-16 |
| DE69032299D1 (en) | 1998-06-18 |
| JPH02206660A (en) | 1990-08-16 |
| CA2008194A1 (en) | 1990-08-03 |
| JP2686635B2 (en) | 1997-12-08 |
| US5135969A (en) | 1992-08-04 |
| DE69032299T2 (en) | 1998-12-10 |
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