JPH04136079A - Organic solvent base thermosetting coating composition - Google Patents

Abstract

PURPOSE:To improve characteristics wherein a good balance is kept between the storage stability of an org. solvent base thermosetting coating compsn. and the curability of a coating film prepared therefrom by compounding a resin contg. hydroxyl and carboxyl groups with a specified epoxy compd. as a crosslinking agent and a quat. ammonium compd. as a reaction catalyst. CONSTITUTION:The title compsn. contains a resin contg. hydroxyl and carboxyl groups, an epoxy compd. contg., on average, two or more epoxy groups on an alicyclic hydrocarbon ring and/or epoxy groups directly bonded to the carbon atom forming an alicyclic hydrocarbon ring in the molecule and a quat. ammonium compd. as the essential ingredients. Examples of the above epoxy compd. usable herein include an alicyclic polyepoxy compd. obtd. by reacting an epoxy compd. contg. a hydroxyl group and an epoxy group prevent on the alicyclic hydrocarbon ring with a polyisocyanate compd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application J] The present invention relates to a novel organic solvent-based thermosetting coating composition.

[Prior Art and its Problems] Conventionally, as an organic solvent layer coating, a coating is known in which a resin composition containing a hydroxyl group-containing polycarboxylic acid resin and an aminoaldehyde resin is dissolved or dispersed in an organic solvent. However, this method requires baking at a temperature of 180° C. or higher and has the disadvantage that the resulting coating film has poor chemical properties such as corrosion resistance and acid resistance. Furthermore, problems such as coating film cracking and environmental pollution due to condensates (such as formalin) generated during baking remain. Furthermore, in the above-mentioned conventional paints, when a bisphenol epichlorohydrin type epoxy resin is used in place of the aminoaldehyde resin, the paint system thickens and gels during storage, and does not provide a practical organic solvent layer paint.

[Means for Solving the Problems 1] As a result of intensive research aimed at improving the storage stability of organic solvent-based coating compositions and the curability of coating films, the present inventors discovered that hydroxyl groups An organic solvent-based coating composition containing a thermosetting resin composition in which a specific epoxy compound as a crosslinking agent and a quaternary ammonium compound as a reaction catalyst are blended with a resin having a carboxyl group can achieve the above object. The present invention was completed based on this discovery.

Thus, the present invention provides a resin (A) having a hydroxyl group and a carboxyl group (hereinafter referred to as "resin (A)"), an epoxy group on an alicyclic hydrocarbon ring, and/or an alicyclic hydrocarbon ring. Epoxy compounds (B) having an average of two or more epoxy groups in one molecule directly bonded to carbon atoms forming a ring (hereinafter referred to as "epoxy compounds (B)"), and quaternary ammonium compounds ( An organic solvent-based thermosetting coating composition characterized by containing C) as an essential component (hereinafter referred to as "coating composition of the present invention (1)").
)J), and an alicyclic polyepoxy compound (D) obtained by reacting the resin (A), an epoxy compound having a hydroxyl group and an epoxy group on an alicyclic hydrocarbon ring, and a polyisocyanate compound. (hereinafter referred to as "epoxy compound (D)") and a quaternary ammonium compound (C) as essential components. The present invention provides a coating composition (referred to as "coating composition (2) of the present invention").

In the coating composition of the present invention, in the presence of a base in the quaternary ammonium compound (C), the hydroxyl group and carboxyl group in the resin (A) and the epoxy group in the epoxy compound (B) or (D) are combined. It is thought that reactions between functional groups hardly proceed at temperatures around room temperature, and reactions between functional groups proceed rapidly when baked at temperatures around 100°C. It is believed that the composition exhibits particularly excellent storage stability and low-temperature curability of the coating film.

The coating composition of the present invention will be explained in more detail below.

The resin (A) used in the coating composition (1) of the present invention is not limited as long as it has a hydroxyl group and a carboxyl group, and for example, it may be based on vinyl resin, polyester resin, polyether resin, etc. Any resin conventionally known in the paint art can be used. Representative examples of such resins are as follows.

