JPH02255874A - Resin composition for cationic electrodeposition coating material - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in stability, curability, adhesion of a coating film, etc., without using any organotin compound and any blocked isocyanate by mixing a resin having an OH group and a cationic group with a specified epoxy resin. CONSTITUTION:A resin (A) having OH groups in an amount of 205000 in terms of a hydroxyl equivalent and cationic groups in an amount of 3-200 in terms of an amine value (KOH mg/g solid matter), desirably a reaction product obtained by reacting the epoxy groups of a polyepoxide compound obtained from a polyphenol compound and epichlorohydrin with a cationizing agent and an epoxy resin (B) having at least two epoxy functional groups on the average per molecule and prepared by bonding epoxy groups to an alicyclic skeleton and/or an organic alicyclic skeleton are dispersed in water, and a pigment, a dispersant, a cure accelerator, a nonionic surfactant, etc. are optionally added to the dispersion.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention eliminates the need to use block polyisocyanate as a curing agent or organotin compound as a curing catalyst,
The present invention relates to a resin composition for cationic electrodeposition coatings that has excellent stability and curability, and also has excellent properties such as coating film adhesion, weather resistance, and low-temperature curability.

Conventionally, resin compositions for cationic electrodeposition coatings have been mainly composed of polyamine resins such as amine-added 1-boxy resins and aromatic polyisocyanate compounds (curing agents) blocked with alcohols, etc. The most commonly used H, A film has been highly evaluated for its anticorrosion properties. 1
However, the essential problem with this coating resin composition is that it has a high curing initiation temperature (170°C or higher).
2. Lower the curing start temperature. Second, when an organic tin compound is used as a curing catalyst, the tin compound may poison the exhaust combustion catalyst of the baking furnace: Furthermore, in order to harden the coating film. When heated at high temperatures, the block polyisocyanate thermally decomposes to produce tar and soot, which causes yellowing, bleeding, and curing inhibition of the top coat, and significantly reduces the weather resistance of the top coat and film. It has serious drawbacks such as being susceptible to whitening, and there is a strong desire to improve it.

For this reason, the present inventors have developed a cationic electrodeposition method that has the excellent advantages of isocyanate curing type without using block polyisocyanate compounds or organic tin compounds, and eliminates the disadvantages caused by using these. We have conducted extensive research in order to provide a resin composition for paints.

However, the use of self-crosslinking and curing by ring-opening reaction of epoxy groups without using a curing agent 1. Resins for coating printing are also known, for example, Japanese Patent Publication No. 49-31736,
Japanese Patent Publication No. 49-23807, Japanese Patent Publication No. 48-6989
Publication No. 6, JP-A-47-! Although these methods have been proposed in Japanese Patent No. 3432, etc., none of these methods can achieve both the bath stability of the electrodeposition paint and the curability of the coating film. For example, among these, the most common glycidyl ether type polygovoxy compound has excellent curability but poor bath stability.

Therefore, the present inventors have found that by using certain types of polyfunctional polymers as curing agents, they have excellent stability and curing properties without reducing corrosion resistance. The various defects mentioned above due to the use of polyiso-anate compounds can be eliminated, and since there is no distortion due to volumetric shrinkage, it has excellent adhesion, significantly improves the weather resistance of the coating film, and has low curing properties. The present inventors have discovered a resin composition for cationic electrodeposition coatings that has excellent properties, and have completed the present invention.

According to the present invention, the resin (A) containing a hydroxyl group and a cationic group: 1poA'-cy group is bonded to the alicyclic skeleton and/or the bridged alicyclic skeleton. Provided is a resin composition for a cationic electrodeposition coating, which contains as a main component an epoxy resin (B) having an average of two or more epoxy group-containing functional groups per molecule.

The electrodeposition coating film formed using the resin composition for cationic electrodeposition coating of the present invention is cured at a temperature of about 250° C. or lower. In particular, when one or more compounds containing metals such as lead, zirniconium, cobalt, aluminum, manganese, copper, zinc, iron, chromium, and nickel are mixed with a catalyst, the temperature rises from about 0°C to about 160°C. It can be cured even when heated at low temperatures. In these curing processes, the epoxy groups contained in the epoxy resin (B) ring-open and the hydroxyl groups in the resin (A) (
It is presumed that the Evo-1'-C groups in the resin (B) react with each other to form ether bonds, resulting in crosslinking and curing.

Therefore, the resin composition for cationic electrodeposition coatings of the present invention can be cured at a low temperature of 160°C or higher without using a tin catalyst;・The various defects mentioned above can be solved by using compound 1 since its derivatives are not used.
Shows good adhesion with no volume shrinkage due to thermal decomposition; no aromatic urethane bonds or aromatic urea bonds are introduced during cross-linking, so there is little loss of weather resistance; corrosion resistance of electrodeposited coatings and It has excellent advantages such as: good curability and good stability of electrodeposition bath.

Resin (A) having a hydroxyl group and a canonical group used in the composition of the present invention (hereinafter referred to as "base resin")
A)") includes any cationic group containing a hydroxyl group capable of reacting with the epoxy group of component (B) and a sufficient number of cationic groups to form a stable aqueous dispersion. The resin is included. However, the base resin (A
) include, for example, the following:

(+) React the polyepoxy resin and Al+ canane 1. (ii) A condensate of a polycarboxylic acid and a polycarboxylic acid (see US Pat. No. 2,450,940) with an acid (1.:I): (i) Polyadducts of polyisocyanates and polyols with mono- or polyamines, protonated with acids; (iv) Copolymers of acrylic or vinyl monomers containing hydroxyl groups and amino groups, protonated with acids. (Special Publication No. 45-12395, Special Publication No. 45-1
No. 2396): (V) An adduct of a polycarboxylic acid resin and an alkylene imine protonated with an acid (U.S. Patent No. 3,40)
3,088); etc.

For specific examples and manufacturing methods of these cationic resins, see, for example, Japanese Patent Publication No. 45-12395,
-12396, Japanese Patent Publication No. 4923087, U.S. Patent No. 2.450°940, U.S. Patent No. 3,
403,088, U.S. Pat. No. 3,891.52
9, Japanese Patent No. 3,963,663, etc., these citations will be replaced with detailed descriptions here.

Particularly desirable as the base resin (A) in the present invention is a polyepoxide compound, which is included in the above (i) and is obtained by reacting a cationizing agent with the epoxy group of a polyepoxide compound having excellent corrosion resistance obtained from a polyphenol compound or epichlorohydrin. The resulting reactive product.

