Resin composition for aqueous paint

A resin composition for aqueous paint contains, as main components, (A) a resin obtained by reacting a certain epoxy resin, an amine compound and a phenol compound and substantially containing neither primary or secondary amino group nor epoxy group; (B) a resin having phenolic hydroxyl groups and substantially containing neither primary nor secondary amino group, and (C) a resin compound having glycidyl groups or epoxy groups. The composition is excellent in dispersibility of each component and in storage stability. It has an extremely low heating loss of the coating film, and is excellent in smoothness, corrosion resistance, adhesion, etc.

This invention relates to a resin composition for aqueous paint, and, in 
particular, relates to a resin composition for aqueous paint such that 
when it is applied as a resin composition for cationic electrodeposition 
coating composition, it becomes unnecessary to use a blocked isocyanate 
compound (curing agent), an organotin compound (curing catalyst) or the 
like, which has so far been used. As a result, the heating loss of the 
coating film is reduced, catalyst-poisoning resistance, etc. are enhanced, 
and moreover the adhesion, weather resistance, low temperature curability, 
etc. of the coating film are improved. 
Heretofore, as resin compositions for cationic electrodeposition coating 
composition, there have widely been used those containing as main 
components a polyamine resin (substrate resin) such as an amine addition 
epoxy resin and a blocked polyisocyanate compound (curing agent). These 
resin compositions are good in the corrosion resistance of the coating 
film, but have grave drawbacks, as intrinsic problems, for example that 
the curing initiation temperature of the coating film is high (170.degree. 
C. or higher); when an organotin compound (curing catalyst) is used in 
order to lower the curing initiation temperature, the tin compound 
sometimes poisons the exhaust gas combustion catalyst of the kiln; when 
the coating film is heated at a high temperature in order to cure it, the 
blocked polyisocyanate compound thermally decomposes and gum, soot, etc. 
occur, and moreover the yellowing, bleeding and curing inhibition of the 
topcoat film are caused and weather resistance is lowered. Improvement on 
these points has strongly be desired. 
On the other hand, cationic electrodeposition coating compositions using no 
curing agent and using a self-crosslinkable resin based on the ring 
opening reaction of the epoxy groups are proposed, for example, in GB 
1306101, GB 1306102 and CA 904202 (Japanese Patent Publication No. 
31736/1974), GB 1327071 (Japanese Patent Publication No. 23807/1974), GB 
1411249 (Japanese Laid-Open Patent Publication No. 69896/1973), U.S. Pat. 
No. 4,001,101 (Japanese Laid-Open Patent Publication No. 13432/1972), 
etc., but it is difficult in all of them to make the bath stability of the 
electrodeposition coating composition and the curability of the coating 
film compatible. For example, glycidyl ether type polyepoxy compounds most 
general among them are excellent in the curability of the coating film but 
have a drawback of poor bath stability. 
The present inventors had intensely studied for development of cationic 
electrodeposition coating compositions wherein the above drawbacks are 
obviated, and as a result they found that specific epoxy compounds wherein 
epoxy groups bind directly to the alicyclic skeleton are useful as a 
curing agent for cationic electrodeposition coating compositions 
substituting for the blocked polyisocyanate compounds, and proposed 
previously (EP-B-356970). However, it has been revealed that there are 
some points to be improved, for example that since the amine concentration 
is high, acid concentration in the bath lowers, and since the residual 
amine concentration in the cured coating film is high, anticorrosive 
properties against untreated steel plates is not sufficient. 
The object of this invention is to provide a cationic electrodeposition 
coating composition free of the necessity of use of a blocked 
polyisocyanate compound or an organic tin compound, having a low amine 
concentration therein and excellent in anticorrosive properties against 
untreated steel plates, having good acid concentration stability in 
bathes, excellent in dispersibility in water and having only a small 
heating loss at the time of the curing of the coating film with heating. 
According to this invention there is provided a resin composition for 
aqueous paint which contains as main components 
(A) a resin intrinsically containing neither a primary or secondary amino 
group nor an epoxy group and obtained by reacting an epoxy resin (A-1-1) 
having per molecule at least three epoxy group-containing functional 
groups represented by the following formula (I) 
##STR1## 
wherein m is an interger of 2 to 4, and/or a novolak phenol type glycidyl 
ether group-containing resin (A-1-2) having per molecule at least three 
glycidyl ether groups and represented by the following formula (II) 
##STR2## 
wherein R.sub.1 and R.sub.2, which are the same or different, 
independently represent a hydrogen atom, an alkyl group having 1 to 8 
carbon atoms, an aryl group, an aralkyl group or a halogen atom, 
R.sub.3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon 
atoms, an aryl group, an aralkyl group, an allyl group or a halogen atom, 
R.sub.4 and R.sub.6, which are the same or different, independently 
represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, 
R.sub.5 represents a hydrogen atom, an alkyl group having 1 to 10 carbon 
atoms, an aryl group, an aralkyl group, an allyl group or a halogen atom, 
and 
n is an integer of 1 to 38, 
a primary or secondary amine compound (A-2) having per molecule at least 
one primary hydroxyl group, and a phenol compound (A-3) having per 
molecule at least one phenolic hydroxyl group; 
(B) a resin containing per molecule at least two phenolic hydroxyl groups 
or at least two in total of phenolic hydroxyl groups and primary hydroxyl 
groups originating in an alkanolamine, and intrinsically containing 
neither primary nor secondary amino groups; and 
(C) at least one component selected from the group consisting of a novolak 
phenol type glycidyl ether group-containing resin (C-1) represented by the 
following formula (III) 
##STR3## 
wherein R'.sub.1 and R'.sub.2, which are the same or different, 
independently represent a hydrogen atom, an alkyl group having 1 to 8 
carbon atoms, an aryl group, an aralkyl group or a halogen atom, 
R'.sub.3 represents a halogen atom, an alkyl group having 1 to 10 carbon 
atoms, an aryl group, an aralkyl group, an allyl group or a halogen atom, 
R'.sub.4 and R'.sub.6, which are the same or different, independently 
represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, 
R'.sub.5 represents an alkyl group having 1 to 10 carbon atoms, an aryl 
group, an aralkyl group, an allyl group or a halogen atom, and 
n' is an integer of 1 to 38, 
an epoxy resin (C-2) having per molecule at least three epoxy 
group-containing functional groups represented by the following formula 
(IV) 
##STR4## 
wherein p is an integer of 2 to 4, and a compound (C-3) having per 
molecule two or more glycidyl groups originating in glycidylamino groups 
directly binding to the carbon atom of the aromatic ring and represented 
by the following formula (V) 
##STR5## 
wherein R is a hydrogen atom or a glycidyl group. 
The resin composition for aqueous paint of this invention is described in 
more detail below. 
Component (A); 
A resin having primary hydroxyl groups and cationic groups but 
intrinsically containing neither a primary or secondary amino group nor an 
epoxy group, obtained by reacting an epoxy resin (A-1-1) having per 
molecule at least three epoxy group-containing functional groups and 
represented by the above formula (I) and/or a novolak phenol type glycidyl 
ether group-containing resin (A-1-2) having per molecule at least three 
glycidyl ether groups and represented by the above formula (II), a primary 
or secondary amine compound (A-2) having per molecule at least one primary 
hydroxyl group, and a phenol compound (A-3) having per molecule at least 
one phenolic hydroxyl group. 
Description is made first about the above component (A-1-1), component 
(A-1-2), component (A-2) and component (A-3). 
Component (A-1-1): 
An epoxy resin having per molecule at least three epoxy group-containing 
functional groups represented by the following formula 
##STR6## 
wherein m is an integer of 2 to 4. 
As such epoxy resin components (A-1-1), there can be used those known per 
se and disclosed, for example, in Japanese Laid-Open Patent Publication 
No. 170620/1985, Japanese Laid-Open Patent Publication No. 135467/1987, 
Japanese Laid-Open Patent Publication No. 166675/1985, Japanese Laid-Open 
Patent Publication No. 161973/1985, U.S. Pat. No. 4,565,859, etc. 
Further, the components (A-1-1) include those wherein the residue of the 
polymerization initiator component, namely the active hydrogen-containing 
organic compound residue binds to the terminus of the above formula (I), 
and as examples of the active hydrogen-containing organic compound which 
is its precursor, there can, for example, be mentioned alcohols, phenols, 
carboxylic acids, amines, thiols, etc. 
Among them, alcohols may either be monohydric alcohols or polyhydric 
alcohols including dihydric or higher alcohols, and, specifically, there 
can be exemplified aliphatic monohydric alcohols such as methanol, 
ethanol, propanols, butanols, pentanols, hexanols and octanols; aromatic 
monohydric alcohols such as benzyl alcohol; polyhydric alcohols such as 
ethylene glycol, diethylene glycol, triethylene glycol, polyethylene 
glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 
1,4-butanediol, pentanediols, 1,6-hexanediol, neopentyl glycol, oxypivalic 
acid neopentyl glycol ester, cyclohexanedimethanol, glycerol, diglycerol, 
polyglycerol, trimethylolpropane, trimethylolethane, pentaerythritol and 
dipentaerythritol; etc. 
As phenols, there can, for example, be mentioned phenol, cresol, catechol, 
pyrogallol, hydroquinone, hydroquinone monomethyl ether, bisphenol A, 
bisphenol F, 4,4'-dihydroxybenzophenone, bisphenol S, phenol resins, 
cresol novolak resins, etc. 
As carboxylic acids, there can be exemplified formic acid, acetic acid, 
propionic acid, butyric acid, fatty acids from animal and vegetable oils, 
fumaric acid, maleic acid, adipic acid, dodecanedioic acid, trimellitic 
acid, pyromellitic acid, polyacrylic acid, phthalic acid, isophthalic 
acid, terephthalic acid, etc., and there can also be used compounds having 
both hydroxyl groups and carboxyl groups such as lactic acid, citric acid 
and oxycaproic acid. 
Further, as other compounds having active hydrogen(s), there can be used 
polyvinyl alcohols, partial hydrolyzates of polyvinyl acetates, starches, 
cellulose, cellulose acetate, cellulose acetate butyrate, 
hydroxyethylcellulose, allylpolyol resins, styrene-allyl alcohol copolymer 
resins, styrene-maleic acid copolymer resins, alkyd resins, polyester 
polyol resins, polycaprolactone polyol resins, etc. Further, compounds 
having active hydrogen(s) may have an unsaturated double bond together 
with the active hydrogen(s) in the skeleton, and may be those having such 
a structure that the double bond is epoxidized. 
A component (A-1-1) can, for example, be obtained by subjecting a 
vinylcycloalkene oxide represented by the formula (VI) 
##STR7## 
wherein m is an integer of 2 to 4, for example, 
4-vinylcyclohexene-1-oxide, either alone or in coexistence with another 
epoxy group-containing compound, to ring opening (co)polymerization 
through epoxy groups contained therein, using the above active 
hydrogen-containing organic compound as the initiator, to form a polyether 
resin, and then epoxidizing vinyl groups existing in the side chains of 
the resin and originating in the above vinylcycloalkene oxide, with an 
oxidizing agent such as a peroxide or a hydroperoxide or the like, to 
introduce a functional group represented by the above formula (I). 
4-vinylcyclohexene-1-oxide can, for example, be obtained by partially 
epoxidizing with peracetic acid vinylcyclohexene obtained by dimerization 
reaction of butadiene. Further, vinylcyclopentene-1-oxide or 
vinylcyclobutene-1-oxide can be obtained by partially epoxidizing 
vinylcyclopentene or vinylcyclobutene with peracetic acid. 
As for other epoxy group-containing compounds, there is no particular 
limitation so long as they are compounds having an epoxy group, but 
compounds having one epoxy group in one molecule are preferred in view of 
their preparation, and, specifically, there can be mentioned 
.alpha.-olefin epoxides represented by the formula 
##STR8## 
wherein L is an integer of 2 to 25, such as ethylene oxide, propylene 
oxide and butylene oxide; oxides of unsaturated compounds such as styrene 
oxide; glycidyl ethers of compounds having a hydroxyl group such as allyl 
glycidyl ether, 2-ethylhexyl glycidyl ether, methyl glycidyl ether, butyl 
glycidyl ether and phenyl glycidyl ether; glycidyl esters of organic acids 
such as fatty acids; etc. 
Further, cyclic epoxy group-containing compounds represented by the 
following formulae (1) to (12) can also be used as other epoxy 
group-containing compounds. 
##STR9## 
In each of the above formulae, R.sub.11 represents a hydrogen atom or a 
methyl group, R.sub.12 represents a divalent aliphatic saturated 
hydrocarbon group having 1 to 6 carbon atoms, and R.sub.13 represents a 
divalent hydrocarbon group having 1 to 10 carbon atoms. 
In the above, as the divalent aliphatic saturated hydrocarbon group having 
1 to 6 carbon atoms represented by R.sub.12, there can be mentioned a 
straight-chain or branched alkylene group such as, for example, a 
methylene, ethylene, propylene, tetramethylene, ethylethylene, 
pentamethylene or hexamethylene group. Further, as the divalent 
hydrocarbon group having 1 to 10 carbon atoms represented by R.sub.13, 
there can, for example, be mentioned a methylene, ethylene, propylene, 
tetramethylene, ethylethylene, pentamethylene, hexamethylene, 
polymethylene, phenylene, 
##STR10## 
group, or the like. 
Further, there can also, for example, be used as other epoxy 
group-containing compounds compounds represented by the following general 
formula (VII) 
##STR11## 
wherein R.sub.11 and R.sub.12 have the same meanings as defined above, for 
example, glycidyl acrylate and glycidyl methacrylate; and alicyclic 
unsaturated compounds accessorily produced by partial epoxidation of 
vinylcyclohexene and represented, for example, by the following formula 
(VIII) 
##STR12## 
Further, 4-vinylcycloheptene (vinylnorbornene), etc. can also be used. 