(1) Examples of vinyl resins include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, polycaprolactone diol mono(meth)acrylate, polyoxyethylene glycol mono(meth)acrylate, etc. Hydroxyl group-containing monomers Carboxyl group-containing monomers such as (meth)acrylic acid, carboxyethyl acrylate, itaconic acid: and further as necessary methyl (meth)acrylate, ethyl (meth)acrylate, 1-propyl (meth)acrylate, n - Reacts with hydroxyl groups and carboxyl groups of butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, acrylonitrile, acrylamide, styrene, vinyltoluene, vinyl acetate, i-propyl vinyl ether, n-butyl hinyl ether, methoxyethyl vinyl ether, etc. Examples include those obtained by copolymerizing radically polymerizable unsaturated group-containing monomers that do not have functional groups.

(2) Examples of polyester resins include trimethylolethane, trimethylolpropane, pentaerythritol, glycerin, ethylene glycol, propylene glycol, 1,3-butylene glycol, neopentyl glycol, and (2).

Obtained by polycondensation of a polyol component such as 6-hexanediol and a polycarboxylic acid component such as (anhydrous) phthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, adipic acid, (anhydrous) trimellitic acid. Polyester resin; polyester resin modified with fatty acid or epoxy resin; and acrylic-grafted modified polyester resin; acid anhydride such as maleic anhydride added to an esterified product obtained by modifying bisphenol/epichlorohydrin type epoxy resin with fatty acid etc. Examples include modified polyester resins obtained by

(3) As the polyether resin, for example, one obtained by polymerizing a bisphenol/epichlorohydrin type epoxy resin in the presence of a catalyst and adding polycarboxylic acid or the like can be suitably used.

Among the above-mentioned resins (A), it has excellent cosmetic properties, weather resistance, etc.; Since a coating film can be obtained, it is possible to copolymerize a hydroxyl group-containing upper layer, a carboxyl group-containing upper layer, and other monomers as necessary. Particularly suitable are acrylic copolymers obtained by.

The resin (A) generally has an acid value of about 1 to about 100, preferably about 10 to about 80, and a hydroxyl value of about 10 to about 80.
Desirably, it is within the range of about 5,000, preferably about 20 to about 2,000. If the acid value is less than about 1, there will be fewer ester bonds in the cured paint film and the weather resistance of the paint film will be reduced.On the other hand, if the acid value is more than about 100, the storage stability of the paint and the water resistance of the paint film will be affected. This is not very desirable as it can cause a bad effect. In addition, when the hydroxyl value is less than about 1O, the curability of the coating film decreases, and coating film performance such as hardness and bending resistance tends to decrease.On the other hand, when the hydroxyl value is greater than about 5°000, the water resistance decreases. , is not very preferable because it reduces coating film performance such as corrosion resistance.

In addition, the resin (A) generally has a number average molecular weight of about 1°000.
~ about 100,000, preferably about 2.000 to about 80
,000 and a softening point of 130°C or less, preferably about 115°C or less. If the number average molecular weight is less than about 1.000, coating film performance such as hardness, bending resistance, and corrosion resistance tends to deteriorate.On the other hand, if the number average molecular weight is greater than about 100°000, the appearance of the coating film such as smoothness will deteriorate. There is a tendency to Also, the softening point is about 130
If the temperature is higher than ℃, the appearance of the coating film such as smoothness tends to deteriorate.

In addition to the above-mentioned hydroxyl groups and carboxyl groups, functional groups such as phenolic hydroxyl groups and alkoxysilane groups (and hydroxysilane groups) may be introduced into the resin (A) as necessary. The method of introducing these functional groups is not particularly limited and any known method can be used. For example, the introduction of phenolic hydroxyl groups can be achieved by bisphenol modification (
Meth)acrylate is used as a monomer component of the vinyl resin, and in order to introduce an alkoxysilane group (and hydroxysilane group), compounds such as γ-methacryloxypropyltrimethoxysilane and a hydrolyzate thereof are added to the vinyl resin. This can be carried out by copolymerizing the monomer components of

Epoxy compound used in the coating composition (1) of the present invention (
B) contains at least one epoxy group selected from an epoxy group on an alicyclic hydrocarbon ring and an epoxy group directly bonded to a carbon atom forming an alicyclic hydrocarbon ring.
At least two or more alicyclic hydrocarbon rings are present in the molecule, and the alicyclic hydrocarbon ring may be from a small 3-membered ring to a 7-membered ring or more. It may be a ring or a polycyclic ring, and the ring may further constitute a bridged hydrocarbon ring. containing an epoxy group on the alicyclic hydrocarbon ring,
Further, as the epoxy group directly bonded to the carbon atom forming the alicyclic hydrocarbon ring, for example, as the epoxy resin (B), an industrially available one can be used,
Specific examples of such epoxy resins include the following.

