JP3042033B2 - Latent carboxyl compound and thermosetting composition containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel latent carboxyl compound and a thermosetting composition containing the same. More specifically, the present invention has good chemical performance, physical performance and weather resistance, and is particularly excellent in storage stability, for example, a thermosetting composition suitable for paints, inks, adhesives, molded articles, and the like. And latent carboxyl compounds that can provide this.

[0002]

2. Description of the Related Art Conventionally, a compound having a carboxyl group and a reactive functional group capable of forming a chemical bond with the carboxyl group by heating, for example, an epoxy group, a silanol group, an alkoxysilane group, a hydroxyl group, an amino group, an imino group , Isocyanate group, blocked isocyanate group,
Thermosetting compositions comprising a combination with a compound having a cyclocarbonate group, vinyl ether group, vinyl thioether group, aminomethylol group, alkylated aminomethylol group, acetal group, ketal group and the like are known.
These thermosetting compositions, the chemical performance of the resulting cured product,
Because of its excellent physical performance and weather resistance,
For example, it is widely used in the fields of paints, inks, adhesives, and plastic molded products. However, since the carboxyl group and the reactive functional group have high reactivity, in a composition in which a carboxyl group-containing compound and a compound containing the reactive functional group coexist, gelation occurs during storage, Problems such as shortened pot life occur. As a method for solving such a problem, for example, a method has been proposed in which a carboxyl group is blocked as a t-butyl ester, and the carboxyl group is regenerated into a free carboxyl group by elimination and decomposition of isobutene by heating (Japanese Patent Laid-Open No. 1-146646). Gazette). However, this method requires a high temperature of about 170 to 200 ° C. for the thermal decomposition of the t-butyl group, and is not necessarily a satisfactory method from the viewpoint of resource saving and energy saving in recent years. The present inventors have previously proposed a latent carboxyl compound obtained by blocking a carboxyl group of a polycarboxyl compound with a monofunctional vinyl ether compound, and a thermosetting composition containing the same (Japanese Patent Application No. 3-89510). The above compound regenerates a free carboxyl group at a relatively low temperature to give a cured product having good chemical performance and physical performance.In this case, a part of the monofunctional vinyl ether compound as a blocking agent is partially cured. Volatilizes out of the system without being trapped by the reactive functional groups inside. Discharge of the blocking agent to the outside is not preferable from the viewpoints of resource saving and reduction of the effective component of the thermosetting composition, although the toxicity of the monofunctional vinyl ether compound itself is extremely low and safe.

[0003]

SUMMARY OF THE INVENTION The present invention provides a cured product excellent in chemical performance, physical performance and weather resistance at a relatively low temperature, has good storage stability, and has a high solid content. An object of the present invention is to obtain a thermosetting composition that can be used as a one-pack type and a latent carboxyl compound useful for providing the same.

[0004]

The present inventors have conducted intensive studies to develop a latent carboxyl compound capable of providing a thermosetting composition having the above-mentioned preferable properties.
The object can be achieved by reacting a specific low molecular weight polycarboxyl compound with a monofunctional vinyl ether compound and a bifunctional vinyl ether compound (divinyl ether) to block a carboxyl group in the polycarboxyl compound. And completed the present invention based on this finding.

That is, the present invention relates to (a) a compound having two or more carboxyl groups per molecule and having an acid equivalent of 1000 g;
/ Mol or less and a number average molecular weight of 4000 or less, (b) 1 vinyl ether group per molecule
Value obtained by reacting (c) a compound having two vinyl ether groups per molecule with an acid value of 10 mg
A non-gel-like latent carboxyl compound of less than KOH / g, and two or more reactive functional groups capable of forming a chemical bond by heating with a carboxyl group as a component (A) and a compound (B) as a component (B) in one molecule The present invention also provides a thermosetting composition comprising a compound having the above-mentioned formula (I) and optionally a heat-latent acid catalyst having activity as a component (C) during heat curing.