The ring opening (co)polymerization reaction of epoxy groups of the 
vinylcycloalkene oxide of the above formula (VI), for example 
4-vinylcyclohexene-1-oxide alone or in coexistence of another epoxy 
group-containing compound is preferably carried out in the presence of the 
active hydrogen-containing organic compound using a catalyst. As usable 
catalysts, there can, for example, be mentioned amines such methylamine, 
ethylamine, propylamine and piperazine; organic bases such as pyridines 
and imidazoles; organic acids such as formic acid, acetic acid and 
propionic acid; inorganic acids such as sulfuric acid and hydrochloric 
acid; alkali metal alcoholates such as sodium methylate; alkalis such as 
KOH and NaOH; Lewis acids such as BF.sub.3, ZnCl.sub.2, AlCl.sub.3 and 
SnCl.sub.4 or their complexes; and organometallic compounds such as 
triethylaluminum and diethylzinc. 
These catalysts can be used in the range of 0.001 to 10 wt. %, preferably 
0.1 to 5 wt. % based on the reactants. Temperature for the ring opening 
(co)polymerization is generally -70.degree. to 200.degree. C., preferably 
-30.degree. to 100.degree. C. The reaction can be carried out using a 
solvent and it is preferable to use as the solvent an ordinary organic 
solvent having no active hydrogen. 
By epoxidizing the vinyl groups contained in the side chains of the thus 
obtained polyether resin (ring opening (co)polymer), the functional group 
represented by the above structural formula (I) can be introduced to 
obtain a component (A-1-1). The epoxidation can be carried out using a 
peracid, a hydroperoxide or the like. There can be used as peracids, for 
example performic acid, peracetic acid, perbenzoic acid, 
pertrifluoroacetic acid or the like, and as hydroperoxides, for example 
hydrogen peroxide, tert-butyl peroxide, cumene peroxide or the like. The 
epoxidation reaction can, if necessary, be carried out using a catalyst. 
By epoxidizing the vinyl group in the vinylalkene oxide of the formula 
(VI), for example 4-vinylcyclohexene-1-oxide, the functional group 
represented by the above structural formula (I) is formed. When the above 
alicyclic oxirane group-containing compound or the like coexists as 
another epoxy group-containing compound in this epoxidation reaction, the 
vinyl group contained in the compound is sometimes epoxidized, too. 
The use or non-use of a solvent or reaction temperature in the epoxidation 
reaction can appropriately be adjusted depending on an apparatus to be 
used or the physical properties of raw materials. 
Commercial products can also be used as such components (A-1-1), and, for 
example, EHPE 3150 (trade name, produced by DAICEL CHEMICAL INDUSTRIES, 
LTD.) can be mentioned. This is one obtained by epoxidizing the vinyl 
groups in the ring opening polymer of 4-vinylcyclohexene-1-oxide, and has 
an average polymerization degree of 4 to 15. 
The amount of the epoxy group-containing functional group represented by 
the structural formula (I) may be such that three or more such functional 
groups are contained per molecule of the component (A-1-1), and is, in 
terms of epoxy equivalent, in the range of preferably 140 to 1,000, more 
preferably 170 to 300. 
Component (A-1-2): 
Novolak phenol type glycidyl ether group-containing resins having at least 
three glycidyl ether groups per molecule and represented by the following 
formula (II) 
##STR13## 
wherein R.sub.1 and R.sub.2, which are the same or different, 
independently represent a hydrogen atom, an alkyl group having 1 to 8 
carbon atoms, an aryl group, an aralkyl group or a halogen atom; 
R.sub.3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon 
atoms, an aryl group, an aralkyl group, an allyl group or a halogen atom; 
R.sub.4 and R.sub.6, which are the same or different, independently 
represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; 
R.sub.5 represents a hydrogen atom, an alkyl group having 1 to 10 carbon 
atoms, an aryl group, an aralkyl group, an allyl group or a halogen atom; 
and 
n is an integer of 1 to 38. 
In the above general formula (II), "alkyl group" is straight chain or 
branched chain, and includes, for example, methyl, ethyl, propyl, 
isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, hexyl, 
heptyl, octyl, 2-ethylhexyl, nonyl, decyl, etc. groups. "Aryl group" may 
be either monocyclic or polycyclic, and includes, for example, phenyl, 
naphthyl, etc. groups. In particular, a phenyl group is preferred. 
"Aralkyl group" is an aryl-substituted alkyl group of which the aryl and 
alkyl moieties have the aforementioned meanings, respectively. Examples 
thereof include, for example, benzyl, phenethyl, etc. groups, with a 
benzyl group being preferred. 
"Halogen atom" includes a fluorine atom, a chlorine atom, a bromine atom 
and an iodine atom. 
"Organic group having a glycidyloxyphenyl group" which can be represented 
by R.sub.4 and/or R.sub.6 is an organic group having a group represented 
by formula 
##STR14## 
wherein W is a hydrogen atom or alkyl group having 1 to 10 carbon atoms. 
Preferred examples of the organic group include, for example, 
glycidyloxyphenyl, glycidyloxyphenylmethyl, glycidyloxyphenylethyl, 
glycidyloxyphenylpropyl, glycidyloxyphenylbutyl, glycidyloxyphenylpentyl, 
glycidyloxyphenylhexyl, glycidyloxyphenyloctyl, glycidyloxyphenylnonyl, 
etc. groups. 
In the general formula (II), R.sub.1 and R.sub.2 are preferably a hydrogen 
atom, a methyl group, a chlorine atom, or a bromine atom, with a hydrogen 
atom, a methyl group and a bromine atom being particularly preferred. 
R.sub.3 and R.sub.5 are preferably a methyl group, a tert-butyl group, a 
nonyl group, a phenyl group, a chlorine atom or a bromine atom, with a 
methyl group, a tert-butyl group, a phenyl group and a bromine atom being 
particularly preferred. Further, R.sub.4 and R.sub.6 are preferably a 
hydrogen atom, and n is preferably 1 to 25, and more preferably 1 to 8. 
It is preferred that the epoxy resin (A-1-2) has a number average molecular 
weight within the range of generally about 400 to 8,000, particularly 500 
to 3,000 and more preferably 600 to 2,000, as measured by a vapor 
pressure-osomotic pressure method. For this number average molecular 
weight one can calculate a number average repeating unit number (n+2). 
Also, it is preferred that the epoxy resin (A-1-2) has in average 
generally 3.5 to 10, particularly 3.5 to 8, and more particularly 4 to 7, 
glycidyl groups per molecule, and that the epoxy rein (A-1-2) has an epoxy 
equivalent within the range of about 180 to about 2,000, particularly 180 
to 1,000 and more particularly 200 to 600. 
The epoxy resin (A-1-2) can be prepared, for example, by reacting 
epihalohydrin (a-5) with a phenol-novolak type resin (a-4) which is 
obtained by polycondensation reaction between a bifunctional phenyl 
compound (a-1) represented by the following general formula (IX) 
##STR15## 
wherein R.sub.1, R.sub.2 and R.sub.3 have the same meanings as defined 
above, 
and an aldehyde compound (a-2) represented by the following general formula 
(X) 
EQU R.sub.4 --CHO 
wherein R.sub.4 has the same meaning as defined above, 
and/or a ketone compound (a-3) represented by the following general formula 
(XI) 
EQU R.sub.4 --CO--R.sub.6 
wherein R.sub.4 and R.sub.6 have the same meanings as defined above, to 
introduce a glycidyl ether group in the phenol-novolak type resin (a-4). 
During or after the reaction for obtaining the aforementioned 
phenol-novolak resin (a-4), a monofunctional phenol compound (a-6) 
represented by the following general formula (XII) 
##STR16## 
wherein R.sub.7 represents an alkyl group having 1 to 10 carbon atoms, an 
aryl group, an aralkyl group, an allyl group or a halogen atom; and 
R.sub.1 and R.sub.2 have the same meanings as defined above, 
may be used in combination as a terminal blocking agent, as necessary. 
Specific examples of the group represented by R.sub.7 in the formula (XII) 
above include a methyl group, an ethyl group, a propyl group, a n-butyl 
group, a tert-butyl group, a pentyl group, a hexyl group, a nonyl group, 
an ethylene group, a propylene group, a phenyl group, a benzyl group, a 
chlorine atom, a bromine atom, and an iodine atom, with a methyl group, a 
tert-butyl group, a nonyl group, a phenyl group, a chlorine atom, and a 
bromine atom being particularly preferred. 
The term "bifunctional" as used for the phenol compound as component (a-1) 
above means that in general formula (IX), two hydrogen atoms are bonded 
directly to the benzene nucleus at the ortho and/or para-position with 
respect to the hydroxyl group. The hydrogen atoms will react with carbonyl 
group (C.dbd.O) in the components (a-2) and (a-3) above by condensation 
reaction with dehydration to form a phenol-novolak resin (a-4). 
The term "monofunctional" as used for the phenol compound as component 
(a-6) means that in the general formula (XII), one hydrogen atom is bonded 
to the benzene ring at the ortho- or para-position with respect to the 
hydroxyl group. The hydrogen atom will react with carbonyl group (C.dbd.O) 
in the component (a-2) or (a-3) above by condensation reaction with 
dehydration to form terminals of the phenol-novolak type resin (a-4). 
As the bifunctional compound (a-1) represented by the formula (IX) above, 
there can be cited, for example, phenol, p-propenylphenol, o-benzylphenol, 
6-n-amyl-n-cresol, o-cresol, p-cresol, o-ethylphenol, o-phenylphenol, 
p-phenylphenol, p-tert-pentylphenol, p-tert-butylphenol, o-chlorophenol, 
p-chlorophenol, 4-chloro-3,5-xylenol, o-allylphenol, nonylphenol, 
o-bromophenol, p-cumylphenol, etc. 
As the aldehyde compound (a-2) represented by the formula (X) above, there 
can be cited, for example, acetaldehyde, formaldehyde, etc. Also, m- (or 
p-) hydroxybenzaldehyde may be used as the aldehyde compound (a-2), and 
after the reaction with the component (a-1), the hydroxybenzaldehyde may 
be converted to glycidyl ether with the epihalohydrin (a-5). The benzene 
nucleus of the hydroxybenzaldehyde may be substituted with an alkyl group 
having 1 to 10 carbon atoms. 
As the ketone compound (a-3) represented by the formula (XI) above, there 
can be cited, for example, acetone, methyl ethyl ketone, methyl isobutyl 
ketones, etc. Further, use of 2-acetylphenyl-2-hydroxyphenylpropane makes 
it possible to introduce a glycidyloxyphenyl group in the resin 
represented by the formula (II) above. 
This makes at least a portion of 
##STR17## 
Further, as the epihalohydrin (a-5), there can be cited, for example, 
epichlorohydrin, epibromohydrin, etc. 
The phenol-novolak resin (a-4) can be obtained by polycondensing the (a-1) 
component above with the (a-2) and/or (a-3) component above. The 
polycondensation reaction can be performed similarly to an ordinary 
production method for phenol-novolak resin which is known by itself. More 
specifically, the reaction may be performed by a batch method, or by the 
continuous method as described, for example, in Japanese Laid-Open Patent 
Publication No. 130498/1976. For example, the (a-4) component can be 
obtained by blending each component in proportions such that the repeating 
unit number (n) in the formula (II) above is within the range of 1 to 38, 
and the number average molecular weight and epoxy equivalent are within 
the aforementioned ranges, followed by reaction. In this reaction, there 
may be used a catalyst such as inorganic acids, e.g., hydrochloric acid, 
phosphoric acid, sulfuric acid, etc.; organic acids, e.g., 
p-toluenesulfonic acid, oxalic acid, etc.; metal salts, e.g., zinc 
acetate, etc. 
In the production of the (a-4) component, the monofunctional phenol 
compound (a-6) represented by the formula (IX) above may be reacted as a 
terminal blocking agent during or after polycondensation reaction of the 
(a-1) component with the (a-2) component and/or (a-3) component as 
necessary. 
Specific examples of the monofunctional phenol compound (a-6) represented 
by the formula (IX) above include, for example, 
2-tert-butyl-4-methylphenol, 2,4-xylenol, 2,6-xylenol, 2,4-dichlorophenol, 
2,4-dibromophenol, dichloroxylenol, dibromoxylenol, 2,4,5-trichlorophenol, 
6-phenyl-2-chlorophenol, etc. 
The polycondensation of the (a-6) component with the (a-1) component, (a-2) 
component and/or (a-3) component above can be performed in the same manner 
as described above. Novolak-phenol resin obtained using the (a-6) 
component in combination is also included in the category of the (a-4) 
component. 
The (A-1-2) component can be obtained by reacting the (a-5) component with 
phenolic hydroxyl groups in the (a-4) component to convert them into 
glycidyl ether. More specifically, for example, the (a-4) component is 
dissolved in the (a-5) component, and an aqueous solution of an alkali 
metal hydroxide is continuously added to the resulting solution, followed 
by distilling off water and unreacted (a-5) component in the reaction 
mixture. From the distillate can be removed (a-5) component, which can be 
reused. This reaction can be performed preferably in the presence of an 
ether type solvent such as dioxane, diethoxyethane, etc. 
The component (A-1-2) may be one which has been produced as described above 
or one which is commercially available. As such a commercially available 
product, there can be cited, for example, DEN-438 and DEN-439 (trade names 
for products by Dow Chemical Japan Co., Ltd.) as polyglycidyl ether 
product of phenol-novolak resin; EPICRON N-695 (trade names for a product 
by DAI-NIPPON INK AND CHEMICALS INCORPORATED.), ESCN-195XHH (trade names 
for a product by SUMITOMO CHEMICAL CO., LTD.), EOCN-102S, EOCN-1020 and 
EOCN-104S (trade names for a product by NIPPON KAYAKU CO., LTD.) as 
polyglycidyl ether products of cresol-novolak resins; BREN-S (trade name 
for a product by NIPPON KAYAKU CO., LTD.) as polyglycidyl ether product of 
bromine-modified phenol-novolak resin; ESMB-260 (trade name for a product 
by SUMITOMO CHEMICAL CO., LTD.) as polyglycidyl ether product of 
long-chain alkyl-modified phenol-novolak resin; etc. 