The polyepoxide compound is an epoxy group compound, generally at least 200, preferably from 400 to 4,000,
More preferably, those having a number average molecular weight within the range of 800 to 2.000 are suitable. As such polyepoxide compounds and io, those known per se can be used, for example, the polyglycidyl compounds of borifue, which can be produced by reacting a polyphenol compound with epichlorohydrin in the presence of an alkali. Dell is included. Examples of polyphenol compounds that can be used here include bis(4
-hydroxyphenyl)-2,1-propane, 4,4'
-dihydroxybenzophenone, his(4-hydroxyphenyl)-1,1-ethane, his-(4-hydroxyphenyl)-1,! -isobutane, bis(4-hydroxy-tert-butyl-phenyl)-2,2-propane, bis(2-hydroxynaphthyl)methane, 1,5-dihydroxynaphthalene, bis(2,4-dihydroxyphenyl)methane, tetra (4-hydroxyphenyl)-
Examples thereof include 1,1,2,2-ethane, 4,4'-dihydroxydiphenyl 1-thyl, 4,4'-dihydroxydiphenyl sulfone, phenol novolak, and cresol novolak.

Among the polyepoxide compounds mentioned above, those particularly suitable for the preparation of base resin A have a number average molecular weight of at least about 38
0, more preferably about 800 to about 2,000, and an epoxy equivalent weight of 190 to 2,000, preferably 400 to i,
It is a polyglycidyl needle of a polyphenol compound within the range of o o o, especially one represented by the following formula % formula %. The polyepoxide compound may be partially reacted with polyols, polyether polyols, polyester polyols, polyisocyanates, etc., and may also be graft-polymerized with δ-4 caprolactone, acrylic monomers, etc. Good too.

On the other hand, as the cationizing agent for introducing a cationic group into the polyepoxide compound, aliphatic, t- or alicyclic or aromatic-aliphatic primary or secondary amines,
Examples include tertiary amine salts, secondary sulfide salts, and tertiary bosphine salts.

These react with epoxy groups to form cationic groups. Furthermore, a tertiary amino monoisocyanate obtained by reacting a tertiary amino alcohol with a diisocyanate can be reacted with a hydroxyl group of an epoxy resin to form a cationic group.

Examples of the amine compound in the cationizing agent include:
For example, the following can be exemplified.

(1) Methylamine, ethylamine, n- or 1so
-7' pyramine, monoethanolamine, n-mataha1
Primary amines such as so-propanolamine: (2) diethylamine, jetanolamine, di-n-
or secondary amines such as 1so-7' lovanolamine, N-methylethanolamine, N-ethylethanolamine; (3) ethyldiamine, diethylenetriamine, hydroxyethylaminoethylamine, ethylaminoethylamine, methylaminopropylamine , dimethylaminoethylamine, and polyamines such as dimethylaminoethylamine.

Among these, alkanolamines having a hydroxyl group are preferred. Alternatively, the primary amine group may be blocked in advance with a ketone and then reacted with an epoxy group using the remaining active hydrogen.

Furthermore, in addition to the above-mentioned amine compounds, basic compounds such as ammonia, hydroxylamine, hydrazine, hydroxyethylhydrazine, and N-hydroxyethylimidacillin compounds can also be used. The basic group formed using these compounds can be protonated to a cationic group with an acid, particularly preferably a water-soluble organic carboxylic acid such as formic acid, acetic acid, glycolic acid or lactic acid.

Furthermore, triethylamine, triethanolamine, N
, N-dimethylethanolamine, N-methyljetanolamine, N, N-'; ethylethanolamine, N
- Tertiary amines such as ethyljetanolamine can also be used, and these can be preprotonated with acid and reacted with epoxy groups to form quaternary salts.

In addition to amino compounds, sulfides such as di-1 delsulfide, diphenyl sulfide, tetramethylene sulfide, and thiogetanol, and salts such as boric acid, carbonic acid, and organic monocarboxylic acids can be reacted with epoxy groups to form a tertiary compound.
Class sulfonium salts may also be used.

Furthermore,! - Phosphines such as ethylphosphine, phenyldimethylphosphine, diphenylmethylphosphine, and triphenylphosphine, etc. A quaternary phosphonium salt may be obtained by reacting a salt with an acid such as those listed in 2 above with an epoxy group.

In the hydroxyl group and 17 of the base resin (A) used in the present invention, for example, the alkanolamine in the above-mentioned cationizing agent, the ring-opened product of caprolactone that may be introduced into the epoxy compound, and the primary compound that can be introduced from polyol, etc. Hydroxyl groups; secondary hydroxyl groups in epoxy resins, etc. can be opened. Of these, the first introduced by alkanolamine
Hydroxyl groups are preferred because they have excellent crosslinking and curing reactivity with the epoxy resin (B). As such alkanolamines, those exemplified as the cationizing agent are preferable.

The content of hydroxyl groups in the base resin (A) is 20 to 5°000 in terms of hydroxyl equivalent, especially 10
It is preferably within the range of 0 to 1.000, and in particular, it is desirable that the primary hydroxyl equivalent is within the range of 200 to 1,000. In addition, the content of cationic groups is as follows:
It is preferable that the required minimum amount is enough to stably disperse the KO
Generally 3 to 2 in terms of H (mg/g solid content) (amine value)
00, particularly preferably within the range of lO to 80.

However, even if the content of cationic groups is 3 or less, it is possible to use a surfactant or the like [7] to form an aqueous dispersion. It is desirable to adjust the cationic group so that the pH is usually 4-9, more preferably 6-7.

The base resin (A) used in the present invention has a hydroxyl group and a cationic group, and preferably does not contain free epoxy groups in principle.

Next, the epoxy resin (B), which is a curing agent used in combination with the base resin (A), will be explained.

The epoxy resin (B) (hereinafter referred to as "curing resin")
B)") is a curing agent for forming a crosslinked cured coating film mainly through etherification reaction with the base resin (A) as described above, and It has an average of 2 or more functional groups per molecule, preferably 3 or more.

That is, the curable group-containing functional group in the curing resin (B) consists of an alicyclic skeleton and/or a bridged alicyclic skeleton and an epoxy group, and the alicyclic skeleton has 4 to 10 members, preferably The bridged alicyclic skeleton contains a 5- to 6-membered saturated carbocyclic ring or a condensed ring in which two or more of these rings are condensed, and the bridged alicyclic skeleton is
A straight chain or branched CI-s (preferably Cl
-6) Alkylene group [e.g. -CHX CH2C
H2-CH(CH3) CHz(CHs)CHz
--C(CH3) 2 CH(Cx Hs) C
H! -, etc.] contains a ring bonded to a bridge (endomedilene, endoedylene, etc.).

On the other hand, in an epoxy group (>C-cQ), one of the carbon atoms in the epoxy group is directly bonded to a ring carbon atom in the alicyclic skeleton or the bridged alicyclic skeleton [e.g. , see the following formulas (I) and (n)], or two carbon atoms of the epoxy group and two adjacent carbon atoms constituting a ring in the alicyclic skeleton or bridged alicyclic skeleton. have in common [
For example, see the following formulas (III) and (IV)] is important.

Specific examples of such epoxy group-containing functional groups include those represented by the following formulas (I) to (IV).

h8　h.

In the formula, R8, R2, R1, R,, R,, R2, RIO and R+□ each represent H, CH, or CmH6, and R4, R1 and R5 each represent I] or C1
4.