Hereinafter, the present invention will be described in detail. The polycarboxyl compound (a) serving as a raw material of the latent carboxyl compound of the present invention has two or more carboxyl groups, preferably 2 to 50 carboxyl groups per molecule, and has an acid equivalent of 1000 g / mol or less and a number average. Those having a molecular weight of 4000 or less are used. In the case where the number of carboxyl groups per molecule in the polycarboxyl compound is less than 2 or the acid equivalent exceeds 1000 g / mol, the final target thermosetting composition may be insufficiently cured. When the number average molecular weight exceeds 4,000, the thermosetting composition tends to have a high viscosity and a decrease in workability.

The polycarboxyl compound (a), which is the parent of the latent carboxyl compound of the present invention, comprises: (1) a half of a polyol having two or more, preferably 2 to 50 hydroxyl groups per molecule and an acid anhydride. Esterification, (2) two or more isocyanate groups per molecule,
(3) Carboxyl group-containing α, β-unsaturated monomer is homopolymerized or other α, β-unsaturated monomer is added, preferably a polyisocyanate compound having 2 to 50 amino acids and a hydroxycarboxylic acid or an amino acid. And (4) synthesizing a carboxyl group-terminated polyester resin.

The polyols having two or more hydroxyl groups per molecule include, for example, ethylene glycol, 1,2- and 1,3-propylene glycol, 1,3
-Butanediol, 1,4-butanediol, 2,3-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, pentanediol, dimethylbutanediol, hydrogenated bisphenol A,
Glycerin, sorbitol, neopentyl glycol,
1,8-octanediol, 1,4-cyclohexanedimethanol, 2-methyl-1,3-propanediol,
2,6-hexanetriol, 1,2,4-butanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, quinitol, mannitol,
Polyhydric alcohols such as trishydroxyethyl isocyanurate and dipentaerythritol; ring-opened adducts of these polyhydric alcohols with lactone compounds such as γ-butyrolactone and ε-caprolactone; Isocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate,
Adduct of isocyanate compound such as isophorone diisocyanate with alcohol in excess of alcohol; vinyl ether compound such as polyhydric alcohol and ethylene glycol divinyl ether, polyethylene glycol divinyl ether, butanediol divinyl ether, pentanediol divinyl ether, hexanediol divinyl ether, etc. Adduct with an excess of alcohol; and the polyhydric alcohol and an alkoxysilicone compound such as KR-
213, KR-217, and KR-9218 (all manufactured by Shin-Etsu Chemical Co., Ltd., trade name) in the presence of an excess of alcohol.

On the other hand, acid anhydrides to be reacted with these polyols include, for example, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid, phthalic acid, maleic acid, trimellitic acid, and pyromellitic acid. Acid anhydrides such as acid, 3,6-endomethylenetetrahydrophthalic acid, tetrabromated phthalic acid, hexahydrophthalic acid, phthalic acid tetrachloride, hexic acid, tetrahydrophthalic acid, and hexahydrophthalic acid can be exemplified. . Also,
Examples of the polyisocyanate compound having two or more isocyanate groups per molecule include p-phenylene diisocyanate, biphenyl diisocyanate, tolylene diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, and 1,4-tetramethylene Diisocyanate, hexamethylene diisocyanate,
2,2,4-trimethylhexane-1,6-diisocyanate, methylene bis (phenyl isocyanate), lysine methyl ester diisocyanate, bis (isocyanate ethyl) fumarate, isophorone diisocyanate, methylcyclohexyl diisocyanate, 2-isocyanatoethyl-2,6- Examples thereof include diisocyanatohexanoate and burettes and isocyanurates thereof.