Component (A-2): Primary or secondary amine compound having at least one 
primary hydroxyl group per molecule 
This component reacts with the component (A-1-1) and/or (A-1-2) above and 
serves to introduce primary hydroxyl group and basic group(s) in the 
component (A-1-1) and/or (A-1-2). 
Reaction between amino groups in the component (A-2) and glycidyl groups 
represented in the component (A-1-1) and/or (A-1-2) produces cationic 
resin having primary hydroxyl groups and basic groups. The cationic resin 
is superior in water dispersibility and throwing power even after partial 
neutralization or at high pH over the aforementioned conventional cationic 
resin produced by reaction between the conventional bisphenol A type epoxy 
resin, and does not deteriorate curability and corrosion resistance of a 
coating film formed. 
As the component (A-2), there can be cited the following compounds. 
(1) Monoalkanolamines such as monoethanolamine, monopropanolamine, 
monobutanolamine, etc. 
(2) N-Alkylalkanolamines or N,N-dialkanolamines such as 
N-methylethanolamine, N-ethylethanolamine, N,N-diethanolamine, 
N,N-di-n-(or iso-)propanolamine, N,N-dibutanolamine, etc. 
(3) Addition product of monoalkanolamine and .alpha.,.beta.-unsaturated 
carbonyl compound: for example, addition product of monoethanolamine and 
N,N-dimethylaminopropylacrylamide, addition product of monoethanolamine 
and hydroxylethyl (meth)acrylate, addition product of monoethanolamine and 
hydroxypropyl (meth)acrylate, addition product of monoethanolamine and 
hydroxybutyl (meth)acrylate, etc. 
(4) Hydroxyalkylaminoalkylamine such as hydroxyethylaminoethylamine. 
(5) Condensation product between at least one compound selected from 
hydroxyethylamine, hydroxyethylhydrazine and hydroxybutylhydrazine and a 
ketone compound, for example, dimethyl ketone, methyl ethyl ketone, methyl 
isobutyl ketone, dibutyl ketone, dipropyl ketone, etc. 
(6) Amine compound having a primary hydroxyl group, a secondary amino group 
and an amido group in one molecule simultaneously, represented by the 
following general formula (XIII) 
##STR18## 
wherein q is an interger of 1 to 6; 
R.sub.21 is hydrocarbon chain having 4 to 36 carbon atoms which may contain 
a hydroxyl group and/or a polymerizable unsaturated group. 
The amine compound represented by the general formula (XIII) can be 
obtained, for example, by condensation with dehydration between 
N-hydroxyalkylalkylenediamine, and a monocarboxylic acid having 5 to 37 
carbon atoms. As the amine, there can be used preferably diamines having a 
primary hydroxyl group, such as hydroxyetheylaminoethylamine, 
N-hydroxyethylpropylenediamine, N-hydroxyethylbutylenediamine, 
N-hydroxyetheylpentylenediamine, N-hydroxyethylhexylenediamine, etc. As 
the monocarboxylic acid, there can be cited, for example, mixed fatty 
acids such as coconut oil fatty acid, castor oil fatty acid, rice bran oil 
fatty acid, soy bean fatty acid, tall oil fatty acid, dehydrated castor 
oil fatty acid, safflower oil fatty acid, linseed oil fatty acid, and tung 
oil fatty acid; caprylic acid, captic acid, lauric acid, myristic acid, 
palmitic acid, stearic acid, oleic acid, ricinolic acid, rinolic acid, 
rinoleic acid, eleostearic acid, 12-hydroxystearic acid, behenic acid, 
etc. 
The reaction between the aforementioned amine and monocarboxylic acid for 
obtaining the amine compound represented by the formula (XIII) above can 
be performed usually by mixing the both components in equimolar 
proportions, removing a predetermined amount of reaction product water 
using an organic solvent such as toluene or methyl isobutyl ketone, and 
then removing the remaining organic solvent by a vacuum evaporation method 
or the like to obtain an amine compound. It is preferred that the amine 
compound thus obtained has an amine (secondary amine) value within the 
range of generally 88 to 350, particularly 120 to 230, and more 
particularly 130 to 200, and a hydroxyl value, preferably primary hydroxyl 
value (KOH mg/g) within the range of generally 44 to 350, particularly 60 
to 230, and more particularly 65 to 200. 
Among (1) to (6) as the component (A-2), the amine compounds (2), (3) and 
(6) above are preferred. In particular, it is preferred to use the amine 
compound represented by the formula (XIII) (especially 
hydroxyethylaminoethyl fatty acid amide) and diethanolamine in combination 
in order to improve properties of the coated surface such as smoothness 
and corrosion resistance. Preferably, the proportion of the amine compound 
(especially hydroxyethylaminoethyl fatty acid amide) to diethanolamine 30 
to 80% by weight, particularly 40 to 80% by weight, of the former and 70 
to 20% by weight, particularly to 60 to 20% by weight, of the latter based 
on total weight of the both components. 
Component (A-3): Phenol compound having at least one phenolic hydroxyl 
group per molecule 
Phenol compound having a phenolic hydroxyl group as the component (A-1) is 
desirably one which has among others at least one, preferably 1 to 4, and 
more preferably 1 to 2 structural units represented by the following 
general formula (XIV) 
##STR19## 
wherein R.sub.33 and R.sub.34, which are the same or different, 
independently represent a hydrogen atom, an alkyl group having 1 to 10 
carbon atoms, an aryl group, an aralkyl group, an allyl group or a halogen 
atom; 
and the component (A-3) has a number average molecular weight within the 
range of usually 94 to 20,000, particularly 150 to 5,000, and more 
particularly 200 to 3,000. 
Specific examples of the component (A-3) include polyphenol compounds such 
as bis(4-hydroxyphenyl)-2,2-propane, 4,4'-dihydroxybenzophenone, 
bis(4-hydroxyphenyl)-1,1-ethane, bis(4-hydroxyphenyl)-1,1-isobutane, 
bis(4-hydroxy-tert-butylphenyl)-2,2-propane, 
bis(2-hydroxynaphthyl)methane, 1,5-dihydroxynaphthalene, 
bis(2,4-dihydroxyphenyl)methane, 1,1,2,2,-tetrakis(4-hydroxyphenyl)ethane, 
4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone, 
phenol-novolak, and cresol-novolak; monophenol compounds such as phenol, 
nonylphenol, .alpha.- or .beta.-naphthol, p-tert-octylphenol, and o- or 
p-phenylphenol. 
In this invention, the corrosion resistance of a coating film can be 
further increased by the use of compounds component (A-3) containing a 
functional group having a phenolic hydroxyl group, represented by the 
following general formula (XV) 
##STR20## 
wherein R.sub.31 and R.sub.32, which are the same or different, 
independently represent an alkyl group having 1 to 4 carbon atoms, and 
R.sub.33 and R.sub.36, which are the same or different, independently 
represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an 
aryl group, an aralkyl group, an allyl group or a halogen atom. 
There is no limitation on the number average molecular weight of the 
component (A-3) containing the functional group having a phenolic hydroxyl 
group represented by the formula (XV) above, and is preferably within the 
range of generally 200 to 20,000, particularly 500 to 5,000, and more 
particularly 800 to 3,000. It is preferred that the component (A-3) 
contains in average 0.3 to 2, particularly 0.5 to 1.5, and more 
particularly 0.8 to 1.2 functional groups having a phenolic hydroxyl group 
represented by the formula (XV) above per molecule. 
In addition, there can be favorably used, as the compound (component (A-3)) 
containing the functional group having a phenolic hydroxyl group 
represented by the formula (XV) above, a compound represented by the 
following general formula (XVI) 
##STR21## 
wherein .gamma. is 0 or integer of 1 to 7; and 
R.sub.38 represents a residual group of an active hydrogen-containing 
compound. 
As the active hydrogen-containing compound which is a precursor of R.sub.38 
in the formula (XVI) above, there can be cited, for example, amines such 
as secondary amines; phenols such as phenylphenol and nonylphenol; organic 
acids such as fatty acids; thiols; alcohols such as alkyl alcohols, 
cellosolve, butylcellosolve, and carbitol; inorganic acids; and so on. 
Among them, particularly preferred are secondary amines having a primary 
hydroxyl group such as dialkanolamines; amine compounds represented by the 
formula (XIII) above; phenols such as nonylphenol, phenylphenol, phenol, 
and hydroquinone monomethyl ether; fatty acids such as stearic acids, 
oleic acid, and soy bean fatty acid; lower organic acids such as acetic 
acid, formic acid, and hydroxyacetic acid; and so on. 
A compound the same as that represented by the formula (XVI) except that 
the both ends thereof are only one of R.sub.38 and --OH instead of 
R.sub.38 and --OH may be present in the component (A-3) as a mixture. It 
is preferred that the compound contains the functional group having a 
phenolic hydroxyl group in an amount of in average 0.5 to 1.5, 
particularly 0.8 to 1.2 per one molecule, and a number average molecular 
weight within the range of 500 to 20,000, particularly 800 to 3,000. 
The component (A-3) containing the functional group having a phenolic 
hydroxyl group can be obtained, for example, by reacting a bisphenol type 
glycidyl ether, a bisphenol type diphenol and an active 
hydrogen-containing compound (for example, N-alkylalkanolamine, 
dialkanolamine, etc.) in the presence of a catalyst and a solvent as 
necessary at a temperature of 30.degree. to 300.degree. C., preferably 
70.degree. to 180.degree. C. In this reaction, there may be present as a 
mixture, polyols such as dimer diol, ethylene glycol, propylene glycol, 
and butylene glycol; polyether polyols such as polyethylene glycol, 
polypropylene glycol, and polybutylene glycol; polyester polyols such 
polycaprolactone; polycarboxylic acids; polyisocyanates; monoisocyanates; 
oxides of unsaturated compounds such as ethylene oxide, propylene oxide, 
butylene oxide, and styrene oxide; glycidyl ethers hydroxyl 
group-containing compounds such as ally glycidyl ether, polypropylene 
glycol diglycidyl ether, 2-ethylhexyl glycidyl ether, methyl glycidyl 
ether, butyl glycidyl ether, and phenyl glycidyl ether; glycidyl esters or 
organic acids such as fatty acids; alicyclic oxirane-containing compounds; 
and so on. Further, d-4-caprolactone, acrylic monomer, etc. may be graft 
polymerized thereon. 
Preparation of component (A): 
A component (A) used in this invention can be obtained by reacting a 
component (A-1-1) and/or a component (A-1-2) described above (hereafter 
these two components are generally referred to as components (A-1)), a 
component (A-2), and a component (A-3). This reaction can be carried out 
by reacting the component (A-2) and the component (A-3) with the component 
(A-1) simultaneously or successively. For example, this reaction can be 
carried out according to a process, for example, which comprises either 
mixing and reacting these components simultaneously, or reacting the 
component (A-2) with the component (A-1) and then reacting the component 
(A-3), or reacting the component (A-3) with the component (A-1) and then 
reacting the component (A-2), and thereby the component (A) is obtained. 
The reaction between the components (A-1) and (A-2) is a reaction between 
the glycidyl group in the component (A-1) and the primary and/or secondary 
amino group in the component (A-2), which reaction produces a secondary 
and/or tertiary amino group, respectively. Also, the reaction between the 
components (A-1) and (A-3) is a reaction between the glycidyl group in the 
component (A-1) and the phenolic hydroxyl group in the component (A-3), 
which reaction produces an ether bond. The component (A) thus obtained 
contains no or substantially no remaining glycidyl group (it contains 
substantially no glycidyl group) since as a rule the glycidyl group 
contained in the component (A-1) is consumed in the aforementioned 
reaction. 
Proportions of the components are not critical and may be selected freely 
depending on the purposes. For example, it is preferred that the reaction 
proceeds such that total mole number of the amino group in the component 
(A-2) and the phenolic hydroxyl group in the component (A-3) is 0.75 to 
1.5 moles, particularly 0.8 to 1.2 moles for 1 mole of glycidyl groups in 
component (A-1). If the total mole number is less than 0.75 mole, the 
viscosity of the product could sometimes become high while use of the 
total mole number above 1.5 moles could result in increased amount of 
remaining unreacted amino group which gives adverse influence on 
electrodeposition characteristics. 
Further, the amount of the component (A-1) to be used is suitably 0.5 to 
75% by weight, particularly 5 to 50% by weight, and more particularly 7 to 
20% by weight, based on total weight of the components (A-1), (A-2) and 
(A-3). If it is less than 0.5% by weight, the resulting resin tends to 
have insufficient water dispersibility, and on the contrary, if it exceeds 
75% by weight, the amine value increases to high enough a level to 
deteriorate corrosion resistance of the resulting coated film. 
It is desirable to use the component (A-2) in amounts such that the 
hydroxyl equivalent of the resulting component (A) is within the range of 
250 to 2,000, preferably 300 to 1,000, and more preferably 300 to 700. If 
the hydroxyl equivalent is below 250, the amine value tends to increase to 
deteriorate the corrosion resistance of the resulting coated film while if 
it exceeds 2,000, the curability of the resin decreases, which causes a 
fear that the corrosion resistance of the resulting coated film decreases. 
On the other hand, it is suitable that the component (A-3) is used in an 
amount within the range of 0.05 to 1.5 moles, particularly 0.2 to 1.2 
moles, and more particularly 0.3 to 1.0 mole, per mole of the component 
(A-1). If the amount of the component (A-3) is less than 0.05 moles, the 
water dispersibility of the resin tend to decrease, while if it exceeds 
1.5 moles smoothness of the coated surface tends to decrease. 
Further, it is preferred that the reaction between the component (A-1), 
(A-2) and (A-3) proceeds at a temperature within the range of usually 
50.degree. to 300.degree. C. particularly 70.degree. to 200.degree. C. 