Examples include bifunctional epoxy resins such as.

In addition to the above, here R is a monovalent or divalent hydrocarbon group of C, , n is 0 to 100, m is 5 to 100, and p is 2 to 100. Epoxy resin containing units such as
It is also possible to use trifunctional or higher functional epoxy resins, such as those described in Japanese Patent Application No. 09667 (in the formula, k is an integer of 0 to 15).

In combination with the above epoxy compound (B), other epoxy resins having epoxy groups such as glycidyl ether type epoxy polymer compounds, aliphatic internal epoxy polymer compounds, etc. can also be used. The other epoxy resin is desirably used in a proportion of about 25% by weight or less based on the total amount of both, from the viewpoint of storage stability of the coating material and coating film curability.

The epoxy resin (B) has an average of 2 or more epoxy groups in one molecule, preferably an average of 2 to 2,000, and more preferably an average of 2 to 400.

If the number of epoxy groups is less than 2 on average, the curability of the coating film decreases, and performance such as hardness, bending resistance, and corrosion resistance deteriorates.

The epoxy resin (B) generally has a number average molecular weight of about 100 to about 2,000, preferably about 110 to about 2,000.
0,000 and the softening point is about 130°
C or less, preferably about 1150 C or less. Those with a number average molecular weight of less than about 100 are difficult to obtain, while those with a number average molecular weight of more than about ioo or ooo are not so preferred because the smoothness of the coated surface deteriorates.

Also, if the softening point is higher than about 130°C, the smoothness of the coating film tends to deteriorate.

The quaternary ammonium compound CC') is -killing: [R'R
"R3R'NΦIXe" can be used. In the above formula, R1, R2, R3 and R4 each represent a hydrocarbon group, and these 11 may be the same or different. may be substituted with a hydroxy group.

X represents a halogen ion or an acid anion residue, such as CQ, Br%F, I, SO,, H3O4, NOx,
Examples include POCoo4, HCOOlCH, Coo, OH, and the like.

Specific examples of the quaternary ammonium compound (C) include, for example, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, methyltriethylammonium chloride, tetramethylammonium bromide, tetraethylammonium fluoride, and tetraethyl ammonium chloride. Tetraalkylammonium nolide such as iodide; tetraalkylammonium organic acid salts such as tetramethylammonium acetate, tetraethylammonium formate, etc.; tetramethylammonium hydrogen sulfate, tetraethylammonium hydrogen sulfate, tetramethylammonium nitrate, tetraethylammonium nitrate, Tetraalkylammonium inorganic acid salts such as tetraethylammonium chlorate, tetraethylammonium phosphate, etc.; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetraisoamyl Ammonium hydroxide, tetradodecylammonium hydroxide, methyltriethylammonium hydroxide, ethyltrimethylammonium hydroxide, tetradecyltrimethylammonium hydroxide, monohydroxyethyltrimethylammonium hydroxide, monohydroxyethyltriethylammonium hydroxide, dihydroxyethyldimethylammonium hydroxide dihydroxyethyldiethylammonium hydroxide, trihydroxyethyl7methylammonium hydroxide, trihydroxyethylmonoethylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, benzylmethyldiethylammonium hydroxide, cyclohexyltrimethylammonium Examples include quaternary ammonium hydroxides such as hydroxide.

Among the above-mentioned quaternary ammonium compounds, quaternary ammonium hydroxide has the advantage of providing a coating composition with excellent storage stability and forming a coating film with excellent water resistance, corrosion resistance, etc. can be used in particular.

The polyepoxy compound (D) used in the coating composition (2) of the present invention is an alicyclic compound obtained by reacting an epoxy compound having a hydroxyl group and an epoxy group in an alicyclic hydrocarbon ring with a polyisocyanate compound. It is a polyepoxy compound.