Examples of the hydroxycarboxylic acid include lactic acid, citric acid, hydroxypivalic acid, 12-hydroxystearic acid, malic acid, and the like. Examples of the amino acid include DL-alanine, L-glutamic acid, and glycine. , L-theanine, glycylglycine, γ-aminocaproic acid, L-aspartic acid, L-
Examples thereof include titrulline, L-arginine, L-leucine, L-serine and the like. Further, examples of the carboxyl group-containing α, β-unsaturated monomer include, for example, acrylic acid, methacrylic acid, itaconic acid, mesaconic acid, maleic acid, fumaric acid, and the like, and other α, β-unsaturated monomers. As the monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl Examples thereof include (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, styrene, α-methylstyrene, p-vinyltoluene, and acrylonitrile.

The carboxyl group-terminated polyester resin can be easily formed according to a general method for synthesizing a polyester resin in an excess of a polybasic acid with respect to a polyhydric alcohol. The non-gel-like latent carboxyl compound of the present invention comprises a polycarboxyl compound obtained by the above method and a general formula

[0012]

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(Wherein R ¹ , R ² , and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms such as an alkyl group, an aryl group, or an alkaryl group. R ² and R ⁴ or R ³ and R ⁴ may be bonded to each other to form a heterocyclic ring having no or having a substituent having oxygen as a hetero atom. Or a heterocyclic compound having a vinyl double bond having an oxygen atom as a hetero atom, and a general formula:

[0014]

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(Wherein R ⁵ , R ⁶ , and R ⁷ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms such as an alkyl group, an aryl group, or an alkaryl group. R ⁸ represents an aliphatic or aromatic diol residue) in the presence of an acidic catalyst, preferably at room temperature to 100 ° C. By converting the carboxyl group into a compound of the general formula

[0016]

Embedded image Or

[0017]

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(R ^{1 to} R ⁸ have the same meanings as described above), and can be easily produced by modifying a blocked carboxyl group. Specific examples of the monovinyl ether compound represented by the general formula [1] include methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, and n
-Butyl vinyl ether, isobutyl vinyl ether,
Aliphatic vinyl ether compounds such as 2-ethylhexyl vinyl ether and cyclohexyl vinyl ether, and furthermore 2,3-dihydrofuran, 3,4-dihydrofuran,
2,3-dihydro-2H-pyran, 3,4-dihydro-2
H-pyran, 3,4-dihydro-2-methoxy-2H-
Pyran, 3,4-dihydro-4,4-dimethyl-2H-pyran-2-one, 3,4-dihydro-2-ethoxy-2
Cyclic vinyl ether compounds such as H-pyran and sodium 3,4-dihydro-2H-pyran-2-carboxylate;

The divinyl ether compound represented by the general formula [2] includes a compound derived from an aliphatic or aromatic diol compound and acetylene.
More specifically, for example, ethylene glycol divinyl ether, 1,2- and 1,3-propylene glycol divinyl ether, 1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether, 2,3-
Butanediol divinyl ether, 1,6-hexanediol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, pentanediol divinyl ether, dimethylbutanediol divinyl ether, hydrogenated bisphenol A divinyl ether, neopentyl glycol divinyl ether, 1, 8-octanediol divinyl ether, 1,
4-cyclohexanedimethanol divinyl ether, 2
-Methyl-1,3-propanediol divinyl ether.

The latent carboxyl compound obtained by the reaction of these three components (a), (b) and (c) preferably has an acid value of less than 10 mg KOH / g.
If it is 0 mgKOH / g or more, the effect of blocking the carboxyl group is weakened, and the storage stability of the final target thermosetting composition is poor, which is not preferable. In addition, since the latent carboxyl compound of the present invention is used in thermosetting compositions such as paints, inks, and plastic molded products, it must be a non-gel compound before it is cured.

(A) a polycarboxyl compound,
In order to obtain a non-gelled reaction product from the three components (b) monovinyl ether compound and (c) divinyl ether compound, the average functional group concentration represented by the following formula is 1.5 to 2.
5, and the highest average functional group concentration that does not cause gelation within this range is found by a trial and error method.