This reaction can be performed in the presence of an organic solvent such 
as an alcohol, a ketone or an ether. 
It is preferred that the component (A) obtained has a number average 
molecular weight within the range of generally 1,000 to 20,000, 
particularly 1,500 to 10,000, and more particularly 1,500 to 4,000. Also, 
it is preferred that the cationic resin, as described above, has a 
hydroxyl equivalent within the range of generally 250 to 2,000, 
particularly 300 to 1,000, and more particularly 300 to 700. 
Upon the production of the component (A), other cationizing agents (A-4) 
described below may be used together with the component (A-2) in order to 
adjust the hydroxyl equivalent. The component (A-4) may be used at an 
initial stage or midway of the aforementioned reaction, or after the 
reaction. 
As the other cationizing agent (A-4), there can be cited, for example, 
primary amines represented by monoalkylamines such as methylamine, 
ethylamine, and n-or iso-propylamine; secondary amines represented by 
dialkylamines such as diethylamine, dipropylamine, and dibutylamine; 
polyamines represented by alkylene polyamines such as ethylenediamine, 
diethylenetriamine, ethylaminoethylamine, methylaminopropylamine, 
dimethylaminoethylamine, and dimethylaminopropylamine; and so on. 
Further, these may be used together with ammonia, hydrazine, 
N-hydroxyethylimidazoline compound, etc. 
It is desirable to react such a cationizing agent so that primary or 
secondary amino groups do not remain in the component (A) after reaction. 
As the other cationizing agent (A-4), there can also be used amine 
compounds which have a secondary hydroxyl group, a secondary amino group 
and an amido group simultaneously in one molecule, obtained by replacing 
the primary hydroxyl group-containing primary and/or secondary diamine by 
a secondary hydroxyl group-containing primary and/or secondary diamine in 
the preparation of the amine compound (6) as described on the component 
(A-2) above. 
Further, tertiary amines such as triethylamine, triethanolamine, 
N,N-dimethylethanolamine, N-methyldiethanolamine, 
N,N'-diethylethanolamine, and N-ethyldiethanolamine may be used as the 
component (A-4). These may also be used in the form of quaternary salts 
obtained by protonating with an acid followed by reaction with an epoxy 
group. 
In addition to the amino compounds, there can be used tertiary sulfonium 
salts obtained by reacting salts of sulfides such as diethyl sulfide, 
diphenyl sulfide, tetramethylene sulfide and thiodiethanol with boric 
acid, carbonic acid, organic monocarboxylic acid or the like with an epoxy 
group. 
Further, there can be used, as the cationizing agent, quaternary 
phosphonium salts obtained by reacting salts of phosphines such as 
triethylphosphine, phenyldimethylphosphine, diphenylmethylphosphine, and 
triphenylphosphine with the above acid with an epoxy group. 
In this invention, while it is necessary to form the component (A) using 
the component (A-2), use of the aforementioned other cationizing agent 
(A-4) is not mandatory. 
The component (A) containing a primary hydroxyl group thus obtained is used 
as a resin for a cationic electrodeposition coating composition. In 
particular, the resin (A) is excellent in water dispersibility and hence 
it can be blended with an organic or inorganic substance having 
insufficient water dispersibility to improve its water dispersibility. 
Therefore, the resin (A) is also useful as a water dispersibility 
improving agent for a cationic electrodeposition coating composition. 
Component (B): 
A resin (B-1) having per molecule at least two phenolic hydroxyl groups, or 
resin (B-2) having per molecule at least one each of a phenolic hydroxyl 
group and a primary hydroxyl group originating in the alkanolamine (at 
least two in total). It is preferable that these intrinsically have 
neither primary nor secondary amino group. 
It is possible, by using them, to enhance the curability, corrosion 
resistance, water resistance, etc. of the formed coating film. The number 
average molecular weight of the component (B) is not particularly limited, 
but it is preferable that it is in the range of generally about 200 to 
about 20,000, particularly about 200 to about 15,000, and further 
particularly about 200 to about 10,000. 
Component (B-1): 
A resin having per molecule at least two phenolic hydroxyl groups. 
The component (B-1) can have per molecule at least two, preferably 2 to 38, 
and more preferably 2 to 15 phenolic hydroxyl groups. As such resins 
(B-1), those exemplified below can be used preferably. 
As resins (B-1-1) having per molecule two phenolic hydroxyl groups, there 
can, for example, be mentioned bis(4-hydroxyphenyl)-2,2-propane (bisphenol 
A), bis(4-hydroxyphenyl)-2,2-methane (bisphenol F), 
4,4'-dihydroxybiphenyl, 4,4'-(1-.alpha.-methylbenzylidyne)bisphenol, 
2,2'-bis(4-hydroxy-3-methylphenyl)propane, methylenebis-p-cresol, 
4,4'-ethylidenebisphenol, bis(4-hydroxy-3,5-dimethylphenyl)methane, 
2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, dihydroxybenzophenone, 
1,1-bis(4-hydroxyphenyl)cyclohexane, etc. 
As resins (B-1-2) having per molecule three phenolic hydroxyl groups, there 
can, for example, be mentioned 4,4'4"-methylidenetrisphenol, 
4,4'-[(4-hydroxyphenyl)methylene]bis[2-methoxyphenol], 
4,4'-[(4-hydroxyphenyl)methylene]bis[2,6-dimethylphenol], 
4,4'4"-ethylidenetrisphenol, 
4,4-[1-[4-(2-(4-hydroxyphenyl)-2-propyl)phenyl]ethylidene]bisphenol, etc. 
As resins (B-1-3) having per molecule more than three phenolic hydroxyl 
groups, there can, for example, be mentioned phenol type novolak resins 
represented by the following formula (XVII), 
##STR22## 
wherein R.sub.51 and R.sub.52, which are the same or different, 
independently represent a hydrogen atom, an alkyl group having 1 to 8 
carbon atoms, an aryl group, an aralkyl group or a halogen atom; 
R.sub.53 represents a hydrogen atom, an alkyl group having 1 to 10 carbon 
atoms, an aryl group, an aralkyl group, an allyl group or a halogen atom; 
R.sub.54 and R.sub.56, which are the same or different, independently 
represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; 
R.sub.55 represents a hydrogen atom, an alkyl group having 1 to 10 carbon 
atoms, an aryl group, an aralkyl group, an allyl group or a halogen atom; 
and 
s is an integer of 1 to 38. 
In the above general formula (XVII), "alkyl group" is straight-chain or 
branched chain one, and there can, for example, be mentioned methyl, 
ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 
isoamyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl and decyl groups, etc. 
Further, the "aryl group" may either be monocyclic or polycyclic, and 
there can, for example, be mentioned phenyl and naphthyl groups, etc. and 
a phenyl group is particularly preferred. Further, "aralkyl group" is an 
aryl-substituted alkyl group, and, for example, benzyl and phenethyl 
groups, etc. are included, and a benzyl group is preferred among them. 
The "halogen atoms" includes fluorine, chlorine, bromine and iodine atoms. 
In the above formula (XVII), as R.sub.51 and R.sub.52, a hydrogen atom, a 
methyl group, a chlorine atom, and a bromine atom are preferred, and a 
hydrogen atom, a methyl group and a bromine atom are particularly 
preferred. Further, as R.sub.53 and R.sub.55, a methyl group, a tert-butyl 
group, a nonyl group, a phenyl group, a chlorine atom and a bromine atom 
are preferred, and a methyl group, a tert-butyl group, a phenyl group and 
a bromine atom are particularly preferred. Further, R.sub.54 and R.sub.56 
are preferably hydrogen atoms, and s is particularly preferably 1 to 8. 
It is preferable that the number average molecular weight of the component 
(B-1-3) is in the range of generally about 400 to about 20,000, 
particularly about 500 to about 15,000, further particularly preferably 
600 to 10,000 based on measurement according to the vapor 
pressure-osomotic pressure method. A number average repeating unit number 
(s+2) can be calculated from this number average molecular weight. 
Further, the component (B-1-3) preferably has per molecule 3 to 15 
phenolic hydroxyl groups, and it is preferred that the phenolic hydroxyl 
group equivalent of the component (B-3) is in the range of generally about 
120 to about 2,000, particularly 140 to 600. 
A (B-1-3) component can, for example, be obtained by condensation 
polymerizing a bifunctional phenyl compound represented by the following 
formula (XVIII) 
##STR23## 
wherein R.sub.51, R.sub.52 and R.sub.53 have the same meanings as defined 
above, 
with an aldehyde compound represented by the following formula (XIX) 
EQU R.sub.54 --CHO 
wherein R.sub.54 has the same meaning as defined above, 
and/or a ketone compound represented by the following (XX) 
EQU R.sub.54 --CO--R.sub.56 
wherein R.sub.54 and R.sub.56 have the same meanings as defined above. 
It is possible to use together therewith, during or after the reaction for 
obtention of the phenolic type novolak resin of the above formula (XVII), 
if necessary, as a terminal blocking agent, a monofunctional phenol 
compound represented by the following formula (XXI) 
##STR24## 
wherein R.sub.57 represents an alkyl group having 1 to 10 carbon atoms, an 
aryl group, an aralkyl group, an allyl group or a halogen atom; and 
R.sub.51 and R.sub.52 have the same meanings as defined above. 
Specific examples of the group represented by R.sub.57 in the formula (XXI) 
above include a methyl group, an ethyl group, a propyl group, a n-butyl 
group, a tert-butyl group, a pentyl group, a hexyl group, a nonyl group, 
an ethylene group, a propylene group, a phenyl group, a benzyl group, a 
chlorine atom, a bromine atom, and an iodine atom, with a methyl group, a 
tert-butyl group, a nonyl group, a phenyl group, a chlorine atom, and a 
bromine atom being particularly preferred. 
The term "bifunctional" as used for the phenol compound means that in 
general formula (XVIII), two hydrogen atoms are bonded directly to the 
benzene nucleus at the ortho and/or para-position with respect to the 
hydroxyl group. The hydrogen atoms will react with carbonyl group 
(C.dbd.O) in the aldehyde compound and the ketone compound above by 
condensation reaction with dehydration to form a phenol-novolak resin. 
The term "monofunctional" as used for the phenol compound means that in the 
general formula (XXI), one hydrogen atom is bonded to the benzene ring at 
the ortho- or para-position with respect to the hydroxyl group. The 
hydrogen atom will react with carbonyl group (C.dbd.O) in the aldehyde 
compound or the ketone compound by condensation reaction with dehydration 
to form terminals thereof. 
As the bifunctional phenol compound represented by the formula (XVIII) 
above, there can be cited, for example, phenol, p-propenylphenol, 
o-benzylphenol, 6-n-amyl-n-cresol, o-cresol, p-cresol, o-ethylphenol, 
o-phenylphenol, p-phenylphenol, p-tert-pentylphenol, p-tert-butylphenol, 
o-chlorophenol, p-chlorophenol, 4-chloro-3,5-xylenol, o-allylphenol, 
nonylphenol, o-bromophenol, p-cumylphenol, etc. 
As the aldehyde compound represented by the formula (XIX) above, there can 
be cited, for example, acetaldehyde, formaldehyde, etc. Also, m- (or p-) 
hydroxybenzaldehyde may be used as the aldehyde compound, and after the 
reaction with the bifunctional phenyl compound, the hydroxybenzaldehyde 
may be converted to glycidyl ether with an epihalohydrin. The benzene 
nucleus of the hydroxybenzaldehyde may be substituted with an alkyl group 
having 1 to 10 carbon atoms. 
As the ketone compound represented by the formula (XX), there can be cited, 
for example, acetone, methyl ethyl ketone, methyl isobutyl ketones, etc. 
Further, use of 2-acetylphenyl-2-hydroxyphenylpropane makes it possible to 
introduce a glycidyloxyphenyl group in the resin represented by the 
formula (XVII) above. 
This makes at least a portion of 
##STR25## 
Further, as the epihalohydrin, there can be cited, for example, 
epichlorohydrin, epibromohydrin, etc. 
The phenol-novolak resin (B-1-3) can be obtained by polycondensing the 
bifunctional phenyl compound above with the aldehyde compound and/or 
ketone compound above. The polycondensation reaction can be performed 
similarly to an ordinary production method for phenol-novolak resin which 
is known by itself. More specifically, the reaction may be performed by a 
batch method, or by the continuous method as described, for example, in 
Japanese Laid-Open Patent Publication No. 130498/1976. For example, the 
component (B-3) can be obtained by blending each component in proportions 
such that the repeating unit number (s) in the formula (XVII) above is 
within the range of 1 to 38, and the number average molecular weight and 
epoxy equivalent are within the aforementioned ranges, followed by 
reaction. In this reaction, there may be used a catalyst such as inorganic 
acids, e.g., hydrochloric acid, phosphoric acid, sulfuric acid, etc.; 
organic acids, e.g., p-toluenesulfonic acid, oxalic acid, etc.; metal 
salts, e.g., zinc acetate, etc. 
In the production of the component (B-1-3), the monofunctional phenol 
compound represented by the formula (XXI) above may be reacted as a 
terminal blocking agent during or after polycondensation reaction of the 
bifunctional phenyl compound with the aldehyde compound and/or the ketone 
compound as necessary. 
Specific examples of the monofunctional phenol compound represented by the 
formula (XXI) above include, for example, 2-tert-butyl-4-methylphenol, 
2,4-xylenol, 2,6-xylenol, 2,4-dichlorophenol, 2,4-dibromophenol, 
dichloroxylenol, dibromoxylenol, 2,4,5-trichlorophenol, 
6-phenyl-2-chlorophenol, etc. 
The polycondensation of the monofunctional phenyl compound with the 
bifunctional phenyl compound, the aldehyde compound and/or the ketone 
compound above can be performed in the same manner as described above. 
Novolak-phenol resin obtained using the monofunctional phenol compound in 
combination is also included in the category of the component (B-1-3). 