The epoxy compound having a hydroxyl group and an epoxy group in an alicyclic hydrocarbon ring to obtain the polyepoxy compound (D) is a compound having one hydroxyl group and one or more alicyclic epoxy groups in one molecule. , the alicyclic epoxy group is an epoxy group on an alicyclic hydrocarbon ring, and the alicyclic hydrocarbon ring is a 3-membered small ring to a 7-membered ring or more. Furthermore, the ring may be a single ring or a polycyclic ring, and the ring may further constitute a bridged hydrocarbon ring.

Examples of the hydroxyl group-containing alicyclic epoxy compound include those shown in the following (1) to (7).

[In the formula, R'l represents a C8-2° divalent hydrocarbon group, Rs are the same or different and each represents a CI-, divalent hydrocarbon group, and R3 is a hydrogen atom or a methyl group. and q is an integer from 1 to 10] Examples of the divalent hydrocarbon group in the above general formula include an alkylene group, a cyclic alkylene group, a phenylene group, and a substituted phenylene group. The alkylene group can be linear or branched, specifically 01
~． Examples include methylene, ethylene, ethylethylene, propylene, butylene, pentamethylene, hexamethylene, octamethylene, etc.
01~. . In addition to the above C1-, examples include decanemethylene, dodecanemethylene, tetradecanemethylene, octadecanemethylene and the like.

Preferred specific examples of the hydroxyl group-containing alicyclic epoxy compound represented by the above general formula include the following.

The polyisocyanate compound to be reacted with the above hydroxyl group-containing alicyclic epoxy compound to obtain the polyepoxy compound (D) is a compound having two or more isocyanate groups in one molecule, and the compound is aliphatic, aliphatic, etc. Any type of polyisocyanate compound may be cyclic, aromatic, or aromatic-aliphatic, such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, decamethylene diisocyanate, etc. Aliphatic diisocyanate compounds: Alicyclic diisocyanate compounds such as isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate; Aromatic diisocyanate compounds such as tolylene diisocyanate and diphenylmethane diisocyanate; xylylene diisocyanate, tetra Examples include aromatic-aliphatic diisocyanate compounds such as methylxylylene diisocyanate. In addition to the above, adducts of the diisocyanate compounds and polyols (e.g., ethylene glycol, trimethylolpropane, etc.), biuret compounds or incyanurate compounds of the aliphatic diisocyanate compounds or alicyclic diisocyanate compounds, etc. Polyisocyanates can also be used.

Among these, it is desirable to use aliphatic, alicyclic, and aromatic-aliphatic polyisocyanate compounds because they are less susceptible to deterioration and provide a coating film with excellent weather resistance.

The reaction between the hydroxyl group-containing alicyclic epoxy compound and the polyisocyanate compound can be carried out by a conventionally known reaction between a hydroxyl group and an isocyanate group. in a nitrogen atmosphere until substantially free of isocyanate groups, e.g.
This can be carried out by continuing the reaction at a temperature of about 80°C for about 200 to about 24 hours. The above mixture can be used as an organic solvent solution dissolved or dispersed in an inert organic solvent such as an ester, ketone, ether, or aromatic hydrocarbon containing no active hydrogen.

Further, in this reaction, organic metals such as dibutyltin laurate, dibutyltin 2-ethylhexoate, lead octenoate, and zinc naphthenate can be added as a reaction catalyst.

The blending ratio of the hydroxyl group-containing alicyclic epoxy compound and the polyisocyanate compound is not strictly limited, but generally, the equivalent ratio of the hydroxyl group in the epoxy compound to the isocyanate group in the polyisocyanate compound is about 0.
．． It is desirable that the ratio be within the range of 9 to about 1.1.

The epoxy compound (D) thus obtained has an average of 2 or more, preferably an average of 2 to 2,000, and more preferably an average of 2 to 400 alicyclic epoxy groups in one molecule. When the number of epoxy groups is less than 2 on average, the curability of the coating film tends to decrease, and coating film performance such as hardness, bending resistance, and corrosion resistance tends to decrease.