[0022]

(Equation 1)

F: average functional group concentration [a]: number of moles of compound (a) [b]: number of moles of compound (b) [c]: number of moles of compound (c) n: one molecule of compound (a) Carboxyl groups per unit

The latent carboxyl compound (A) of the present invention
Is used in a thermosetting composition, a compound having two or more, preferably 2 to 50, reactive functional groups in one molecule capable of forming a chemical bond by reacting with a free carboxyl group regenerated by heating (B ) Is desirably used in combination. There is no particular limitation on the reactive functional group, for example, an epoxy group, a silanol group, an alkoxysilane group,
Preferable examples include a hydroxyl group, an amino group, an imino group, an isocyanate group, a blocked isocyanate group, a cyclocarbonate group, a vinyl ether group, a vinyl thioether group, an aminomethylol group, an alkylated aminomethylol group, an acetal group, and a ketal group. One of these reactive functional groups may be contained, or two or more thereof may be contained.

Specific examples of the compound (B) having such a reactive functional group include bisphenol epoxy resin, alicyclic epoxy resin, glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth).
Epoxy group-containing compounds such as homopolymers or copolymers such as acrylates and polyglycidyl compounds obtained by reacting a polyol with epichlorohydrin;

[0026]

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(Wherein R ⁹ and R ¹⁰ are alkyl or aryl groups having 1 to 18 carbon atoms, and n is 0, 1 or 2), a condensate of a compound represented by the formula: Homopolymers or copolymers of α, β-unsaturated silane compounds such as methoxysilane, methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltri-n-butoxysilane, and silanols such as hydrolysis products of these compounds Group or alkoxysilane group-containing compound; aliphatic polyols, phenols, polyalkyleneoxy glycols, α-, β-unsaturated compounds such as 2-hydroxy (meth) acrylate and 2-hydroxypropyl (meth) acrylate Coalesced or copolymers and the ε of these polyols
A hydroxyl group-containing compound such as a caprolactone adduct; an amino group-containing compound such as an aliphatic or aromatic diamino compound or polyamino compound and a polyamino compound obtained by reducing a cyanoethylation reaction product of the polyol; An imino group-containing compound such as an aromatic polyimino compound; p-phenylene diisocyanate, biphenyl diisocyanate, tolylene diisocyanate;
3,3'-dimethyl-4,4'-biphenylene diisocyanate, 1,4-tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, methylene bis (phenyl isocyanate), lysine methyl Ester diisocyanate, bis (isocyanate ethyl) fumarate, isophorone diisocyanate, methylcyclohexyl diisocyanate, 2-isocyanate ethyl-2,
6-diisocyanate hexanoate and burettes and isocyanurates thereof, as well as isocyanate group-containing compounds such as adduct compounds of these diisocyanates and the polyols; phenols, lactams and active methylene of the isocyanate group-containing compounds , Alcohols, acid amides, imides, amines, imidazoles, ureas, imines, oximes and other blocked isocyanate group-containing compounds; 3- (meth) acryloyloxypropylene carbonate A cyclocarbonate group-containing compound such as a coalesced or copolymer, a polyvalent cyclocarbonate group-containing compound obtained by reacting the epoxy group-containing compound with carbon dioxide; A polyvalent vinyl ether compound obtained by a reaction with a vinyl ether, a hydroxyalkyl vinyl ether and a compound containing a polyvalent carboxyl group or a polyvinyl ether compound obtained by a reaction with the polyisocyanate compound, a vinyloxyalkyl (meth) acrylate and α, Vinyl ether compounds such as copolymers with β-unsaturated compounds; melamine formaldehyde resins, glycolyl formaldehyde resins, urea formaldehyde resins, homopolymers of α, β-unsaturated compounds containing aminomethylol groups or alkylated aminomethylol groups or Aminomethylol group or alkylated aminomethylol group-containing compounds such as copolymers; for reacting polyhydric ketones, polyhydric aldehyde compounds, polyhydric vinyl ether compounds and the like with alcohols and orthoacid esters Thus obtained polyvalent acetal compounds, condensates of these with polyol compounds, and acetal such as homopolymers or copolymers of the above-mentioned adducts of vinyloxyalkyl (meth) acrylate with alcohols or orthoacid esters And ketal group-containing compounds.