Further, the component (B-1) also includes a product (B-1-4) obtained by 
reacting a mono- or polyglycidyl compound with at least one component 
selected from the above components (B-1-1) to (B-1-3), if necessary in the 
presence of a catalyst and a solvent, at a temperature of 30.degree. to 
300.degree. C., preferably 70.degree. to 180.degree. C. 
As mono- or polyglycidyl compounds, there can, for example, be mentioned 
bisphenol type diglycidyl ethers; oxides of unsaturated compounds such as 
ethylene oxide, propylene oxide, butylene oxide and styrene oxide; 
glycidyl ethers of compounds having a hydroxyl group such as allyl 
glycidyl ether, polypropylene glycol diglycidyl ether, 2-ethylhexyl 
glycidyl ether, methyl glycidyl ether, butyl glycidyl ether and phenyl 
glycidyl ether; glycidyl esters of organic acids such as fatty acids; etc. 
Further, it is also possible to further coexist the following components in 
the formation reaction of the components (B-1-4) so long as the reaction 
products have per molecule two or more phenolic hydroxyl groups. For 
example, there can coexist polyols such as dimerdiols, ethylene glycol, 
propylene glycol and butylene glycol; polyether polyols such as 
polyethylene glycol, polypropylene glycol and polybutylene glycol; 
polyester polyols such as polycaprolactones; polycarboxylic acids; 
polyisocyanates; monoisocyanates; alicyclic oxirane-containing compounds; 
etc. Further, it is also possible to graft polymerize 
.delta.-4-caprolactone, an acrylic monomer or the like. 
Component (B-2): 
A resin having per molecule two or more in total of phenolic hydroxyl 
groups wherein a hydroxyl group directly binds to the benzene ring and 
primary hydroxyl groups introduced by an alkanolamine, and intrinsically 
having neither primary nor secondary amino group. 
A component (B-2) can be obtained by reacting a resin (B-1) described above 
and having per molecule two or more phenolic hydroxyl groups, a 
polyglycidyl compound and an alkanolamine, if necessary in the presence of 
a catalyst and a solvent, at a temperature of 30.degree. to 300.degree. 
C., preferably 70.degree. to 180.degree. C. 
As resins (B-1) having per molecule two or more phenolic hydroxyl groups 
and polyglycidyl compounds, the same ones as described above can be used. 
Further, it is preferred to use as alkanolamines at least one compound 
selected from compounds mentioned in (1) to (6) exemplified in the 
description of the component (A-2). 
Further, it is also possible to further coexist a component described below 
in the formation reaction of the component (B-2) so long as the reaction 
product has per molecule two or more in total of phenolic hydroxyl groups 
and hydroxyl groups originating in the alkanolamine. For example, it is 
possible to coexist a polyol such as a dimerdiol, ethylene glycol, 
propylene glycol or butylene glycol; a polyether polyol such as 
polyethylene glycol, polypropylene glycol or polybutylene glycol; a 
polyester polyol such as polycaprolactone; a polycarboxylic acid; a 
polyisocyanate; a monoisocyanate; an alicyclic oxirane-containing 
compound; or the like. Further, it is also possible to graft polymerize a 
.delta.-4-caprol actone, acrylic monomer or the like. 
Component (C): 
At least one resin or compound selected from the following components 
(C-1), (C-2) and (C-3) is used. 
Component (C-1): 
A novolak phenol type glycidyl ether group-containing resin represented by 
the following formula (III) 
##STR26## 
wherein R'.sub.1 and R'.sub.2, which are the same or different, 
independently represent a hydrogen atom, an alkyl group having 1 to 8 
carbon atoms, an aryl group, an aralkyl group or a halogen atom, 
R'.sub.3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon 
atoms, an aryl group, an aralkyl group, an allyl group or a halogen atom, 
R'.sub.4 and R'.sub.6, which are the same or different, independently 
represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, 
R'.sub.5 represents an alkyl group having 1 to 10 carbon atoms, an aryl 
group, an aralkyl group, an allyl group or a halogen atom, and 
n' is an integer of 1 to 38. 
The component (C-1) is structurally analogous the component (A-1-2) used in 
preparation of the above component (A) and represented by the formula 
(II), and a different point is that R.sub.3 in the formula (II) can be not 
only an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl 
group, an allyl group or a halogen atom, but also a hydrogen atom, whereas 
R'.sub.3 in the formula (III) is an alkyl group having 1 to 10 carbon 
atoms, an aryl group, an aralkyl group, an allyl group or a halogen atom, 
and cannot be a hydrogen atom, and both are common in all the other 
points. Therefore, since the above description on the component (A-1-2) is 
applied, as it is, to the component (C-1), description on the component 
(C-1) is omitted herein. 
Component (C-2): 
An epoxy resin having per molecule at least three epoxy group-containing 
functional groups represented by the following formula (IV) 
##STR27## 
wherein p is an integer of 2 to 4. 
It is possible to use, as the component (C-2), the same epoxy resin as 
described as the component (A-1) used for preparation of the component 
(A). Therefore, since the above description on the component (A-1-1) is 
applied, as it is, to the component (C-2), description on the component 
(C-2) is omitted herein. 
Component (C-3): 
A compound having per molecule two or more glycidyl groups originating in 
glycidylamino groups binding directly to the carbon atoms of the aromatic 
rings and represented by the following formula (V) 
##STR28## 
wherein R is a hydrogen atom or a glycidyl group. 
The component (C-3) has per molecule aromatic rings and glycidyl groups, 
and the glycidyl groups are introduced in a form of glycidylamino groups 
represented by the above formula (V), and the nitrogen atom (N) in the 
formula (V) binds directly to a carbon atom of the aromatic ring. 
A component (C-3) can, generally, be obtained by subjecting the amino group 
(--NH.sub.2) of an aniline derivative and an epihalohydrin (preferably 
epichlorohydrin) to dehydrohalogenation (condensation) reaction in the 
presence of a catalyst such as an aqueous alkali metal hydroxide solution. 
This reaction can be carried out by a process known per se. 
When one mole of an epihalohydrin is reacted per mole of the amino group in 
this reaction, one glycidyl group is introduced, theoretically, into the 
amino group and one hydrogen atom remains in a binding state in the amino 
group and this hydrogen atom corresponds to the hydrogen atom as R in the 
formula (V). When 2 moles of the epihalohydrin is reacted in this 
reaction, two glycidyl groups are introduced into the amino group and one 
glycidyl group among them corresponds to R in the formula (V). 
In the above, the "aniline derivatives" have a broad sense and include 
compounds having one or two or more amino groups (--NH.sub.2) directly 
binding to ring carbon atoms of an aromatic ring such as a benzene ring or 
naphthalene ring, and, for example, there can be mentioned monoaniline 
derivatives wherein one amino group (--NH.sub.2) directly binds to a ring 
carbon atom of a benzene ring or a naphthalene ring, such as aniline, 
o-toluidine, m-toluidine, p-toluidine, o-ethylaniline, m-ethylaniline, 
p-ethylaniline, p-cresidine, 2,4-xylidine, 3,4-xylidine, o-anisidine, 
p-anisidine and naphthylamine; dianiline derivatives wherein two amino 
groups (--NH.sub.2) directly bind to ring carbon atoms of a benzene ring 
or a naphthalene ring, such as phenylenediamine, 2,4-toluylenediamine, 
diaminobenzanilide, dianisidine, diaminodiphenyl ether, 
3,5-diaminochlorobenzene, 3,3'-dimethylbenzidine and 1,5-naphylendiamine; 
etc., and particularly preferred are phenylenediamine and 
toluylenediamine. 
There can also be used as the aniline derivative a polycondensate wherein 
plural aromatic rings are bound through methylene groups or the like and 
which is obtained by reacting an aldehyde (e.g., formamide, acetaldehyde 
or the like) or a ketone (e.g., acetone, methyl ethyl ketone, methyl 
isobutyl ketone or the like) with a monoaniline derivative or dianiline 
derivative described above in the presence of a catalyst, for example, an 
inorganic acid such as hydrochloric acid, phosphoric acid or sulfuric 
acid; an organic acid such as paratoluenesulfonic acid or oxalic acid; a 
metal salt such as zinc acetate; or the like. It is preferably that this 
polycondensate has a repeating unit of the aromatic ring in the range of 2 
to 40, particularly 2 to 20. As specific examples of such polycondensate, 
there can be mentioned diaminodiphenylmethane, 
3,3-dimethyl-4,4-diaminodiphenylmethane, 
3,3-diethyl-4,4-diaminodiphenylmethane, etc., but such polycondensates are 
not limited thereto. 
Part of the glycidyl groups of the component (C-3) obtained as above can be 
modified by reacting therewith one or more selected from a phenol such as 
bisphenol A, bisphenol F, phenylphenol, nonylphenol or phenol; a higher 
fatty acid such as a dimer acid, stearic acid, oleic acid or a soybean oil 
fatty acid; an organic acid such as acetic acid, formic acid or 
hydroxyacetic acid; an alcohol such as an alkyl alcohol, a cellosolve or a 
carbitol; and so on. Particularly preferable among them are phenols and 
high fatty acids. It is preferable to use in this modification a catalyst 
such as zinc borofluoride or tetramethylammonium chloride. 
It is preferable that the component (C-3) used in this invention has a 
number average molecular weight, measured by the vapor pressure-osmotic 
pressure method, in the range of about 200 to 8,000, particularly 500 to 
5,000, further particularly 500 to 2,000, and an epoxy equivalent in the 
range of 100 to 2,000, particularly 100 to 1,000, further particularly 100 
to 600. It is possible to use commercial products as such components 
(C-3), and there can, for example, be mentioned GAN (N,N-diglycidylaniline 
produced by NIPPON KAYAKU CO., LTD.), GOT (N,N-diglycidyl-o-toluidine 
produced by NIPPON KAYAKU CO., LTD.), MY 720 
(N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane produced by Japan 
Ciba-Geigy Co.), MY 722 
(N,N,N',N'-tetraglycidyl-3,3'-dimethyl-4,4'-diaminodiphenylmethane 
produced by Japan Ciba-Geigy Co.), etc. 
Resin composition for aqueous paint: 
The composition for aqueous paint of this invention contains as main 
components the above-described components (A), (B) and (C), and can, for 
example, be prepared by neutralizing the basic groups of the component (A) 
with an acid, and dispersing this together with the components (B) and (C) 
in an aqueous medium. The neutralization of the component (A) can be made 
at any point of time before, during or after mixing of the above 
components. When the component (B) has basic groups, it is also possible 
to neutralize them in the same manner as in the component (A). There is no 
particular limitation about the mixing order of the above components, and 
the mixing can be made by any order, and, for example, processes can be 
adopted which comprises mixing and dispersing all the components all at 
once; mixing the components (A) and (B) and then mixing the component (C); 
mixing the components (A) and (C) and then mixing the component (B); 
mixing the components (B) and (C) and then mixing the component (A); and 
the like. Further, as neutralizing agents usable for the neutralization of 
the component (A), formic acid, acetic acid, lactic acid, butyric acid, 
etc. are, for example, preferable. 
The compounding ratio of the above components (A), (B) and (C) are not 
particularly limited and can be varied over a wide range depending on uses 
of the resin composition, etc., but, in general, it is preferable that the 
compounding ratio is in the range of 10 to 60 wt. % particularly 15 to 50 
wt. %, further particularly 25 to 45 wt. % of the component (A), and in 
the range of 90 to 40 wt. %, particularly 85 to 50 wt. %, further 
particularly 75 to 55 wt. % in total of the component (B) and the 
component (C), based on the total solid weight of the three components. 
Further, it is preferable that the amount of the glycidyl groups (epoxy 
groups) of the component (C) is in the range of 0.3 to 3 moles, 
particularly 0.6 to 2 moles, further particularly 0.8 to 1.5 moles per 
mole of total of the hydroxyl groups contained in the components (A) and 
(B). 
The resin composition for aqueous paint of this invention can, if 
necessary, contain, besides the components (A), (B) and (C), an extender 
pigment, an anticorrosive pigment, a dispersing agent, a cissing 
inhibitor, a curing accelerator, etc. It is preferable that the pigments 
among them are compounded as a pigment dispersion paste (Y) described 
below. 
Pigment dispersion paste (Y): 
A pigment dispersion paste (Y) can be prepared by mixing pigments (color 
pigment, extender pigment, anticorrosive pigment, etc.) with at least one 
resin selected from the components (A) and dispersing the former into the 
latter, and, if necessary, a plasticizer, a wetting agent, a surfactant or 
antifoaming agent, etc. can further be compounded. 
The mixing and dispersion of these components can be carried out using a 
ball mill, a sand mill, a Crowles dissolver, a continuous dispersing 
machine or the like, and, for example, it is preferable to disperse the 
pigments to a desired size and make them wet with the above components 
(A). The particle size of the pigment after the dispersion is preferably 
10 microns or smaller (about 6 to 8 in terms of the degree of Helmann 
fineness-of-grind gauge). This dispersion is preferably carried out in 
water. In this occasion, it is preferable to neutralize part or all of the 
basic groups in the component (A) with an acidic compound as 
above-mentioned and protonate them, and make a water dispersion. The 
addition amount of the acidic compound is, preferable, adjusted so that 
the neutralization value of these resins gets to be in the range of 
usually 5 to 200, particularly 10 to 150 in terms of KOH (mg/g). The water 
content in the aqueous divisional liquid of the pigment dispersion paste 
(Y) is not particularly limited, but it is preferable that the water 
content is in the range of usually about 20 to 80 wt. %, particularly 40 
to 60 wt. %. 