The epoxy resin (B) used in the present invention has the above formula (I) ~
Each molecule can have an average of at least 2, preferably 2 or more, and more preferably 4 or more epoxy group-containing functional groups selected from (IV), for example, an epoxy group represented by formula CI) or (It). It can have at least one type of containing functional group, or it can have at least one type of epoxy group-containing functional group represented by formula (III) or (TV). Furthermore, epoxy resin (
B) comprises at least one epoxy group-containing functional group represented by formula (I) or (IN) and at least one epoxy group-containing functional group represented by formula (III) or (IV). can be in the same molecule or in different molecules.

Among the above, epoxy group-containing groups represented by formulas (1) and (III) are preferred, and epoxy group-containing functional groups represented by the following formula (V) and epoxy group-containing functional groups represented by the following formula are particularly preferred. suitable.

Furthermore, the epoxy weight and molecular weight of the epoxy resin (B) used in the present invention are not strictly limited, and can be changed depending on the manufacturing method and the use of the final resin composition. Generally speaking, the epoxy equivalent is usually 1
00 to 2,000, preferably 150 to 500, more preferably 150 to 250,
Moreover, the number average molecular weight is usually 400 to 100,000. Preferably 700 to 50,000, more preferably 70
It is suitably within the range of 0 to 30,000.

The epoxy resin [curing resin (B)] having two or more such epoxy group-containing functional groups in one molecule is, for example,
] Publication No. 56-8016 JP 57-47365
No. 6, JP-A No. 6 O-1f35675, JP-A No. 6 O-1f35675, JP-A No. 6
It is described in documents such as No. 122112i and Japanese Patent Application Laid-Open No. 63-234028, and those known per se can be used.

Alternatively, the epoxy resin (B) having an epoxy group-containing functional group can be obtained by a method known per se, and the main manufacturing methods thereof are listed below, but are not limited thereto.

First production method: After partially epoxidizing a part of the double bonds of an alicyclic compound having two carbon-carbon double bonds in one molecule and ring-opening polymerization of the carbon-carbon double bonds, , a method of epoxidizing the double bonds remaining in the polymer.

Second production method - A method of ring-opening polymerizing an alicyclic compound having two or more of one epoxy group in the molecule, based on the epoxy group, to such an extent that all of the epoxy groups are not erased.

Third manufacturing method - A method of polymerizing a compound having an epoxy group-containing functional group and a polymerizable unsaturated bond in the molecule.

Hereinafter, these manufacturing methods will be explained in more detail.

In order to epoxidize a part of the double bonds contained in an alicyclic compound having two carbon-carbon double bonds in one molecule (hereinafter abbreviated as "alicyclic compound (A)"), partial epoxy compound), then ring-opening polymerization of the epoxy group to obtain a ring-opening polymer of the partially epoxidized compound, and then curing by epoxidizing some or all of the double bonds remaining in the polymer. A resin (13) is obtained.

The alicyclic compound (A) has an alicyclic ring or a bridged alicyclic ring structure as described above for the alicyclic skeleton or a bridged alicyclic skeleton as a basic skeleton, and further has a double bond that constitutes the ring. It is a compound that contains at least two or more double bonds that exist between two adjacent carbon atoms or are based on other carbon atoms and are directly bonded to a carbon atom that constitutes the ring structure.

The alicyclic compound (A) can also be obtained, for example, by heating a conjugated diene compound according to a known method. Conjugated diene compounds contain one double bond in a conjugated relationship in one molecule.
Suitable aliphatic or alicyclic metal compounds having 4 to 30 carbon atoms, preferably 1 to 5 pairs, include -C, specifically butadiene, isoprene, birylene, 1,3-hexadiene, 2゜4-\xadiene, 2.4-hebutage〉
・, 2-methyl-6-me'f-1, so 2. Fuoctagie〉・,2.6-di2meflu1.5.7-octaI
・Jien, Cyclobe〕・Tajie〉・, Cyclohekiji 1
', 4-gotyl-2-methylcyclobentazoene, 3-iso, / tJbiru-1methylcyclobentadiene]..., 5-isopropylcyclopentadiene 1.2
．． 3.1-ta”] Loveenylsik II Pentagene,
1,2.4-1 ~ Rife: Le Nck [7 bentadiene,
l, 4-diphenylcyclopentadiene, ■, 3-ocucchlorpentadiene, hexyl-oxy-1,2,3,4-tetonchlorpentadiene Pentadicorn, 1, 2, 3, 4.5
-Pentachlorcyclobentazico87,i,2.3.4
~te]lachlorune clobentadiene, 1.3-', , arborvitae]/tajene, 1.3-ra clooctadiene, l
, 3.5-dichlorooctatriene, 1,3.6-cyclooctatatriene, citalooctadetraene, chlorocyclooctatetraene, bromcyclooctatetraene,
Examples include 5-cyclohegylidenecyclopentadiene, and these can be used alone or in combination of two or more.

When the conjugated diene compound is reacted under heating using a Ziegler catalyst if necessary, the alicyclic compound (A) is obtained. This heating reaction can be carried out by a method known per se, for example, by the method disclosed in JP-A-49102643. Representative examples of the alicyclic product (A) obtained in this manner are as follows.

Among the above conjugated diene compounds, compounds having an alicyclic structure such as cyclopentadiene, cyclohexadiene, 4-ethyl-2-methylcyclopentadiene, sylvestrene, 2.8(9)-p-,' 7tadiene, vironene, l,3-dimethyl-1-ethyl-3,5-cyclohexadiene, terpinene, phelandrene, dipentene,
Isolimonene, limonene, etc. are already alicyclic compounds (A
), it can be used as it is without being subjected to the above thermal reaction.

First, a part of the carbon-carbon double bonds contained in the alicyclic compound (A) is modified into an epoxy group using a peroxide or the like (
Partial epoxidation), partial epoxidation products are those in which some of the double bonds contained in the alicyclic compound (A) are modified into epoxy groups, and specific examples thereof are as follows. .

It can also be used as a partially epoxidized product.

The partially epoxidized product has at least one epoxy group and at least one carbon-carbon double bond in one molecule,
It is necessary that the double bond exists between two adjacent carbon atoms constituting a ring, or that a double bond based on another carbon atom is bonded to a carbon atom of an alicyclic ring (7>1).