In the thermosetting composition, these compounds have a reactive functional group equivalent to the blocked carboxyl group in the latent carboxyl compound of the present invention in an equivalent ratio of 0.2: 1.0 to 1.0. : It is desirable to mix in such a ratio as to be 0.2. The latent carboxyl compound of the present invention can easily regenerate the original free carboxyl group simply by heating, but in the presence of an acidic catalyst, the carboxyl group can be regenerated more quickly.

As the acidic catalyst, when the one-part type thermosetting composition is intended for the final purpose, a heat-latent acid catalyst component (C) which shows activity only when heated is preferable. Preferred examples of the component include a compound obtained by neutralizing a protonic acid or a Lewis acid with a Lewis base (a mixture of a Lewis acid and a trialkyl phosphate), sulfonic acid esters, phosphoric acid esters, and onium compounds. Examples of the compound obtained by neutralizing the protonic acid with a Lewis base include halogenocarboxylic acids, sulfonic acids, sulfuric acid monoesters, phosphoric acid mono- and diesters, polyphosphate esters, boric acid mono- and diesters, ammonia, Various amines such as monoethylamine, triethylamine, pyridine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethynolamine, diethanolamine, triethanolamine, etc. or trialkylphosphine, triarylphosphine, trialkylphosphite, triaryl Compounds neutralized with phosphites, and Nailure 2500X, X-47-110, 3525, 52, which are commercially available as acid-base blocking catalysts
25 [trade name, manufactured by King Industry Co., Ltd.].

Compounds obtained by neutralizing a Lewis acid with a Lewis base include, for example, BF ₃ , FeCl ₃ , SnCl ₄ ,
Examples include compounds obtained by neutralizing Lewis acids such as AlCl ₃ , ZnCl ₂ , and CuCl ₂ with the above-mentioned Lewis base substances.
Alternatively, a mixture of the above Lewis acid and a trialkyl phosphate may also be used. As the sulfonic acid esters, for example, a compound represented by the general formula

[0031]

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[0032] (R ¹¹ is a phenyl group in the formula, a substituted phenyl group, a naphthyl group, substituted naphthyl group or alkyl group, R ¹²
Is an alkyl group having 3 to 18 carbon atoms, an alkenyl group, an aryl group, an alkaryl group, an alkanol group, a saturated or unsaturated cycloalkyl or hydroxycyclo which is bonded to a sulfonyloxy group via a primary carbon or a secondary carbon. An alkyl group), specifically, sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, and nonylnaphthalenesulfonic acid, and n-propanol; esterified products with primary alcohols such as n-butanol, n-hexanol and n-octanol or secondary alcohols such as isopropanol, 2-butanol, 2-hexanol, 2-octanol and cyclohexanol; Sulfonic acids and oxirane groups Such as β- hydroxyalkyl sulfonates obtained by the reaction of organic compounds. As the phosphoric esters, for example, the general formula

[0033]

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(Wherein R ¹³ is an alkyl group, cycloalkyl group or aryl group having 3 to 10 carbon atoms, and m is 1 or 2), and more specifically,
Primary alcohols such as n-propanol, n-butanol, n-hexanol, n-octanol and 2-ethylhexanol, or secondary alcohols such as isopropanol, 2-butanol, 2-hexanol, 2-octanol and cyclohexanol Phosphoric acid monoesters or phosphoric acid diesters of alcohols are exemplified.

Further examples of the onium compounds, for example the general formula [R ¹⁴ ₃ NR ^{15] +} X ^- ... [8] [R ¹⁴ ₃ PR ^{15] +} X ^- ... [9] [R ¹⁴ ₂ OR ^{15] +} X ^- ... [10 'and [R ¹⁴ ₂ SR ^{15] + X - ... [11] (} R 14 is an alkyl group having 1 to 12 carbon atoms in the formula, alkenyl group, aryl group, alkaryl group, alkanol group or a cycloalkyl An alkyl group, two R ¹⁴ may be bonded to each other to form a heterocyclic ring having N, P, O or S as a hetero atom, and R ¹⁵ may be a hydrogen atom, a carbon atom having 1 to 12 carbon atoms; And an alkyl group, an alkenyl group, an aryl group, an alkaryl group, and X ⁻ is SbF ₆ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ or BF ₄ ⁻ ).