There is no particular limitation about the kind of the above pigments in 
pigment dispersion pastes (Y), and there can, for example, be mentioned 
color pigments such as carbon black, titanium white, lead oxide and red 
iron oxide; extender pigments such as antimony oxide, zinc oxide, basic 
lead carbonate, basic lead sulfate, barium carbonate, calcium carbonate, 
aluminum silica, magnesium carbonate, magnesium silica, clay and talc; 
anticorrosive pigments such as strontium chromate, lead chromate, basic 
lead chromate, red lead, lead silicate, basic lead silicate, lead 
phosphate, basic lead phosphate, lead tripolyphosphate, lead 
silicochromate, chrome yellow, lead cyanamide, calcium plumbate, lead 
suboxide and lead sulfate. It is preferable that the mixing ratio of these 
pigments with the component (A) is in the range of usually 2/1 to 7/1, 
particularly 3/1 to 5/1 in terms of the weight ratio of the solid matters. 
The resin composition for aqueous paint of this invention can be made into 
a cationic electrodeposition coating composition by a process known per 
se, for example by neutralizing the resin composition with an acid 
component in the same manner as above, and diluting the neutralized 
composition with water to adjust it to a desired concentration. 
A cationic electrodeposition coating composition prepared using the resin 
composition for water paint of this invention can be applied through 
cationic electrodeposition onto a suitable electrically conductive 
substrate (matter to be coated) according to a usual method, and the 
coating film can be cured with heating at a temperature of for example 
80.degree. to 250.degree. C., preferably 120.degree. to 160.degree. C. 
Particularly, when it is desired to cure sufficiently electrodeposition 
coating film, from a cationic electrodeposition coating composition using 
a resin composition for aqueous paint of this invention, at a low 
temperature of 160.degree. C. or lower, it is effective to add one or two 
or more catalysts selected from lead compounds, zirconium compounds, 
cabalt compounds, aluminum compounds, manganese compounds, copper 
compounds, zinc compounds, iron compounds, chromium compounds, nickel 
compounds, tin compounds, etc. As specific examples of these metal 
compounds, there can, for example, be mentioned chelate compounds such as 
zirconium acetylacetonate, cobalt acetylacetonate, aluminum 
acetylacetonate and manganese acetylacetonate; chelation reaction products 
of a compound having .beta.-hydroxyamino structure with lead oxide (II); 
carboxylates such as lead 2-ethylhexanoic acid, lead naphthenate, lead 
octylate, lead benzoate, lead acetate, lead lactate, lead formate, lead 
glycolate and zirconium octylate; etc. 
The above metal compounds can be used in an amount such that the metal 
content based on the resin solid matters is generally 10 wt. % or less, 
preferably 0.5 to 5 wt. %. 
The resin composition for aqueous paint of this invention has an advantage 
that since hydrophilic parts due to tertiary amino groups neutralized with 
the acid, hydroxyl groups, etc., and hydrophobic parts comprising the 
other parts (for example, epoxy group parts) exist with clear distinction 
(being localized) in the resin skeleton of the component (A), the 
components (B) and (C) can readily be dispersed. 
The resin composition for aqueous paint of this invention is crosslinked 
and cured through ether addition of the epoxy groups of the component (C) 
to the hydroxyl groups in the component (B) introduced by the phenolic 
hydroxyl groups and the alkanolamine and the hydroxyl groups in the 
component (A), etc., and since heating loss is extremely small at that 
time, the coating film formed has almost no contraction stress and 
smoothness, corrosion resistance, etc. are remarkably enhanced. Further, 
since the component (A) has excellent dispersibility, it is possible to 
hold its use amount at a low level and as a result basic concentration due 
to the resin composition for aqueous paint gets lower and the acid 
resistance, corrosion resistance, etc. of the coating film are improved. 
There is no particular limitation about methods for formation of 
electrodeposition coating film on an electrically conductive substrate 
using a cationic electrodeposition coating composition using the 
composition of this invention as the base, and the formation can be 
carried out using usual cationic electrodeposition coating conditions. For 
example, if necessary, pigments, a curing catalyst and other additives are 
compounded in the electrodeposition coating composition, and a cationic 
electrodeposition bath is prepared having a bath concentration (solid 
component concentration) in the range of 5 to 40 wt. %, preferably 10 to 
25 wt. % and a bath pH in the range of 4 to 8, preferably 5 to 7. At that 
time, it is preferable to use the substrate to be coated as the cathode 
and a stainless or carbon plate as the anode. Electrodeposition coating 
conditions are not particularly limited, but in general, it is preferable 
to carry out the electrodeposition under conditions of a bath temperature 
of 20.degree. to 30.degree. C., a voltage of 100 to 400 V, preferable 200 
to 300 V, a current density of 0.01 to 3 A/dm.sup.2, an electrification 
time of 1 to 5 minutes, an electrode area ratio (A/C) of 2/1 to 1/2, a 
distance between the electrodes of 10 to 100 cm and a stirred state. 
The above cationic electrodeposition coating composition of this invention 
is excellent in dispersibility in water, storage stability, bath 
stability, anticorrosive properties against untreated steel plates, 
smoothness, etc. because the component (A) is a cationic resin, the 
component (B) is a low basic resin, and the component (C) is a nonbasic 
resin. The electrodeposition coating composition can be applied onto a 
substrate such that at least the surface thereof has an electrically 
conductive metal. As such substrates, there can be mentioned car bodies, 
household appliances, business and office machines, building materials, 
structures, etc., but the substrates are not limited thereto.

This invention is further specifically described below according to 
examples and comparative examples. Parts and % therein are in principle 
weight parts and weight %, respectively. 
I. Preparation of samples 
1. Preparation examples of components (A) and (B) 
These were prepared by reactions based on components and compounding 
amounts shown in Table 1. Preparation examples 1 to 4 are examples to 
prepare components (A) alone, and Preparation examples 5 to 7 are examples 
to prepare components (A) and (B) simultaneously. 
In Preparation examples 1 to 4, the solvent and the component (A-1-1) to 
the component (A-3) shown in Table 1 were put in a flask equipped with a 
stirrer, a thermometer, a dropping funnel and a reflux condenser, the 
mixture was gradually heated with mixing by stirring and reacted at 
150.degree. C., and it was confirmed that the epoxy equivalent got to be 
0, and thereby a component (A) was obtained. 
In Preparation examples 5 to 7, the solvent and the component (A-1-1) to 
the component (A-2) shown in Table 1 were put in a flask equipped with a 
stirrer, a thermometer, a dropping funnel and a reflux condenser, the 
mixture was gradually heated with mixing by stirring and reacted at 
120.degree. C., it was confirmed that the epoxy equivalent reached the 
first stage end point epoxy equivalent, other components were then put 
therein, the mixture was reacted at 150.degree. C., and it was confirmed 
that the epoxy equivalent got to be 0, and thereby a mixture of a 
component (A) and a component (B) was obtained. 
TABLE 1 
__________________________________________________________________________ 
Classi- Preparation example 
fication 
Component 1 2 3 4 5 6 7 
Name A-1 A-2 A-3 A-4 A-5 
A-6 
A-7 
__________________________________________________________________________ 
Component (A) 
Solvent Ethylene glycol 
397 692 534 520 330 
468 
397 
monobutyl ether 
A-1-1 EHPE-3150 900 900 900 
A-1-2 BREN-S 1710 
DEN-438 1080 1080 
EOCN-102S 1290 
A-2 A-2-1 (*1) 
371 742 742 371 371 
371 
Diethanolamine 
315 315 315 420 420 
420 
315 
First stage end point 1320 
1871 
1586 
epoxy equivalent 
A-3 A-3-1 (*2) 
1651 
A-3-2 (*3) 1733 
A-3-3 (*4) 1870 
A-3-4 (*5) 1983 
A-3-5 (*6) 1805 
9025 
Component (B) 
Solvent Ethylene glycol 1587 
1321 
monobutyl ether 
Component 
Diglycidyl ether 2470 
3040 
of bisphenol A 
Bisphenol A 2730 
1824 
Diethanolamine 420 
Diglycidyl ether of 1140 
propylene glycol 
Characteristics 
Component (A) 
Content of (A-1) 
31 41 30 35 31 
33 
30 
Primary hydroxyl 
363 519 454 367 323 
368 
379 
group equivalent 
Amine value 
77 68 77 92 77 
85 
74 
Number average 
2907 
1453 
3633 
3667 
2906 
3315 
3030 
molecular weight 
Component (B) 
Number average 
-- -- -- -- 1587 
1321 
1444 
molecular weight 
Phenolic hydroxyl 
-- -- -- -- 793 
440 
722 
group equivalent 
__________________________________________________________________________ 
In Table 1 
BRENS: Brominemodified novolak phenol polyglycidyl ether having a epoxy 
equivalent of 285 (produced by NIPPON KAYAKU CO., LTD.) 
DEN438: Novolak phenol polyglycidyl ether having an epoxy equivalent of 
180 (produced by Dow Chemical Japan Co., Ltd.) 
EOCN102S: Cresol novolak phenol polyglycidyl ether having an epoxy 
equivalent of 215 (produced by NIPPON KAYAKU CO., LTD.) 
Polypropylene glycol diglycidyl ether: having an epoxy equivalent of 380 
EHPE3150: Alicyclic type epoxy resin having an epoxy equivalent of 180 
(produced by DAICEL CHEMICAL INDUSTRIES, LTD.) 
Bisphenol A glycidyl ether: Epicoat 828 (produced by Yuka shell Epoxy Co. 
Ltd.) 
(*1) A-2-1: 
An amino compound obtained by putting 285 parts of stearic acid, 104 parts 
of hydroxyethylaminoethylamine and 80 parts of toluene in a reaction 
vessel equipped with a thermometer, a stirrer, a reflux condenser and a 
water separator, gradually heating then mixture with mixing by stirring, 
removing toluene according to necessity, separating and removing 18 parts 
of water formed by the reaction with temperature raise, and then removing 
the residual toluene under reduced pressure. Amine value 150, freezing 
point 76.degree. C. 
(*2) A-3-1: 
A product obtained by putting 105 parts of diethanolamine, 760 parts of 
bisphenol A diglycidyl ether having an epoxy equivalent of 190, 456 parts 
of bisphenol A and 330 parts of ethylene glycol monobutyl ether in a flask 
equipped with a stirrer, a thermometer, a dropping funnel and a reflux 
condenser, and reacting the mixture at 150.degree. C. until the residual 
amount of the epoxy groups gets to be 0. Solid component content 80%. 
(*3) A-3-2: 
A product obtained by putting 170 parts of phenylphenol, 760 parts of 
bisphenol A diglycidyl ether having an epoxy equivalent of 190, 456 parts 
of bisphenol A, 0.2 part of tetramethylammonium chloride and 346 parts of 
ethylene glycol monobutyl ether in a flask equipped with a stirrer, a 
thermometer, a dropping funnel and a reflux condenser, and reacting the 
mixture at 150.degree. C. until the residual amount of the epoxy groups 
gets to be 0. Solid component content 80%. 
(*3) A-3-3: 
A product obtained by putting 280 parts of oleic acid, 760 parts of 
bisphenol A diglycidyl ether having an epoxy equivalent of 190, 456 parts 
of bisphenol A, 0.2 part of tetramethylammonium chloride and 374 parts of 
ethylene glycol monobutyl ether in a flask equipped with a stirrer, a 
thermometer, a dropping funnel and a reflux condenser, and reacting the 
mixture at 150.degree. C. until the residual amount of the epoxy groups 
gets to be 0. Solid component content 80%. 
(*3) A-3-4: 
A product obtained by putting 370 parts of the above amine compound 
(A-2-1), 760 parts of bisphenol A diglycidyl ether having an epoxy 
equivalent of 190, 456 parts of bisphenol A, and 397 parts of ethylene 
glycol monobutyl ether in a flask equipped with a stirrer, a thermometer, 
a dropping funnel and a reflux condenser, and reacting the mixture at 
150.degree. C. until the residual amount of the epoxy groups gets to be 0. 
Solid component content 80%. 
(*3) A-3-5: 
A product obtained by putting 0.2 part of tetramethylammonium chloride, 760 
parts of bisphenol A diglycidyl ether having an epoxy equivalent of 190, 
684 parts of bisphenol A, and 361 parts of ethylene glycol monobutyl ether 
in a flask equipped with a stirrer, a thermometer, a dropping funnel and a 
reflux condenser, and reacting the mixture at 150.degree. C. until the 
residual amount of the epoxy groups gets to be 0. Solid component content 
80%. 
2. Preparation examples of components (B) 
(B-1): 
100 parts of Shonol BRG-556 (trade name, novolak polyphenol produced by 
Showa Kobunshi Co., Ltd., phenolic hydroxyl equivalent 122) and 25 parts 
of ethylene glycol monobutyl ether were put in a flax equipped with a 
stirrer, a thermometer and a reflux condenser, and the mixture was heated 
to obtain (B-1) as a solution. 
(B-2): 
100 parts of Shonol CRG-951 (trade name, cresol novolak polyphenol produced 
by Showa Kobunshi Co., Ltd., phenolic hydroxyl equivalent 110) and 25 
parts of ethylene glycol monobutyl ether were put in a flax equipped with 
a stirrer, a thermometer and a reflux condenser, and the mixture was 
heated to obtain (B-2) as a solution. 
(B-3): 
The above A-3-1 was used as such as (B-3). 
(B-4): 
The above A-3-5 was used as such as (B-4). 
3- Preparation examples of components (C) 
(C-1-1): 
1917 parts of EPICLON N-695 (produced by DAI-NIPPON INK AND CHEMICALS, 
INCORPORATED, epoxy equivalent 213, n.apprxeq.7), 590 parts of ethylene 
glycol monobutyl ether, 440 parts of nonylphenol (active 
hydrogen-containing compound) and 0.2 part of tetramethylammonium chloride 
were put in a flask equipped with a stirrer, a thermometer and a reflux 
condenser, and the mixture was reacted at 150.degree. C. until the epoxy 
equivalent got to be 350, whereby (C-1-1) was obtained. 