Further, the polyepoxy compound (D) has a number average molecular weight of about 200 to about 20,000, preferably about 300 to about 10.
．． 000 and a softening point of about 130°C or less, preferably about 115°C or less. Those with a number average molecular weight of less than about 200 are difficult to obtain industrially; on the other hand, those with a number average molecular weight of about 20.000
If it becomes larger, the smoothness of the painted surface tends to decrease. Also,
If the softening point is higher than about 130°C, the smoothness of the coated surface tends to decrease.

Preferred specific examples of the polyepoxy compound (D) include the following.

The resin (A) and quaternary ammonium compound (C) used in the coating composition (2) of the present invention are the same as those used in the coating composition (1) of the present invention.
The same one used in t; can be used. The resin (A) desirably has the type, acid value, hydroxyl value, and number average molecular weight ranges described above for the same reasons as described for the coating composition (1) of the present invention.

Further, as the quaternary ammonium compound (C), it is desirable to use quaternary ammonium hydroxide for the same reason as described for the coating composition (1) of the present invention.

In the present invention, resin (A) and epoxy compound CB)
Or (D) is generally resin (A) in terms of the total amount of both.
about 40 to 97% by weight, preferably about 50 to about 95% by weight
, more preferably about 60 to about 90% by weight, about 3 to about 60% by weight of the epoxy compound (B) or (D), preferably about 5 to about 50% by weight, even more preferably about 3 to about 60% by weight.
It is preferable to mix within the following range. If it is out of the above range, the curability decreases, and coating film properties such as water resistance, corrosion resistance, and bending resistance tend to deteriorate, which is not preferable. Also,
The epoxy compound (B) or (D) is a resin (A
) in which the equivalent ratio (hydroxyl group/epoxy group) is approximately 0.
．． 3 or more, preferably about 0.5 to about 5, more preferably about 0.7 to about 4, and the corresponding ratio is about 0.3. If it is smaller, there will be more unreacted resin (A) tC in the coating film,
There is a tendency for coating film performance such as bending resistance, water resistance, and corrosion resistance to deteriorate. Further, the carboxyl group in the resin (A) has a carboxyl group/epoxy group equivalent ratio of about 0-1 to about 11, preferably about 0.1 to about 0, from the viewpoint of curability, water resistance of the coating film, corrosion resistance, etc. It is desirable to keep it within the range of .6.

The quaternary ammonium compound (C) usually contains the resin (
A), epoxy compound (B) or (D), and quaternary ammonium compound (C) based on the total amount of about 0. O1～
It can be present in amounts ranging from 1 to about 10%, preferably from about 0.1 to about 7%, more preferably from 0.1 to 5% by weight.

For example, the coating composition of the present invention can be prepared by adding an epoxy compound (B) to a solution in which the resin (A) is dissolved or dispersed in an organic solvent.
or (D), or epoxy compound (B) or (
Mixing a solution in which D) is dissolved or dispersed in an organic solvent,
Next, add a quaternary ammonium compound (C) to the resulting mixture.
It can be obtained by blending. The above resin (
The organic solvent that can be used to dissolve or disperse A), epoxy compound (B) or (D) is preferably an organic solvent that is substantially inert to the organic functional groups of these resins. Examples include alcohol solvents, ether solvents, ketone solvents, ester solvents, and hydrocarbon solvents.

The coating composition of the present invention may include, for example, polytetramethylene glycol, bisphenol A,
Polyol resins that do not contain carboxyl groups, such as ethylene oxide adducts, polycaprolactone polyols, polycarbonate diols, polyurethane polyols, vinyl alcohol (co)polymers, and styrene-allyl alcohol copolymers, can also be blended. In addition, for the purpose of curing the coating film at lower temperatures, phenolic compounds (such as catechol) and silanol compounds (
(e.g. diphenylsilanediol), metal chelate compounds (e.g. AI, Ti1Vs Fe s Z n
It is also possible to use (co-)catalysts such as chelates of metals such as 1ZrsSn with β-diketones such as ethyl toacetoacetate, trifluoroacetylacetone, and dibenzoylacetylacetone). Applicable (help)
The amount of the catalyst is usually about 0.01 to 100 parts by weight of the resin (A) and the epoxy compound (B) or (D).
It can be blended within a range of about 10 parts by weight.