Next, the epoxy groups in this partially epoxidized product are subjected to ring-opening polymerization 1 to obtain a polymer of the alicyclic compound (A). It is preferable to use an initiator in this ring-opening polymerization, and a residue X due to the initiator component may be bonded to the end of the curing resin (B), which is the final product. Here, X is a residue of an organic compound having active hydrogen, and examples of the organic compound having active hydrogen, which is a precursor thereof, include alcohols, phenols, carboxylic acids, amines, and guols. can give. Among these, alcohol is
It may be either a monohydric alcohol or a polyhydric alcohol with more than 2 hydric alcohols, specifically, for example, aliphatic monohydric alcohols such as methanol, ethanol, propatool, butanol, pentanol, hexanol, octatool, etc. :
Aromatic monohydric alcohols such as benzyl alcohol; ethyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, l,3-butanediol, 1,4-butanediol, bentane diol, l,6-hexanediol, neopentyl glycol, oxypivalic acid neopentyl glycol ester,
Examples include polyhydric alcohols such as cyclohexane dimetatool, glycerin, diglycerin, polyglycerin, trimethylolpropane, trimethylolethane, pentaerythritol, and dipentaerythritol.

Examples of phenols include phenol, cresol, catechol, frogallol, hydroquinone, hydroquinone monomethyl ether, and bisphenol A1.
Examples include bisphenol F, 4.4' dihydroxybenzophenone, bisphenol S1 phenolic resin, and cresol novolac resin.

Carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, fatty acids from animal and vegetable oils; fumaric acid, 71°ic acid, adipic acid, dodecanoic acid, trimellitic acid, pyromellitic acid, polyacrylic acid, phthalic acid, isophthalic acid. Examples include acids such as terephthalic acid, and compounds having both a hydroxyl group and a carboxylic acid such as lactic acid, citric acid, and oxycaproic acid can also be used.

In addition, other active hydrogen-containing compounds include alkoxysilanes such as tetramethylsilicate, tetramethylsilicate, methyltrimethoxysilane, methyl[.liethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, etc., or mixtures of these with water. Silanol compounds, polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate, cellulose acetate butyrate], hydroxyethyl cellulose, acrylic polyol resin, styrene-allyl alcohol co-st resin, styrene-maleic acid co-polymer Polymer resins, alkyd resins, polyester polymer resins, polyol resins, etc. can also be used. Further, it may have an unsaturated double bond together with active hydrogen, and the unsaturated double bond may be epoxidized. Also,
The catalyst and initiator may be the same, such as an alkoxy metal compound.

Usually, the above-mentioned organic compound having active hydrogen is used as an initiator.
, the above partially epoxidized products, such as 4-vinylcyclohexene-1-oxide, 4-vinylcyclo[2,2,1
13-methyl-4(or 5)-t-propenyl~l-
Cyclohexene oxide, 2,4- or 1,4-dimethyl-4-ethynyl-1-cyclohexene oxide, 4
Ring-opening polymerization is carried out using one or more of -vinylcyclo[2,2,1]hebutene-1-oxide (vinylnorbornene oxide), 2-methyl-4-isopropanyl-cyclohexene oxide, and the like.

At this time, it is also possible to further include another epoxy compound that does not belong to the above-mentioned partially epoxidized products and carry out ring-opening copolymerization. Other epoxy compounds that can be copolymerized include:
Any compound having an epoxy group may be used, but suitable examples include oxides of unsaturated compounds such as ethylene oxide 1:, propylene oxide, butylene oxide, and styrene oxide; allyl glycidyl ether, 2 Glycidyl ether compounds such as edylhexyl grindyl ether, methyl glycidyl ether, butyl glycidyl needle, phenyl grindyl ether, etc. Glycidyl ester compounds of unsaturated organic carboxylic acids such as niacrylic acid and methacrylic acid: to 3.4-epoxycyclo Examples include alicyclic oxirane group-containing vinyl monomers such as xylmethyl (meth)acrylate.

The ring-opened 1i f3 isomer can be obtained by ring-opening polymerization (ether bonding) of the epoxy groups contained in the partially epoxidized product alone or in combination with other epoxy compounds as necessary.

The composition ratio of other epoxy compounds in the ring-opened polymer can be arbitrarily selected depending on the purpose, but specifically, the proportion of the structural formula (I) per molecule of the ring-opened copolymer obtained is
- (IV) It is desirable to select a measuring tool having an average of 2 measuring tools or more, preferably 3 or more, more preferably 4 or more on average.

The number average molecular weight of the (co)polymer thus obtained is generally from 400 to ioo, ooo, especially from 700 to 50.
,000, more preferably within the range of 700 to 30,000.

The ring-opening polymerization reaction is generally preferably carried out in the presence of a catalyst, and examples of catalysts that can be used include amines such as 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 alcoholades such as sodium methylate; Alkali such as KOH%NaOH 11. B
F,,ZnCQx,A 4CI2. ．． Examples include Lewis acids such as 5nCQ or complexes thereof; organometallic compounds such as triethylaluminum, aluminum acetylacetonate, titanium acedelacetonate, and diethylzinc.

These catalysts generally have a concentration of 0.001 to 1 O relative to the reactants.
It can be used in a range of 0.001 to 5% by weight. The ring-opening polymerization reaction temperature is generally about -70~
About 200°C, preferably within the range of about -30°C to about 100°C. The reaction can be carried out using a solvent, and it is preferable to use a conventional organic solvent that does not contain active hydrogen.

A double bond based on the alicyclic compound (A) is present in the ring-opened 1fL combination, and an epoxy resin (B) can be obtained by epoxidizing all or part of it. Single epoxidation of double bonds can be carried out using epoxidizing agents such as peracids and hydroperoxides. Whether or not a solvent is used during the epoxidation reaction and the reaction temperature are as follows:
It can be adjusted as appropriate depending on the equipment used and the physical properties of the raw materials. Depending on the conditions of the epoxidation reaction, side reactions may occur simultaneously with the epoxidation of double bonds in the raw ring-opening polymer, and modified substituents may be included in the skeleton of the epoxy resin (B). Examples of this modified substituent include, for example, when peracetic acid is used as an epoxidizing agent, the substituent has the following structure, and this is thought to be due to the reaction between the generated epoxy group and the by-produced acetic acid. .

゛′? The proportion of these modified substituents is determined by the type of epoxidizing agent, the molar ratio of the epoxidizing agent to the unsaturated group, and the reaction conditions.

The epoxy equivalent of the epoxy resin (B) obtained in this way is generally 100 to 2,000, particularly 150 to 500.
, more preferably within the range of 150 to 250,
stomach.

Such an epoxy resin (B) and 1. 71j products can also be used, for example, EHPE ~ 3150, EHPE
-3100, E HP Diko - 1150[da,
Isel Chemical Industry Co., Ltd.'s product name 1 is an epoxy resin having the following structural formula and having a cyclohexane skeleton using 4-vinylcyclohexene oxide.

In the formula, n is 2 or more, preferably 3 or more, more preferably 4 or more.

Second production method: For example, it can be obtained by epoxidizing at least two of the double bonds contained in the alicyclic compound (A), and then ring-opening polymerization so that the epoxy group remains.

The epoxidized compounds having an average of two or more epoxy groups per molecule are representative of the following monocyclic or condensed ring compounds.

Specifically, one or more of the above-mentioned epoxides are prepared in the same manner as described in the first manufacturing method, and if necessary, an initiator,
Epoxy resin (B) is obtained by carrying out a ring-opening polymerization reaction using a catalyst and stopping the reaction at a predetermined reaction point where an epoxy group remains.