(C-1-2): 
1917 parts of EPICLON N-695 (produced by DAI-NIPPON INK AND CHEMICALS, 
INCORPORATED, epoxy equivalent 213, n.apprxeq.7), 620 parts of ethylene 
glycol monobutyl ether, 560 parts of tall oil fatty acid (active 
hydrogen-containing compound) and 0.2 part of tetramethylammonium chloride 
were put in a flask equipped with a stirrer, a thermometer and a reflux 
condenser, and the mixture was reacted at 150.degree. C. until the epoxy 
equivalent got to be 370, whereby (C-1-2) was obtained. 
(C-1-3): 
100 parts of EPICLON N-695 (produced by DAI-NIPPON INK AND CHEMICALS, 
INCORPORATED, epoxy equivalent 213, n.apprxeq.7) and 25 parts of ethylene 
glycol monobutyl ether were put in a flask equipped with a stirrer, a 
thermometer and a reflux condenser, and the mixture was heated to obtain 
(C-1-3) as a solution. 
(C-1-4): 
100 parts of BREN-S (produced by NIPPON KAYAKU CO., LTD., epoxy equivalent 
280, n.apprxeq.2) and 25 parts of ethylene glycol monobutyl ether were put 
in a flask equipped with a stirrer, a thermometer and a reflux condenser, 
and the mixture was heated to obtain (C-1-4) as a solution. 
(C-1-5): 
100 parts of ESBM-260 (produced by SUMITOMO CHEMICAL COMPANY, LIMITED, 
epoxy equivalent 260) and 25 parts of ethylene glycol monobutyl ether were 
put in a flask equipped with a stirrer, a thermometer and a reflux 
condenser, and the mixture was heated to obtain (C-1-5) as a solution. 
(C-1-6): 
100 parts of ESN-195 (produced by Nippon Steel Chemicals Co., Ltd., epoxy 
equivalent 290) and 25 parts of ethylene glycol monobutyl ether were put 
in a flask equipped with a stirrer, a thermometer and a reflux condenser, 
and the mixture was heated to obtain (C-1-6) as a solution. 
(C-1-7): 
122 parts of 2,6-xylenol (monofunctional phenol compound), 54 pars of 
o-cresol (bifunctional phenol compound), 28 parts of 7.6% aqueous 
formaldehyde solution and 4 parts of p-toluenesulfonic acid were put in a 
flask equipped with a stirrer, a thermometer and a reflux condenser, the 
mixture was heated to 100.degree. C. and reacted under reflux for 4 hours, 
300 parts of toluene and 8.4 parts of 10% aqueous NaOH solution were 
added, the mixture was stirred, and the toluene layer was separated and 
concentrated under reduced pressure to obtain 164 parts of 2,6-xylenol- 
and o-cresol-cocondensed novolak. 
Then 750 parts of epichlorohydrin was added, the mixture was heated to 
100.degree. C., 120 parts of 50% aqueous NaOH solution was added dropwise 
over a period of 5 hours, and water in the system was removed by azeotropy 
with epichlorohydrin. After completion of the reaction, excess 
epichlorohydrin was removed under reduced pressure, the product was 
dissolved in 300 parts of toluene, the salt as a by-product was separated 
and removed, toluene was removed by reduced pressure to obtain 200 part of 
a 2,6-xylenol- and o-cresol-cocondensed novolak glycidyl ether resin. Its 
epoxy equivalent was 210. 
100 parts of the synthesized 2,6-xylenol- and o-cresol-cocondensed novolak 
glycidyl ether resin and 25 parts of ethylene glycol monobutyl ether were 
put in a flask equipped with a stirrer, a thermometer and a reflux 
condenser, and the mixture was heated to obtain (C-1-7) as a solution. 
(C-2-1): 
32.6 parts of EHPE 3150 (epoxy equivalent 175-195, produced by DAICEL 
CHEMICAL INDUSTRIES, LTD.) and 8.2 parts of propylene glycol monomethyl 
ether were heated at 100.degree. C. to obtain as a solution 40.8 parts of 
a resin for curing (C-2-1) having a solid content of 80% and an epoxy 
equivalent of 190. The number average molecular weight of the resin was 
about 1,500. 
(C-2-2): 
200 parts of 10% ethyl acetate solution of BF.sub.3 -etherate was added 
dropwise at 50.degree. C. over a period of 4 hours to 136 parts of 
vinylnorbornene oxide, 124 parts of 4-vinylcyclohexene-1-oxide and 18 
parts of trimethylolpropane to carry out ring opening polymerization. 
Ethyl acetate was added, the mixture was washed with water, and the ethyl 
acetate layer was concentrated. 130 parts of ethyl acetate was newly added 
to the concentrate to dissolve it, 160 parts of peracetic acid was added 
dropwise thereto at 50.degree. C. over a period of 4 hours as an ethyl 
acetate solution, and the mixture was aged further at 50.degree. C. for 2 
hours to carry out epoxidation reaction. After removal of acetic acid, 
ethyl acetate and peracetic acid, the residue was dissolved in 500 parts 
of ethyl acetate at 40.degree. C., the solution was washed four times with 
250 parts of distilled water, and then ethyl acetate was removed. The 
residue was dissolved in 78 parts of propylene glycol monomethyl ether at 
80.degree. C. to obtain a resin for curing (C-2-2) having a solid content 
of 80% and an epoxy equivalent of 202. The number average molecular weight 
of the resin was about 1,300. 
(C-2-3): 
200 parts of 10% ethyl acetate solution of BF.sub.3 -etherate was added 
dropwise at 50.degree. C. over a period of 4 hours to 304 parts of 
partially epoxidized product of limonene 
(2-methyl-4-isopropenyl-1-cyclohexene oxide) and 18 parts of 
trimethylolpropane. Subsequent operations were carried out in the same 
manner as in the case of the resin B-2 for curing, and the resultant 
product was dissolved in 80 parts of ethylene glycol monobutyl ether at 
80.degree. C. to obtain a resin for curing (C-2-3) having a solid content 
of 80% and an epoxy equivalent of 205. The number average molecular weight 
of the resin was about 1,000. 
(C-2-4): 
The same operations as in the case of the resin for curing (C-2-2) were 
made using 304 parts of 2,4- or 1,4-dimethyl-4-ethenyl-1-cyclohexene oxide 
to obtain a resin for curing (C-2-4) having a solid content of 80% and an 
epoxy equivalent of 199. The number average molecular weight of the resin 
was about 950. 
(C-2-5): 
0.1 part of distilled water was added to 460 parts of Celoxide, 3,000 
##STR29## 
(trade name, produced by DAICEL CHEMICAL INDUSTRIES, LTD.), 0.3 part of 
aluminum acetylacetonate and 5 parts of tetraethoxysilane, the mixture was 
held at 80.degree. C. for 1 hour and then reacted at 120.degree. C. for 3 
hours, and 116 parts of ethylene glycol monobutyl ether was added to 
obtain a resin for curing (C-2-5) having a solid content of 80% and an 
epoxy equivalent of 280. The number average molecular weight of the resin 
was about 1,100. 
(C-2-6): 
132 parts of the dimer of cyclopentadiene was dissolved in 70 parts of 
ethyl acetate, 160 parts of peracetic acid was added dropwise thereto at 
35.degree. C. over a period of 7 hours as an ethyl acetate solution, and 
the mixture was then aged at 40.degree. C. for 6 hours. After removal of 
acetic acid, ethyl acetate and peracetic acid, the residue was dissolved 
in 500 parts of ethyl acetate at 40.degree. C., the solution was washed 
five times each with 250 parts of distilled water, ethyl acetate was 
removed, and the residue was dissolved in 43 parts of methyl isobutyl 
ketone at 80.degree. C. to obtain a compound (1) having a solid content of 
80% and an epoxy equivalent of 90. 
94 parts of 4-vinylcyclohexene was dissolved in 75 parts of ethyl acetate, 
160 parts of peracetic acid was added dropwise, as an ethyl acetate 
solution, thereto at 50.degree. C. over a period of 4 hours, and the 
mixture was then aged at 50.degree. C. for 2 hours. After the removal of 
acetic acid, ethyl acetate and peracetic acid, the residue was dissolved 
in 500 parts of ethyl acetate at 40.degree. C. and washed five times each 
with 250 parts of distilled water, ethyl acetate was removed, and the 
residue was dissolved in 32 parts of methyl isobutyl ketone at 80.degree. 
C. to obtain a compound (2) having a solid content of 80% and an epoxy 
equivalent of 65. 
0.2 part of aluminum acetylacetonate and 10 parts of trimethylolpropane 
were added to 225 parts of the compound (1) and 163 parts of the compound 
(2), the mixture was held at 100.degree. C. for 1 hour and reacted at 
150.degree. C. for 3 hours, 60 parts of ethylene glycol monobutyl ether 
was added, and the mixture was cooled to obtain a resin for curing (C-2-6) 
having a solid content of 70% and an epoxy equivalent of 210. The number 
average molecular weight of the resin was 1,100. 
(C-2-7): 
A solution of 2 parts of azobisdimethylvaleronitrile in 33.4 parts of METHB 
(3,4-epoxycyclohexylmethyl methacrylate) was added dropwise over a period 
of 2 hours to a mixed solvent of 10 parts of methyl isobutyl ketone and 10 
parts of butylcellosolve heated to 100.degree. C., and the mixture was 
aged for 1 hour, heated to 125.degree. C. and further aged at that 
temperature for 1 hour to obtain 54 parts of solution for curing (C-2-7) 
having a solid content of 60% and an epoxy equivalent of 196. The number 
average molecular weight of the resin was 10,000. 
(C-2-8): 
A solution of 2.4 parts of azobisdimethylvaleronitrile in the mixture of 
32.0 parts of METHB monomer with 8.0 parts of hydroxyethyl acrylate was 
added dropwise over a period of 2 hours to 24 parts of butylcellosolve 
heated to 100.degree. C., and the mixture was aged for 1 hour, heated to 
125.degree. C. and further aged at that temperature for 1 hour to obtain 
64.8 parts of a resin for curing (C-2-8) having a solid content of 60% and 
an epoxy equivalent of 245. The number average molecular weight of the 
resin was 12,000. 
(C-2-9): 
A solution of 2.4 parts of azobisdimethylvaleronitrile in the mixture of 37 
parts of 3,4-epoxycyclohexylmethyl acrylate with 3 parts of hydroxyethyl 
acrylate was then treated in the same manner as in the case of the resin 
curing (C-2-8) to obtain a resin for curing (C-2-9) having a solid content 
of 60% and an epoxy equivalent of 200. The number average molecular weight 
of the resin was about 15,000. 
(c-3-1): 
100 parts of N,N-diglycidyl-o-toluidine (produced by NIPPON KAYAKU CO., 
LTD., GOT) and 25 parts of ethylene glycol monobutyl ether were put in a 
flask equipped with a stirrer, a thermometer and a reflux condenser, and 
the mixture was heated to obtain (C-3-1) as a solution. The solid content 
was 80%, and the epoxy equivalent was 117. 
(C-3-2): 
100 parts of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane (produced 
by Japan Ciba-Geigy Co., MY720) and 25 parts of ethylene glycol monobutyl 
ether were put in a flask equipped with a stirrer, a thermometer and a 
reflux condenser, and the mixture was heated to obtain (C-3-2) as a 
solution. The solid content was 80%, and the epoxy equivalent was 115. 
(C-3-3): 
100 parts of 
N,N,N',N'-tetraglycidyl-3,3'-dimethyl-4,4'-diaminodiphenylmethane 
(produced by Japan Ciba-Geigy Co., MY722) and 25 parts of ethylene glycol 
monobutyl ether were put in a flask equipped with a stirrer, a thermometer 
and a reflux condenser, and the mixture was heated to obtain (C-3-3) as a 
solution. The solid content was 80%, and the epoxy equivalent was 125. 
(C-3-4): for comparison 
100 parts of N,N,N',N'-tetraglycidyl-m-xylylenediamine (TETRA-X produced by 
MITSUBISHI GAS CHEMICAL COMPANY INC.) and 25 parts of ethylene glycol 
monobutyl ether were put in a flask equipped with a stirrer, a thermometer 
and a reflux condenser, and the mixture was heated to obtain (C-3-4) as a 
solution. The solid content was 80%, and the epoxy equivalent was 101. 
(C-3-5): for comparison 
250 parts of MDI (4,4'-diphenylmethane diisocyanate) was put in a flask 
equipped with a stirrer, a thermometer and a reflux condenser and melted 
with heating at 80.degree. C. A mixture of 130 parts of 2-ethylhexyl 
alcohol with 134 parts of diethylene glycol monoethyl ether was added 
thereto with retention of 80.degree. C. over a period of 60 minutes. The 
mixture was then heated to 120.degree. C., it was confirmed by IR 
(infrared analysis) that absorption due to the isocyanato group vanished, 
and thereafter 128.5 parts of ethylene glycol monobutyl ether was 
compounded to obtain (C-3-5). The solid content was 80%, and the blocked 
isocyanate equivalent was 257. 
II. Examples and Comparative examples 
The above samples were mixed and dispersed based on the compounding amounts 
shown in the following Tables 2 to 4 to prepare compositions of this 
invention and compositions for comparison. 