Furthermore, the coating composition of the present invention may contain coloring pigments (for example, titanium, carbon black, red iron, etc.) as necessary.
, extender pigments (eg, clay, talc, silica, etc.) and other paint additives (eg, pigment dispersants, anti-cissing agents, fluidity modifiers, etc.) can also be included.

There are no particular restrictions on the method of forming a coating film using the coating composition of the present invention; for example, it may be applied to the surface of a substrate by means such as electrodeposition coating, spray coating, dip coating, roller coating, or brush coating, and then dried. This can be done by Although there are no particular restrictions on the coating film thickness, a range of 10 to 1100 p is usually considered sufficient. The paint film usually dries for about 12
It can be carried out for about 30 minutes at 0°C and for about 10 minutes at about 180°C. The base material to be coated is also not particularly limited, but preferably steel, aluminum, alumite, copper, plated steel in which the surface of steel is plated with zinc, tin, chromium, aluminum, etc., or the surface of steel is plated with chromic acid,
It can be applied to a wide range of metals, including those treated chemically or electrolytically with phosphoric acid.

[Examples] Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

"Parts" and "%" in Examples and Comparative Examples are based on weight.

Example 1 89 parts of methylpropertool was charged into 4 flasks 1
Heat to 10°C. A mixture of 3 parts of acrylic acid, 20 parts of hydroxyethyl acrylate, 57 parts of methyl methacrylate, and 20 parts of styrene, and a mixture of 1 part of 2゜2'-azobisisobutylnitrile and 710 parts of methyl isobutyl keto were added dropwise over 1 hour. do. After further aging for 1.5 hours, a resin having an acid value of 23, a hydroxyl value of 97, a number average molecular weight of about 20,000, and a solid content of 50% was obtained. In addition to this, EHPE-3150 (
25 parts of epoxidized polyvinyl cyclohexene oxide, epoxy equivalent weight 190, average molecular weight approximately 1500; product name manufactured by Daicel Chemical Industries, Ltd.) and 6.3 parts of methylglobanol.
Add 31.3 parts of an 80% EHPE-3150 solution dissolved in the powder, then add 19.5 parts of a 20% methanol solution of tetraethylammonium hydroxide, stir, and dilute with Kijirol to obtain a clear paint with a solid content of 30%. Obtained.

The storage stability of the obtained clear paint was 100, and there were no abnormalities in the paint condition and film performance. In addition, the dry film thickness of the clear paint before the storage test was approximately 2
It was spray coated to a thickness of 0 μm, dried at 80° C. for 10 minutes, and then further dried at 120° C. for 20 minutes to obtain a coated product. The coated product has a coating film smoothness of 3 (1) good, 1 bottle 3] resistance to slip spray, and a pencil hardness (4) 2H1, 11 in bending resistance.
I passed the exam.

Furthermore, the gel fraction of the coating film6) was 90%.

Example 2 4 parts of methacrylic acid, 25 parts of hydroxyethyl methacrylate, 10 parts of 2-ethylhexyl methacrylate, and methyl methacrylate were prepared under the same conditions as in Example 1 except that all the monomer components in Example 1 were replaced with those listed below. 5
An acrylic resin with a 7-mer composition of 1 part of styrene and 10 parts of styrene was synthesized, and the acid value was 26, the hydroxyl value was 108, and the number average molecular weight was 25.
000, 200 parts of a resin with a solid content of 50% was obtained. 8 to this
Added 18.8 parts of 0% EHPE3150 (solid content: 15
part), and further 1 part of tetramethylammonium hydroxide
16.2 parts of 0% methanol solution was added and stirred to obtain a clear paint with a solid content of 30%. Regarding the storage stability of the obtained clear paint (1), there was no abnormality in both the paint condition and film performance. The clear paint before the storage test was coated and dried in the same manner as in Example 1 to obtain a coated product. The coated product had good coating film smoothness (2), salt spray resistance (13'), pencil hardness (6)2H, and bending resistance (car (1)).Furthermore,
The gel fraction of the coating film (Kyo 6) was 92%.