The amount of the heat latent acidic catalyst component (C) to be used is not particularly limited, but is usually 0.01 to 10% based on the total solid content of the thermosetting composition using the latent carboxyl compound of the present invention. Preferably it is in the range of 10% by weight.
If the amount of the acidic catalyst is less than 0.01% by weight, the catalytic effect is not sufficiently exhibited. If the amount is more than 10% by weight, the cured product finally obtained may be colored or the water resistance may be reduced, Not preferred. Regarding the temperature and time required for curing the thermosetting composition using the latent carboxyl compound of the present invention, a free carboxyl group is regenerated from the blocked functional group represented by the general formula [3] or [4]. The curing is usually completed by heating at a temperature in the range of 50 to 200 ° C. for about 2 minutes to 10 hours, depending on the temperature, the type of the reactive functional group, the presence or absence of the acidic catalyst, and the type. Further, when using the latent carboxyl compound of the present invention in a thermosetting composition, if necessary, a coloring pigment,
A filler, a solvent, a curing catalyst, a flow regulator, an ultraviolet absorber, an antioxidant, and the like can be blended and used for a paint, an ink, an adhesive, a molded article, and the like.

[0037]

Next, the present invention will be described in more detail by way of examples.
As will be explained, the present invention is in no way limited by these examples.
It is not something to be done. Example 1(A) Production of polycarboxyl compound (a-1)  Four-necked flask equipped with thermometer, reflux condenser and stirrer
134.0 parts by weight of trimethylolpropane,
462.0 parts by weight of drophthalic anhydride, methyl isobutyl
Charge 149.0 parts by weight of ketone and heat with stirring.
The reflux temperature was maintained for 6 hours. The acid value of the mixture is then
1 / water weight ratio = 9/1.
Heat treated solution at 30 ° C for 30 minutes
Continue to heat and stir until the solution titration is 226 or less.
Has three carboxyl groups per molecule
And a polycarboxyl having a molecular weight of 596 and an acid equivalent of 199.
An 80 wt% solution of the compound (a-1) was obtained.

[0038](B) Latent carboxyl compound (A-
Production of 1)  The polycarboxyl compound (a-
Using the solution of 1), prepare the following composition in the same flask as above.
And stirred at 70 ° C. 4 hours at the same temperature
When the reaction is continued and the acid value of the mixture reaches 4.0 mgKOH / g
The reaction was terminated at this point and immediately cooled, and the acid value was 8.0 mgKOH / g.
50 of non-gel-like latent carboxyl compound (A-1)
A wt% solution was obtained. The average functional group concentration in this reaction
Was 2.0. 418.7 parts by weight of the above polycarboxyl compound (a-1) solution 55.4 parts by weight of isobutyl vinyl ether 109.4 parts by weight of 1,4-cyclohexanedimethanol divinyl ether 2.0 parts by weight of monooctyl phosphate xylene 414.5 parts by weight Parts by weight

Embodiment 2(A) Production of polycarboxyl compound (a-2)  Pentaerythritol 13 was added to the flask described in Example 1.
6.0 parts by weight, 616.0 parts by weight of hexahydrophthalic anhydride
And 188.0 parts by weight of methyl ethyl ketone.
The mixture was heated with stirring, and the reflux temperature was maintained for 8 hours. After this
The acid value of the compound (measured by the same method as described above) is 239 or more
By continuing heating and stirring until it is below, one molecule
Per carboxyl group, molecular weight 752, acid equivalent
80 of the polycarboxyl compound (a-2) having an amount of 188
A wt% solution was obtained.