TABLE 2 
__________________________________________________________________________ 
Deio- 
Component A 
Component B 
Component C 
Formic 
Lead oc- 
nized 
Name Amount 
Name 
Amount 
Name 
Amount 
acid 
tenoate 
water 
Note 
__________________________________________________________________________ 
Example 
1 A-1 19 B-3 50 0.7 2.6 114 Emulsion mixing 
A-2 19 C-1-1 
38 0.5 93 
2 A-3 19 B-4 50 0.7 2.6 114 Emulsion mixing 
A-4 19 C-1-2 
38 0.5 93 
3 A-5 69 0.7 2.6 114 Emulsion mixing 
A-1 19 C-1-3 
38 0.5 93 
4 A-6 75 0.7 2.6 124 Emulsion mixing 
A-1 13 C-1-4 
38 0.5 83 
5 A-7 63 0.6 2.6 104 Emulsion mixing 
A-2 25 C-1-5 
38 0.5 104 
6 A-5 88 C-1-6 
38 1.2 2.6 207 
7 A-6 88 C-1-7 
38 1.2 2.6 207 
8 A-1 31 B-2 13 C-1-8 
38 1.2 2.6 207 
B-3 31 
9 A-2 38 B-1 13 C-1-9 
38 1.2 2.6 207 
B-4 38 
Comparative example 
1 A-1 38 B-5 50 C-1-1 
38 1.2 2.6 207 
2 A-8 38 B-3 44 C-1-1 
44 1.2 2.6 207 
3 A-6 88 C-10 
38 2.6 DBTDL* Added in 
an amount of 1.2 
__________________________________________________________________________ 
*DBTDL = Dibutyltin dilaurate 
TABLE 2 
__________________________________________________________________________ 
Deio- 
Component A 
Component B 
Component C 
Formic 
Lead oc- 
nized 
Name Amount 
Name 
Amount 
Name 
Amount 
acid 
tenoate 
water 
Note 
__________________________________________________________________________ 
Example 
10 
A-1 19 B-3 50 0.7 2.6 114 Emulsion mixing 
A-2 19 C-2-1 
38 0.5 93 
11 
A-3 19 B-4 50 0.7 2.6 114 Emulsion mixing 
A-4 19 C-2-2 
38 0.5 93 
12 
A-5 69 0.7 2.6 114 Emulsion mixing 
A-1 19 C-2-3 
38 0.5 93 
13 
A-6 75 0.7 2.6 124 Emulsion mixing 
A-1 13 C-2-4 
38 0.5 83 
14 
A-7 63 0.6 2.6 104 Emulsion mixing 
A-2 25 C-2-5 
38 0.5 104 
15 
A-5 88 C-2-6 
38 1.2 2.6 207 
16 
A-6 88 C-2-7 
38 1.2 2.6 207 
17 
A-1 31 B-2 13 C-2-8 
38 1.2 2.6 207 
B-3 31 
18 
A-2 38 B-1 13 C-2-9 
38 1.2 2.6 207 
B-4 38 
Comparative example 
4 
A-1 38 B-5 50 C-2-1 
38 1.2 2.6 207 
5 
A-8 38 B-3 44 C-2-1 
44 1.2 2.6 207 
6 
A-6 88 C-10 
38 2.6 DBTDL* Added in 
an amount of 1.2 
__________________________________________________________________________ 
*DBTDL = Dibutyltin dilaurate 
TABLE 2 
__________________________________________________________________________ 
Deio- 
Component A 
Component B 
Component C 
Formic 
Lead oc- 
nized 
Name Amount 
Name 
Amount 
Name 
Amount 
acid 
tenoate 
water 
Note 
__________________________________________________________________________ 
Example 
19 
A-1 19 B-3 50 0.7 2.6 114 Emulsion mixing 
A-2 19 C-3-1 
38 0.5 93 
20 
A-3 19 B-4 50 0.7 2.6 114 Emulsion mixing 
A-4 19 C-3-2 
38 0.5 93 
21 
A-5 69 0.7 2.6 114 Emulsion mixing 
A-1 19 C-3-3 
38 0.5 93 
22 
A-6 75 0.7 2.6 124 Emulsion mixing 
A-1 13 C-3-1 
38 0.5 83 
23 
A-7 63 0.6 2.6 104 Emulsion mixing 
A-2 25 C-3-2 
38 0.5 104 
24 
A-5 88 C-3-3 
38 1.2 2.6 207 
25 
A-6 88 C-3-1 
38 1.2 2.6 207 
26 
A-1 31 B-2 13 C-3-2 
38 1.2 2.6 207 
B-3 31 
27 
A-2 38 B-1 13 C-3-3 
38 1.2 2.6 207 
B-4 38 
Comparative example 
7 
A-1 38 B-5 50 C-3-1 
38 1.2 2.6 207 
8 
A-8 38 B-3 44 C-3-1 
44 1.2 2.6 207 
9 
A-6 88 C-3-4 
38 1.2 2.6 207 
10 
A-6 88 C-10 
38 2.6 DBTDL* Added in 
amount of 1.2 
__________________________________________________________________________ 
*DBTDL = Dibutyltin dilaurate 
In Tables 2 to 4, 
1) Mixing and dispersion of components were carried out using a disper. 
2) Compounding amounts of components include those of solvents. 
3) The names of the components (A) and the same with those mentioned in the 
preparation examples in Table 1, and among them A-5 to A-7 contain the 
components (B), too. 
4) The component (B-5) in Comparative examples 1, 4 and 7 contains no 
phenol group and has a higher amine value, and was obtained by putting 371 
parts of the amine compound (A-2-1), 105 parts of diethanolamine, 950 
parts of bisphenol A diglycidyl ether, 342 parts of bisphenol A and 442 
parts of ethylene glycol monobutyl ether in a flask equipped with a 
stirrer, a thermometer, a dropping funnel and a reflux condenser, and the 
reacting the mixture at 150.degree. C. until the residual epoxy group 
amount got to be 0, and its solid content was 80%. 
5) (A-8) in Comparative examples 2, 5 and 8 is a component (A) containing 
neither component (A-1-1) nor component (A-1-2), and its preparation 
process is as follows. 
21 parts of diethanolamine, 950 parts of bisphenol A diglycidyl ether 
having an epoxy equivalent of 190, 340 parts of polypropylene glycol 
diglycidyl ether having an epoxy equivalent of 340 and 2052 parts of 
bisphenol A were put in a flask equipped with a stirrer, a thermometer, a 
dropping funnel and a reflux condenser, and the mixture was gradually 
heated with mixing by stirring and reacted at 120.degree. C. After the 
epoxy equivalent was confirmed to be 980, 479 parts of ethylene glycol 
monobutyl ether was added. While the temperature of the system was 
maintained at 100.degree. C., 158 parts of diethanolamine and 43 parts of 
the amino compound (A-2-1) were added, and the mixture was reacted until 
rise in the viscosity ceased, whereby a resin for comparison (A-8) was 
obtained having a solid content of 80%, an amine value of 54 and a primary 
hydroxyl group equivalent of 518. 
6) (C-10) in comparative examples 3, 6 and 10 was obtained by putting 250 
parts of diphenylmethane diisocyanate in a flask equipped with a stirrer, 
a thermometer and a reflux condenser, heating the mixture to 80.degree. 
C., adding dropping a mixture of 130 parts of 2-ethylhexyl alcohol with 
134 parts of diethylene glycol monobutyl ether over a period of 60 
minutes, heating the mixture to 120.degree. C., confirming by IR that 
absorption due to free NCO groups vanished, and then adding 128.5 parts of 
ethylene glycol monobutyl ether. 
7) (C-3-4) in comparative example 9 is a component (C-3) wherein the 
structure represented by the formula (V) does not directly bind to a 
carbon atom of the aromatic ring. 
Preparation example of pigment dispersion paste (Y-1) 
20 parts of titanium white (Tipeck CR93 produced by ISHIHARA SANGYO KAISHA, 
LTD.), 2 parts of carbon (MA-7 produced by Mitsubishi Chemical Industries 
Limited), 4 parts of aluminum tripolyphosphate (K white 84 produced by 
Teikoku Kako Co., Ltd.), 24 parts of clay (Geaklite produced by Geaklite 
Chemical Co., Ltd.), 0.4 part of acetic acid and 39.6 parts of deionized 
water were added to 10 parts of the cationic resin (A-1), the mixture was 
kneaded, and 200 parts of glass beads were added and dispersed by a paint 
shaker to obtain a pigment dispersion paste (Y-1) wherein grits contained 
had a size of 10.mu. or smaller as a value measured by a grindometer and 
which has a solid content of 58%. 
Preparation of electrodeposition coating composition 
75 parts of the pigment dispersion paste (Y-1) was mixed with 333 parts of 
each of the emulsions obtained in Tables 2 to 4, and 310 parts of 
deionized water was added to obtain electrodeposition coating compositions 
having a solid content of 20%. 
Performance test 
Measurement results are shown in arrangement in the following Tables 5 to 7 
of the dispersion particle sizes and MEQ stabilities of the above resin 
compositions (emulsions) as well as the heating losses and salt spray 
resistances of the coating films formed using the above electrodeposition 
coating compositions. 
TABLE 5 
______________________________________ 
MEQ stability 
(milli- 
Dispersion 
equivalent) Heating Salt 
particle 
Initial After loss spray 
size stage storage (%) resistance 
______________________________________ 
Example 
1 0.2 24.5 22.2 3.0 .largecircle. 
2 0.2 25.3 24.0 2.8 .largecircle. 
3 0.15 24.4 21.5 3.8 .largecircle. 
4 0.1 25.3 23.3 2.9 .largecircle. 
5 0.15 24.8 24.0 3.3 .largecircle. 
6 0.1 26.3 25.3 3.8 .largecircle. 
7 0.1 26.0 24.8 4.5 .largecircle. 
8 0.25 25.8 25.1 4.0 .largecircle. 
9 0.25 25.0 23.7 3.5 .largecircle. 
10 0.2 26.3 25.0 4.2 .largecircle. 
Comparative 
example 
1 0.15 24.8 19.5 4.3 X 
2 0.6&lt; 25.0 21.5 4.0 .largecircle. 
3 0.20 26.4 26.7 15.2 .largecircle. 
______________________________________ 
TABLE 6 
______________________________________ 
MEQ stability 
(milli- 
Dispersion 
equivalent) Heating Salt 
particle 
Initial After loss spray 
size stage storage (%) resistance 
______________________________________ 
Example 
10 0.18 25.5 24.8 4.1 .largecircle. 
11 0.19 25.6 25.0 3.5 .largecircle. 
12 0.15 24.8 24.6 4.2 .largecircle. 
13 0.12 24.9 24.4 3.3 .largecircle. 
14 0.20 25.2 25.2 3.8 .largecircle. 
15 0.10 27.3 27.0 4.2 .largecircle. 
16 0.15 26.6 26.0 5.0 .largecircle. 
17 0.22 25.9 26.0 5.1 .largecircle. 
18 0.23 23.0 22.8 3.9 .largecircle. 
19 0.18 25.3 25.0 5.1 .largecircle. 
Comparative 
example 
4 0.12 25.2 25.1 4.4 X 
5 0.6&lt; 26.0 25.8 4.2 .largecircle. 
6 0.20 26.4 26.7 15.2 .largecircle. 
______________________________________ 
TABLE 7 
______________________________________ 
MEQ stability 
(milli- 
Dispersion 
equivalent) Heating Salt 
particle 
Initial After loss spray 
size stage storage (%) resistance 
______________________________________ 
Example 
20 0.25 25.5 23.3 2.8 .largecircle. 
21 0.22 25.4 23.3 2.9 .largecircle. 
22 0.21 24.5 22.5 2.5 .largecircle. 
23 0.15 25.4 23.4 2.9 .largecircle. 
24 0.20 24.9 23.9 3.0 .largecircle. 
25 0.13 26.6 25.6 2.9 .largecircle. 
26 0.14 24.8 23.9 4.0 .largecircle. 
27 0.20 25.9 25.0 3.5 .largecircle. 
28 0.25 24.4 23.4 3.5 .largecircle. 
Comparative 
example 
7 0.20 24.4 24.2 4.0 X 
8 0.6&lt; 25.5 24.5 4.0 .largecircle. 
9 0.21 26.3 17.5 3.5 .largecircle. 
10 0.20 26.4 26.7 15.2 .largecircle. 
______________________________________ 
In Tables 5 to 7, 
(1) Dispersion particle size: 
The diameters of particles of the emulsions (those after a lapse of 12 
hours starting from their preparation) obtained based on the compounding 
of the above Tables 2 to 4 and having a solid content of 30% were measured 
using a Nanosizer N-4 produced by Coulter Co. 
(2) MEQ stability: 
About 10 g each of the emulsions obtained based on the compounding in the 
Tables 2 to 4 and having a solid content of 30% (containing no pigment 
paste) after a lapse of 12 hours starting from the preparation (initial 
stage) and those after closed storage at 30.degree. C. for 20 days were 
accurately weighed, and subjected to titration by a potentiometric 
titration apparatus using 1/10N-KOH alcoholic solution to determine the 
amounts of the acids contained, and MEQ values were calculated according 
to the following equation. Emulsions exhibiting only a small change after 
the storage against the initial value are good. 
EQU MEQ (milliequivalent)=[Titration amount (ml) with the KOH alcoholic 
solution.times.10]/[Sample amount (g).times.0.3] 
(3) Heating loss 
The weight of a zinc phosphate-treated steel plate is expressed as W.sub.0, 
and the treated plate was electrodeposition coated with the above 
electrodeposition coating composition under the above conditions so that 
the thickness of the cured coating film got to be 20.mu., and the coating 
film was dried in a vacuum desiccator under reduced pressure at 80.degree. 
C. for 1 hour. The weight of the coated steel plate is expressed as 
W.sub.1. The plate was then baked with heating at 180.degree. C. for 30 
minutes in an oven. The weight of the resultant plate is expressed as 
W.sub.2. Heating loss was calculated from these values according to the 
following equation. 
EQU Heating loss (%)=[(W.sub.1 -W.sub.2)/(W.sub.1 -W.sub.0)].times.100 
(4) Salt spray resistance: 
An untreated steel plate was electrodeposition coated with the above 
electrodeposition coating composition under the above conditions so that 
the thickness of the cured coating film got to be 20.mu., and heated at 
160.degree. C. for 10 minutes to cure the coating film. This coated plate 
was subjected to the salt spray resistance test according to JIS Z2871 
(time 600 hours). The resultant coating film was judged to stand the test 
(.smallcircle.) when the creek width (one side) from the cut of the 
coating film (linear cut reaching the bare surface) was within 2.00 mm and 
the blister of the coating film of the parts other than the cut part was 
8F (ASTM) or less, and judged not to stand the test (.times.) when they 
were above the values.