Example 3 A mixture of 200 parts of the 50% resin obtained in Example 1, 15 parts of 3.4-epoxycyclohexylcarboxymethylcyclohexene oxide, 17.9 parts of a 10% methanol solution of tetrabutylammonium hydroxide, and 2 parts of triethylamine was added. Stir and further dilute with Kijiroru to reduce the solid content to 3.
A 0% clear paint was obtained. Storage stability of the obtained clear paint 1. There were no abnormalities in both the paint condition and film performance. The clear paint before the storage test was spray-painted on a zinc phosphate-treated steel plate to a dry film thickness of approximately 20 μm.
After drying at 140°C for 10 minutes, the coated product was further dried at 140°C for 20 minutes. The coated product had a good coating film smoothness of 12'.
1 bottle of anti-slip spray 3] Passed, pencil hardness 1412H
1 bending resistance (x5) passed.

Furthermore, the gel fraction of the coating film was 93%.

Example 4 89 parts of methylpropanol was placed in 4 flasks and 1
Heat to 10°C. To this, 2.7 parts of acrylic acid, 15 parts of hydroxyethyl acrylate, 6 parts of methyl methacrylate.
A mixture of 7.3 parts of styrene, 15 parts of styrene, 1 part of azoisobutyronitrile and 10 parts of methyl isobutyl ketone are added dropwise over 1 hour. Aged for another 15 hours to reach an acid value of 2.
1, hydroxyl value 73, number average molecular weight 25,000. Solid content 5
Obtained 0% base resin I;. Next, Duranate TPA-1
00 (Asahi Kasei Co., Ltd. product name, hexamethylene diisocyanate incyanurate, trifunctional isocyanate, incyanate equivalent weight 185) 14.5 parts and 3,4-
10.5 parts of epoxytetrahydrobenzyl alcohol (manufactured by Daicel Chemical Industries, Ltd., epoxy equivalent: 135)
After reacting at 20° C. for 3 hours and confirming that the isocyanate value was 0, 6.3 parts of methyl propatool was added to obtain an epoxy compound with a solid content of 80% and an epoxy equivalent of 325. 200 parts of the above base resin, 31.3 parts of the above epoxy compound, and 19 parts of a 20% tetraethylammonium hydroxide methanol solution were sufficiently stirred and further diluted with Kijirol to obtain a clear paint with a solid content of 30%.

The resulting clear paint had no abnormality in storage stability in 3 bottles or 1.2 in terms of paint condition and film performance. In addition, the clear paint before the storage test was spray-painted on a zinc phosphate-treated steel plate so that the dry film thickness was approximately 20 μm, and the paint was sprayed at 80°C for 10 minutes.
After drying for a minute, it was further dried at 140°C for 20 minutes to obtain a coated article. The coated product has good coating smoothness (2), salt spray resistance (11), pencil hardness (4) 3H1 bending resistance (
I passed Book 1. Also, the gel fraction of the coating film is 99%.
Met.

Example 5 In Example 4, 3 parts of methacrylic acid, 30 parts of hydroxyethyl methacrylate, 10 parts of 2-ethylhexyl methacrylate, and methacrylic acid were prepared under the same conditions as in Example 4, except that all the seven-mer components were replaced with those listed below. An acrylic resin with a monomer composition of 42 parts of methyl acid and 15 parts of styrene was synthesized, with an acid value of 20, a hydroxyl value of 129, and a number average molecular weight of 2.
A base resin having a solid content of 50% was obtained. Next, the IP
17.5 parts of DI-71890100 (Daicel Huels Ltd. Super High Product Name, incyanurate of isophorone diisocyanate, isocyanate equivalent 247) and hepoxide 4000 (Daicel Chemical Industries Ltd. part name; Epoquin equivalent 177) 12. After confirming that the incyanate value was 0, 7.5 parts of methylprobanol was added to reduce the solid content to 80%.
, an epoxy compound with an epoxy equivalent of 425 was obtained. 200 parts of the above base resin, 37.5 parts of the above epoxy compound, and 1
16 parts of a methanol solution of 0% tetramethylammonium hydroquine was added and stirred to obtain a clear paint with a solid content of 30%. Regarding the storage stability of the obtained clear paint 1), there were no abnormalities in both the paint condition and film performance. The clear paint before the storage test was coated and dried in the same manner as in Example 4 to obtain a coated product. The coated product had a good coating film smoothness of 12'.
Passed salt spray resistance 11, pencil hardness value 1゜2H1 bending resistance 6*5). In addition, the gel fraction of the coating film is 6
) was 91%.