Any means such as dilution with a solvent or cooling can be used to stop the reaction. In this production method as well, the epoxy compound having the above properties may be copolymerized in the same manner as in the first production method.

The curable resin (B) thus obtained contains at least one epoxy group-containing functional group represented by the formula (I) or (II) and an epoxy group-containing functional group represented by the formula (III) or (IV). It is also possible to use an epoxy resin having at least one of I and I in the same molecule or in different molecules.

The ring-opened polymer thus obtained [curing resin (B)]
The number average molecular weight of 1 is generally in the range of 400 to 10,000, particularly preferably in the range of 700 to 50,000,
It is also advantageous for the epoxy equivalent weight to generally be in the range 100 to 2,000, particularly 150 to 500, and even 150 to 250.

Third production method: A compound having at least one epoxy group-containing functional group and at least one polymerizable unsaturated bond in the same molecule (hereinafter referred to as
Examples of the "polymerizable epoxy monomer" (sometimes abbreviated as "polymerizable epoxy monomer") include those shown in the following formulas 1 to 0.

■ In the above formula, R11 represents a hydrogen atom or a methyl group, R1° represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R13 represents a divalent hydrocarbon group having 1 to 10 carbon atoms. represents a group.

In the above polymerizable epoxy monomer, the divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms represented by R12 is a linear or branched alkylene group, such as methylene, ethylene, propylene, tetramethylene, ethyl Ethylene, pentamethylene, hexamethylene groups, etc. can be mentioned.

Also, R1! Examples of the divalent hydrocarbon group having 1 to 10 carbon atoms represented by include methylene, ethylene, furopylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, and the like.

Specific examples of the polymerizable epoxy monomers represented by formulas (1) to (@) above include 3.4-epoxycyclohexylmethyl acrylate and 3.4-epoxycyclohexylmethyl acrylate. Examples of these commercially available products include METHB and A manufactured by Daicel Chemical Industries, Ltd.
Examples include ETHB (all trade names), all of which have an epoxy group-containing functional group represented by the formula (I) or (II). Furthermore, 4-vinylcyclohexene oxide can also be used as a polymerizable epoxy monomer.

Epoxy resin (B) can be produced by polymerizing one or more selected polymerizable epoxy monomers, but in this case, other polymerizable unsaturated monomers may be used.
It is also possible to copolymerize.

The above-mentioned other polymerizable unsaturated polymers can be selected from a wide range depending on the desired performance of the resulting (co)polymer, and representative examples thereof are as follows.

(a) Esters of acrylic acid or methacrylic acid: for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, ocdyl acrylate, lauryl acrylate, methyl methacrylate, methacrylic acid Ethyl, propyl methacrylate, isopropyl methacrylate,
C1-18 alkyl esters of acrylic acid or methacrylic acid such as butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate;
Acrylic acid or methacrylic acid with 2 carbon atoms, such as methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, and ethoxybutyl methacrylate
~I8 alkoxyalkyl esters; C2-8 alkenyl esters of acrylic or methacrylic acid such as allyl acrylate and allyl methacrylate; acrylic acids such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxyethyl acrylate or C2-C8 hydroxyalkyl ester of methacrylic acid: C3-C18 alkenyloxyalkyl ester of acrylic acid or methacrylic acid such as allyloxyethyl acrylate and allyloxymethacrylate.

(b) Vinyl aromatic compounds; for example, styrene, a
-Methylstyrene, vinyltoluene, p-chlorostyrene.

(C) Polyolefin compounds: For example, butadicyene, isoprene, chlorobrene.

(d) Others: acrylonitrile, methacrylaterile, methyl isopropenyl ketone, vinyl acetate bivalate (Shell Chemicals), vinylpropione-1,
Vinyl bivalate, a vinyl compound with a polycaprolactone chain (e.g. FM-3X monomer: trade name manufactured by Daicel Chemical Industries, Ltd.) 6 The composition ratio of the polymerizable epoxy monomer and other polymerizable unsaturated monomers is arbitrary depending on the purpose. The number of epoxy group-containing functional groups per molecule of the epoxy resin (B) obtained by these copolymerization reactions is at least 2 on average, preferably 3fi1 on average.
As mentioned above, the epoxy resin (B
) Polymerizable epoxy monomer content in solid content is 5 to 100
It is preferable that the amount is within the range of 20 to 100% by weight, more preferably 20 to 100% by weight.

Epoxy resin (B
) can be produced using the same method and conditions as those for polymerization reactions based on polymerizable unsaturated bonds in ordinary acrylic resins, vinyl resins, and the like. As an example of such a polymerization reaction,
A method can be shown in which each monomer component is dissolved or dispersed in an organic solvent and heated while stirring at a temperature of about 60 to 180° C. in the presence of a radical pre-initiator. The reaction time can usually be about 1 to 10 hours. Further, as the organic solvent, alcohol solvents, ether solvents, ester solvents, hydrocarbon solvents, etc. can be used.

When using a hydrocarbon solvent, it is preferable to use other solvents in view of solubility. Furthermore, any commonly used radical initiator can be used, and specific examples include peroxides such as benzoyl peroxide and t-butylperoxy-2-ethylhexanoate; ;・Azo compounds such as lyle, azobisdimethylvaleronitrile, etc. can be shown.

The epoxy resin (B) of the third production example above generally has a number average molecular weight of about 3.000 to about ioo, oo.

Those within the range of 4,000 to io are preferred, especially 4,000 to io
, ooo is more preferable.

Among the above-mentioned curing resins (B), those that have an epoxy group per molecule are suitable for use in applications that require high performance, such as cationic electrodeposition paints used for automobile bodies. It has on average 3 or more functional groups, more preferably on average 4 or more, most preferably on average 5 or more, and has an epoxy equivalent of preferably 100 to 2°000, more preferably is 150-500,
In particular, it is within the range of 150 to 250, and the number average molecular weight is preferably 400 to 100,000, more preferably 700 to 50,000, particularly preferably 700 to 30.
．． It is within the range of 000. .

The amount of curing resin CB) to be used depends on the type of base resin (A) used, and it ranges from the minimum amount necessary for thermosetting the resulting coating film to the maximum amount that does not impair the stability of the cationic electrodeposition paint. The weight ratio of the solid content of the hardening resin 1111t (B) to the base resin (A) can be changed as appropriate within a large range, but generally the weight ratio of the solid content of the hardening resin 1111t (B) to the base resin (A) is 0.2 to 1.0, particularly 0.25 to 0.
85, more preferably within the range of 0.25 to 0.65.

The composition of the present invention may contain a part of the curable resin ([3) added in advance to the base resin (A).

Thus, the composition consisting of the base resin (A) and the curing resin (B) can be used as a resin for cationic electrodeposition coatings.