Example 6 26.5 parts of an adduct of 1 mole of 3.4-epoxytetrahydrobenzyl alcohol and 2 moles of ε-caprolactone (manufactured by Daicel Chemical Industries, Ltd., epoxy equivalent: 360) and Duranate TPA-100 (same as above) )13.5
part was reacted at 120°C for 3 hours until the isocyanate value was 0.
After confirming that this was the case, 10 parts of methylpropanol was added to obtain an epoxy compound with a solid content of 80% and an epoxy equivalent of 545. 50 parts of this epoxy compound and Example 1
200 parts of a 50% base resin and 18 parts of a 20% tetrabutylammonium hydroxide methanol solution were thoroughly stirred and further diluted with Kijirol to obtain a clear paint with a solid content of 30%. Storage stability of the obtained clear paint (The main mouth had no abnormalities in both the paint condition and film performance.The clear paint before the storage test was sprayed onto a zinc phosphate treated steel plate so that the dry film thickness was approximately 20 μm. Paint and heat at 80℃ for 10
After drying for a minute, it was further dried at 140°C for 20 minutes to obtain a coated article. The coated product had good coating film smoothness (3 points 2), salt spray resistance (11), pencil hardness (41), and H1 heavy crude oil (153). In addition, the gel fraction of the coating film is 9
It was 2%.

Comparative Example 1 Seitl 303 (
Product name, Mitsui Toatsu Co., Ltd., aminoaldehyde resin) 42
and 231 parts of Kijiroll to obtain a clear paint with a solid content of 30%. The paint was spray-painted on a zinc phosphate-treated copper plate to a dry film thickness of approximately 20 μm, and heated at 80°C.
The coated product was dried for 10 minutes at 140°C and further for 20 minutes at 140°C. The coated product had a coating film smoothness of 12' good, a slip resistance of 13' which failed, a pencil hardness of FOA 4 B, and a bending resistance of 3 and 1 which failed. In addition, the gel fraction of the coating film is 1″
) was 70%.

(*1) Storage stability: After being left at 30° C. for one month, sedimentation and separation of the clear paint were visually observed.

In addition, after storage, we apply clear paint and dry it.
The initial appearance of the coating film and the presence or absence of a decrease in coating film performance (slip spray resistance, bending resistance, pencil hardness, etc.) were investigated.

(Car 2) Paint film smoothness: The surface unevenness of the paint film was visually observed.

(Town) Anti-slip spray: Tested according to JIS2-2371, creep from the cut part of the paint film 2u + m on the mountain and river side
Those within the range were considered passed. The test time was 1000 hours.

(*4) Pencil hardness: Tested according to J15K-5400.

(Book 5) Bending resistance: Bend the test plate at right angles for 1 to 2 seconds in an atmosphere at a temperature of 20°C. Items with no abnormalities such as peeling or cracking of the paint film on the bent part were considered to have passed.

(*6) Gel fraction: 300 after peeling off the dried coating film
The mixture was placed in a mesh stainless steel mesh container and extracted for 6 hours at reflux temperature using an acetone/methanol-1/1 solvent in a Soxhlet extractor, and then the gel fraction was calculated according to the following formula.

Gel fraction (%) = (Coating film weight after extraction / Coating film weight before extraction) x 100

Claims (1)

[Claims] 1. Resin (A) having a hydroxyl group and a carboxyl group, an epoxy group on an alicyclic hydrocarbon ring and/or an epoxy group directly bonded to a carbon atom forming the alicyclic hydrocarbon ring Epoxy compound (B) having an average of 2 or more in one molecule
, and a quaternary ammonium compound (C) as essential components. 2. A resin having a hydroxyl group and a carboxyl group (A), an alicyclic polyepoxy compound obtained by reacting an epoxy compound having a hydroxyl group and an epoxy group on an alicyclic hydrocarbon ring with a polyisocyanate compound (D) , and a quaternary ammonium compound (C) as essential components. 3. The organic solvent-based thermosetting coating composition according to claim 1 or 2, wherein the quaternary ammonium compound (C) is quaternary ammonium hydroxide.