In order to prepare the composition for cationic electrodeposition coating of the present invention, for example, after mixing the base resin (A) and the curing resin (B), they are stably dispersed in water, and then, if necessary, carbon black is added. Color pigments such as , titanium white, lead white, lead oxide, red iron; extender pigments such as clay, talc; strontium chromate, lead chromate, basic lead chromate,
Red lead, lead silicate, basic lead silicate, lead phosphate, basic lead phosphate, lead tripolyphosphate, lead silicochromate, yellow lead, lead cyanamide, calcium leadate, lead zinc oxide, lead sulfate, basic This is done by kneading an anticorrosive pigment such as lead sulfate or other additives. Other additives that may be blended include, for example, a small amount of a nonionic surfactant as a dispersant or an anti-repellent agent for the coated surface, a curing accelerator, and the like.

In particular, in order to cure the T-adhesive coating film of the composition of the present invention sufficiently at a low temperature of 160°C or less, lead compounds, zirconium compounds, cobalt compounds, aluminum compounds, manganese compounds, copper compounds, zinc compounds are required. It is effective to add one or five or more metal compounds selected from iron compounds, chromium compounds, nickel compounds, etc. as catalysts. Specific examples of these metal compounds include chelate compounds such as zirconium acetylacetonate, cobalt acetylacetonate, aluminum acetylacetonate, and manganese acetylacetonate; compounds having a β-hydroxyamino structure and lead (n) oxide; Chelation reaction products: carboxylates such as lead 2-ethylhexanoate, lead oxide, lead octoxide, lead benzoate, lead acetate, lead lactate, lead formate, lead glycolate, zirconium octoxide, etc. Can be mentioned.

The above metal compound consists of a base resin (A) and a curing resin (B).
), the metal content is generally 10
It can be used in amounts up to 5% by weight, preferably up to 5% by weight.

The thickness of the coating film obtained by electrodepositing the resin composition for cationic electrodeposition paint thus prepared on a suitable substrate is not strictly limited, but in general, Depending on the film, a range of 3-200μ is suitable, and the coating film can be heated, for example, at 70-250°C, preferably at 120°O-1.
It can be heated and cured at a temperature of between 60°C.

The method of forming an electrodeposition coating film on a substrate using the resin for cationic electrodeposition coating of the present invention is not particularly limited.
It can be carried out using ordinary cationic electrodeposition coating conditions. For example, the base resin (A) and the curing epoxy equivalent (B) according to the present invention are dispersed in water as described above, then pigments, curing catalysts, and other additives are added, and the bath concentration (solid content 40% by weight, preferably 10-2
5% by weight and bath pl (5 to 8, preferably 5.5 to 7). Then, using this electrodeposition bath, a carbon plate having a size of, for example, 5 cm x l 5 em x 1 cm is prepared. As an anode, for example, 5em x 15el
When a zinc phosphate treated plate having a size of xO,7+am is used as a cathode, electrodeposition can be carried out under the following regulations.

Bath temperature: 20-35°C, preferably 25-30°C, DC current current density: 0.005-2 A/am”, preferably 0.01” l A/(J”) Voltage: 10-500V, preferably is lOO~300
V Current application time: 0.5 to 5 minutes, preferably 2 to 3 minutes After the electrodeposition coating, remove the object from the electrodeposition bath and wash it with water. It can be removed by drying means.

The electrodeposition coating film thus formed using the resin composition for cationic electrodeposition coating of the present invention can be heated and cured as described above.

Next, the present invention will be explained in more detail with reference to Examples. In the examples, "part" is "part by weight", and "1%" is "% by weight".

■Production example ■Base resin (1-1) Bisphenol A tights epoxy resin with an epoxy equivalent of 950 [Product name: Epicote 1004, Shell Chemical Co., Ltd.]
1,900 parts of butyl cellosolve were dissolved in 993 parts of butyl cellosolve,
A base resin (A-1) having a solid content of 68%, a primary hydroxyl equivalent of 528, and an amine value of 53 by dropping 210 parts of jetanolamine at 80 to 100°C and holding it at 100°C for 2 hours.
I got it.

■Base resin (A-2) 39 parts of monoethanolamine was kept at 60°C in a reaction vessel, and 11 parts of N,N-dimethylaminopropylacrylamine was added.
00 parts was added dropwise and reacted at 60°C for 5 hours to form N, N-
A monoethanolamine adduct of dimethylaminopropylacrylamide was obtained.

Separately, 950 parts of bisphenol A diglycidyl ether with a J-boxy equivalent of 190, 340 parts of propylene glycol diglycidyl ether with an epoxy equivalent of 340, 456 parts of bisphenol A, and 21 parts of jetanolamine were charged, and the temperature was raised to 120°C until the epoxy value was 1. After reacting until the concentration was 0.02 mmol/g, diluting with 479 parts of ethylene glycol monobutyl ether and cooling, 126 parts of jetanolamine was added while maintaining the temperature at 100°C.
1 part and 43 parts of the monoethanolamine adduct of the above N,N-dimethylaminopropylacrylamide were added, and the reaction was continued until the viscosity stopped increasing. A-2)
I got it.

■Base resin (A-3) 950 parts of bisphenol A diglycidyl ether with epoxy equivalent of IQO, epoxy resin X with epoxy equivalent of 330
330 parts of B-4122 (trade name manufactured by Ciba Geigy), bisphenol A456, and 21 parts of jetanolamine were charged, and the temperature was raised to 120°C, and the epoxy value was 1.0.
After reacting until the concentration was 2 mmol/g, it was diluted with 489 parts of ethylene glycol monobutyl ether, cooled, and while keeping the temperature at 90°C, jetanolamine 12
6 parts, 53.5 parts of the monoethanolamine adduct of the above N,N-dimethylaminopropylacrylamide and N-
18.5 parts of methylamine ethanol was added and the reaction was allowed to continue until the viscosity increase stopped to obtain a base resin (A-3) having a resin solid content of 80%, a primary hydroxyl group of J1592, and an amine value of 55.

■Base resin (A-4) 103 parts of diethylenetriamine and 200 parts of methyl isobutyl ketone were mixed and heated to 100°C to 160°C.
Six parts of condensation water is distilled off to obtain a diethylenetriamine ketimine compound. Separately, epoxy 1950 bisphenol A type epoxy resin [trade name [Epicote 1004]
, manufactured by Shell Chemical Co., Ltd.] was dissolved in 993 parts of butyl cellosolve, 133-5 parts of the above diethylenetriamine ketimine such as 109.5 parts of diethylamine were added dropwise at 70 to 100°C, and the mixture was maintained at 100°C for 2 hours.
A base resin (8-4) having a solid content of 68% and an amine value of 65 was obtained.

■Base resin (A-5) 1900 parts of a bisphenol A type epoxy resin with an epoxy equivalent of 950 [trade name "Ebiko" 1004J, manufactured by Shell Chemical Co., Ltd.] was dissolved in 993 parts of butyl cellosolve, and 146 parts of diethylamine was heated to 70 to 100°C. After the dropwise addition, the mixture was maintained at 100° C. for 2 hours to obtain a base resin (A-5) with a solid content of 67% and an amine value of 55.

■Curing resin (B-1) 32.6 parts of EHPE3150 [epoxy equivalent 175-195, manufactured by Daicel Chemical Industries, Ltd.] and 8.2 m of propylene glycol monomethyl ether were heated and dissolved at 100°C, solid content 80%, 40.8 parts of a curing resin (B-1) having an epoxy equivalent of 190 was obtained. The number average molecular weight of the resin was approximately 1.500.

■Curing resin (B-2) 200 parts of a 10% ethyl acetate solution of BF3-etherate was added to 136 parts of vinylnorbornene oxide, 124 parts of 4-vinylcyclohexene-1-oxide, and 18 parts of trimethylolpropane at 50°C for 4 hours. Ring-opening polymerization was carried out by adding the solution dropwise. Add ethyl acetate and wash with water, concentrate the ethyl acetate layer, add 130 parts of fresh ethyl acetate to dissolve, and add 160 parts of peracetic acid as an ethyl acetate solution at 50°C.
The mixture was added dropwise at C for 4 hours, and further aged at 50°C for 2 hours to carry out an epoxidation reaction. After removing acetic acid, ethyl acetate, and peracetic acid, it was dissolved in 500 parts of ethyl acetate at 40°C, then washed 4 times with 250 parts of distilled water, ethyl acetate was removed, and 78 parts of propylene glycol monomethyl was dissolved at 80°C. Dissolved in ether, solids content 80%, epoxy equivalent weight 202
A curing resin (B2) is obtained. The number average molecular weight of the resin was approximately 1.300.

■Curing resin (B-3) A 10% ethyl acetate solution of BF, -etherate in 304 parts of partially epoxidized limonene (2-methyl-4-impropenyl-1-cyclohexene oxide) and 18 parts of trimethylolpropane. 200 parts were added dropwise at 50°C over 4 hours. The following operations were performed in the same manner as for curing resin B-2, and the resin was dissolved in 80 parts of ethylene glycol monobutyl ether at 80°C, and the solid content was 80% and the epoxy equivalent was 205.
A curing resin (B-3) was obtained. The number average molecular weight of the resin was about 1,000.

■Curing resin (B-4) Using 304 parts of 2,4 or 1,4-dimethyl-4ethynyl-l cyclohexene oxide, curing resin (B-2
), solid content 80%, epoxy equivalent 199
Curing resin B-4 was obtained.

The number average molecular weight of the resin was approximately 950.

0.1 part of distilled water was added to 460 parts of aluminum acetylacetonate, 0.3 parts of aluminum acetylacetonate, and 5 parts of tetraethoxysilane, kept at 80°C for 1 hour, and then heated to 120°C. After reacting for 3 hours, 116 parts of ethylene glycol monobutyl ether was added to obtain a curing resin (B-5) having a solid content of 80% and an epoxy equivalent of 280. The number average molecular weight of the resin was approximately i,ioo.

■Curing resin (B-6) 132 parts of cyclopentadiene dimer and 70 parts of ethyl acetate
160 parts of peracetic acid as an ethyl acetate solution.
The mixture was added dropwise at 5°C over 7 hours, and further aged at 40°C for 6 hours. After removing acetic acid, ethyl acetate, and peracetic acid, it was dissolved in 500 parts of ethyl acetate at 40°C, then washed 5 times with 250 parts of distilled water, ethyl acetate was removed, and 43 parts of methyl isobutyl ketone was dissolved at 80°C. A compound (C) having a solid content of 80% and an epoxy equivalent of 90 was obtained.

94 parts of 4-vinylcyclohexene was dissolved in 75 parts of ethyl acetate, and 160 parts of peracetic acid was dissolved in ethyl acetate at 50°C.
The mixture was added dropwise over 4 hours and further aged at 50°C for 2 hours. After removing acetic acid, ethyl acetate, and peracetic acid, ethyl acetate 50
0 parts at 40°C, then 5 parts with 250 parts of distilled water.
Ethyl acetate was removed from the washed bale, and the mixture was dissolved in 32 parts of methyl isobutyl ketone at 80°C to obtain Compound (D) having a solid content of 80% and an epoxy equivalent of 65. 0.2 parts of aluminum acetylacetonate and 10 parts of trimethylolpropane were added to 225 parts of compound (C) and 163 parts of compound (D), kept at 100°C for 1 hour, and then reacted at 150°C for 3 hours to form ethylene glycol monomer. Add 60 parts of butyl ether and cool. A curing resin (B-6) having a solid content of 70% and an epoxy equivalent of 210 was obtained. @The number average molecular weight of the resin is approximately 1,
It was 100.

■Curing resin (B-7) A solution of 2 parts of azobisdimethylvaleronitrile in 33.4 parts of METHB (3,4-epoxycyclohexylmethyl methacrylate) was mixed with 10 parts of methyl isobutyl ketone heated to 100°C and butyl cellosolve. It was added dropwise over 2 hours to a mixed solvent with 10 parts, and after aging for 1 hour, 1
The temperature was raised to 25°C and further aged for 1 hour, solid content 60%,
Curing resin (B-7) solution with epoxy equivalent of 196 54
I got the department. The number average molecular weight of the resin is about 10,000.

■Curing resin (B-8) 2.4 parts of azobisdimethylvaleronitrile was dissolved in a mixture of 32.0 parts of METHB monomer and 1-8.0 parts of hydroxyethyl acrylic at 100°C.
It was added dropwise over 2 hours to 24 parts of butyl cellosolve heated at ) 64.8 parts were obtained. The number average molecular weight of the resin was approximately 12,000.

■Curing resin (B-9) 3.4-Epoxycyclohexylmethyl acrylate 3
2.4 parts of azobisdimethylvaleronitrile was dissolved in a mixture of 7 parts of hydroxyethyl acrylate and 3 parts of hydroxyethyl acrylate, and the following treatment was carried out in the same manner as for curing resin B-9 to obtain a solid content of 60% and an epoxy equivalent of 200. Resin (B) for use was obtained. The number average molecular weight of the resin was approximately 15,000.

■Pigment paste (P-1) Add 4.4 parts of 10% formic acid to 12.5 parts of base resin (A-2), and add 15 parts of deionized water while stirring. Further, 10 parts of titanium itself, 10 parts of clay, 1 part of carbon, and 2 parts of basic lead silicate were added, and the mixture was dispersed in a ball mill for 24 hours. 11 parts of ionized water (described later) was added to obtain a paste with a solid content of 50%.

■Pigment paste (p-2) Pigment paste (P-2) was obtained by processing in the same manner as pigment base (P-1) except that 2 parts of basic lead silicate was replaced with 3 parts of basic lead sulfate. .

O pigment paste (P-3) 12.5 parts of base resin (A-2) to 1 part of base resin (A-4)
A pigment paste (P-3) was obtained in the same manner as the pigment paste (p-1) except that the amount was changed to 4.7 parts.

Car 1) In the comparative example reaction vessel, epoxy equivalents of 290 to 335 and 58
700 parts of an epoxy resin (Epon 836) produced by the reaction of bisphenol A with a molecular weight of 0 to 680 and shrimp chlorohydrin were charged. Then 78
1 part monoalcohol A and 13 parts 90% formic acid aqueous solution were added. The mixture was heated at 140-150°C for 5 hours, after which volatiles were removed under reduced pressure. The resulting epoxy compound had an epoxy value of about 520. A mixture of 734 parts of the epoxy compound thus obtained and 1 part of ethylene glycol dimethyl ether was heated at 60°C.
heated to. Then 25.4 parts dimethylethanolamine was added over 20 minutes followed by 74 parts deionized water. The mixture was cooled and aqueous acetic acid was added to bring the pH of the solution to 6.
．． 6 and the solids content was kept at 90%. The clear solution was further reduced to 10% solids content using deionized water.

"Monoalcohol A" used here is a reaction product obtained using 415 moles of ethylene oxa per mole of ethanol.

(2) Example 1 An aqueous emulsion was prepared using the base resin and curing resin obtained in the above production example to obtain a resin composition for a cationic electrodeposition paint, which is the object of the present invention. Their compositions and amounts are shown in Table 1 below.

(2) Performance test results: 450 parts of the composition obtained in the above example (aqueous dispersion with a solids content of 20%), 66 parts of the pigment paste and 9 parts of deionized water.
Mix 9 parts to make a 20% electrodeposition bath. Bath temperature 30℃
Electrodeposition was performed on a zinc phosphate-treated plate at 200 to 300 V for 3 minutes and baked at 160° C. for 30 minutes to obtain a cured coating film of 15 to 23 μm. The test results are shown in Table 2 below.

In addition, after storing the above electrodeposition bath at 30'C for 30 days, the impact resistance and slop spray resistance tests were conducted in the same manner as above. As a result, no deterioration was observed in Samples 1 to 13, and t; In sample 14, the results were even worse than the initial results.

The performance test method is as follows.

(1) Impact resistance (DuPont method) After placing the test plate in a constant temperature and humidity room at a temperature of 20°C and 1°C and a humidity of 75 ± 2% for 24 hours, it was placed in a DuPont impact tester with a cradle of the specified size and bombarded. Attach the center, place the test plate with the painted surface facing upward, and then drop a specified weight onto the center of impact from the specified height.The test board is passed if there is no cracking or peeling due to the impact of the coating. .

(2) Slip spray resistance Tested according to JIS 22871, the leak width from the cut (linear cut) part of the paint film is within 2°Qmm on one side, and the blistering of the paint film other than the cut part is 8F (A S T
M) Pass the exam if: The test time was between 1000 and 2000 hours.

(3) The weight of the heat loss treated plate is set to Wo, and after electrodeposition on this treated plate at 30°C for 3 minutes, it is dried under reduced pressure at 80°C for 1 hour in a vacuum drying base. The weight of this material is Wl, and it is heated to 180°C13 in a dryer.
Let the weight after baking for 0 minutes be W. Calculate the heating loss ΔWf from the formula below.

Claims (1)

[Scope of Claims] 1. A resin (A) containing a hydroxyl group and a cationic group; 1. A resin composition for cationic electrodeposition paint, which contains as a main component an epoxy resin (B) having an average of two or more molecules per molecule. 2. The resin composition according to claim 1, wherein the resin (A) is a resin containing a primary hydroxyl group and a cationic group. 3. The resin composition according to claim 1, wherein the resin (A) is a reaction product obtained by reacting a cationizing agent with an epoxy group of a polyepoxide compound obtained from a polyphenol compound and epichlorohydrin. 4. The resin composition according to claim 3, wherein the polyepoxide compound is a polyglycidyl ether of a polyphenol compound having a number average molecular weight of about 800 to about 2,000 and an epoxy equivalent of 190 to 2,000. 5. The resin composition according to claim 1, having a hydroxyl equivalent in the range of 20 to 5,000. 6. The resin composition according to claim 2, having a primary hydroxyl group equivalent within the range of 200 to 1,000. 7. The content of cationic groups is KOH (mg/g solid content)
The resin composition according to claim 1, which is within the range of 3 to 200 in terms of conversion. 8. The epoxy resin (B) has 1 epoxy group-containing functional group.
The resin composition according to claim 1, having an average of 3 or more per molecule. 9. The epoxy group-containing functional groups of epoxy resin (B) are expressed by the following formulas (I) to (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( I ) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲ Mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) In the formula, R_1, R_2, R_3, R_5, R_6, R_
7, R_1_0 and R_1_1 are H, CH_3 respectively
or C_2H_5, and R_4, R_8 and R_9 each represent H or CH_3. The resin composition according to claim 1, wherein the resin composition is at least one selected from the following. 10. The resin composition according to claim 9, wherein the epoxy group-containing functional group is at least one selected from those represented by formulas (I) and (II). 11. The resin composition according to claim 9, wherein the epoxy group-containing functional group is at least one selected from those represented by formulas (III) and (IV). 12. The epoxy resin (B) has the formula (I) or (II)
At least one kind of epoxy group-containing functional group represented by
The resin composition according to claim 9, which is an epoxy resin having at least one epoxy group-containing functional group represented by formula (III) or (IV) in the same molecule or in different molecules. 13. The resin composition according to claim 9, wherein the epoxy resin (B) has an epoxy group-containing functional group represented by the following formula (V). 14. The epoxy resin (B) has an epoxy group-containing functional group represented by the following formula (VI) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (VI) The resin composition according to claim 9. 15. The resin composition according to claim 1, wherein the epoxy resin (B) has an epoxy equivalent weight within the range of 100 to 2,000. 16. The resin composition according to claim 15, wherein the epoxy resin (B) has an epoxy equivalent weight within the range of 150 to 500. 17. The resin composition according to claim 1, wherein the epoxy resin (B) has a number average molecular weight within the range of 400 to 100,000. 18. The resin composition according to claim 1, wherein the epoxy resin (B) has a number average molecular weight within the range of 700 to 50,000. 19. The resin composition according to claim 1, wherein the weight ratio of the solid content of the epoxy resin (B) to the resin (A) is within the range of 0.2 to 1.0. 20. One or more metal compounds selected from lead compounds, zirconium compounds, cobalt compounds, aluminum compounds, manganese compounds, copper compounds, zinc compounds, iron compounds, chromium compounds and nickel compounds are mixed with resin (A) and epoxy The resin composition according to claim 1, wherein the resin composition contains a metal in a proportion of 10% by weight or less based on the total weight of the resin (B). 21. A cationic electrodeposition paint containing the resin composition according to claim 1. 22. A coated product coated with the cationic electrodeposition paint according to claim 21.