[0040](B) Latent carboxyl compound (A-
2) Manufacturing  The polycarboxyl compound (a-
Using the solution of 2), the following flask was placed in the same flask as in Example 1.
A mixture of the composition was charged and stirred at 70 ° C. 5 at the same temperature
The reaction was continued for an hour, and the acid value of the mixture became 4.5 mgKOH / g.
When the reaction was completed, the reaction was immediately cooled and the acid value was adjusted to 9.0 mg KOH.
/ G of the non-gel-like latent carboxyl compound (A-2)
A 50 wt% solution was obtained. In this reaction, the average functional group
The concentration was 2.0. The above polycarboxyl compound (a-2) solution 410.5 parts by weight Isobutyl vinyl ether 87.5 parts by weight 1,4-cyclohexane dimethanol divinyl ether 84.2 parts by weight Monooctyl phosphate 2.0 parts by weight Methyl isobutyl ketone 415 .8 parts by weight

Comparative Example 1Latent carboxyl compound (A
-3) Manufacturing  Example 1 (a) polycarboxyl compound (a-1)
And the mixture of the following composition was prepared in the same manner as in Example 1 (b).
The acid value is 7.8 mgKOH / g.
50 wt% of gel-like latent carboxyl compound (A-3)
A solution was obtained. Polycarboxyl compound (a-1) solution of Example 1 (a) 416.0 parts by weight Isobutyl vinyl ether 167.2 parts by weight Monooctyl phosphate 2.0 parts by weight Xylene 414.8 parts by weight

Application Examples 1 and 2 and Comparative Application Example 1 (1) Synthesis of resin (Synthesis of component B) 40.00 weight of xylene was charged into a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel. Then, the mixture was heated under stirring and kept at 100 ° C. Next, the mixture of the monomer and the polymerization initiator (dropping component) shown in Table 1 was dropped at a constant speed from the dropping funnel over 2 hours at a temperature of 100 ° C. After completion of the dropwise addition, the temperature of 100 ° C. was maintained for 1 hour, and a polymerization initiator solution (additional catalyst) having the composition shown in Table 1 was added.
When the temperature of 0 ° C. was maintained for 2 hours, the reaction was terminated, and resin solutions A and B having the properties shown in Table 1 were obtained.

[0043]

[Table 1]

Note 1) Non-volatile content measurement conditions: 50 ° C., 0.1 mmHg for 3 hours 2) Viscosity; Gardner viscosity (25 ° C.) JIS K-5400 (1979) 4.2.2 Using a viscometer.

(2) Production of clear paint The raw materials having the compositions shown in Table 2 were mixed to obtain a one-pack clear paint. Each of the obtained paints was diluted to 1 poise (measured at 20 ° C. with a Brookfield viscometer) using thinner (xylene / n-butyl acetate = 8/2 weight ratio), and then diluted with 5 wt.
Stored sealed at 0 ° C. After storage at 50 ° C. for 30 days, the viscosity was measured again. As shown in Table 3, almost no increase in viscosity was observed, indicating excellent storage stability.

[0046]

[Table 2]

Note 1) Acid catalyst A: p-toluenesulfonic acid (1-methylheptyl) xylene solution stirrer, thermometer, dropping funnel,
2-octanol 3 in a four-necked flask equipped with a condenser
After adding 15 parts by weight and cooling with ice, 44.9 parts by weight of potassium-t-butoxide was added and dissolved, and 53.4 parts by weight of p-toluenesulfonyl chloride in which 300 parts by weight of diethyl ether was dissolved was added for 30 minutes. It dripped over. One hour after the addition, the ice cooling was stopped, and the reaction was further performed for 1 hour. After completion of the reaction, the reaction mixture was washed three times with 300 parts by weight of water, and then molecular sieve 4A1 / 16 [Wako Pure Chemical Industries, Ltd.
And the solvent was distilled off with an evaporator to obtain 43 parts by weight of p-toluenesulfonic acid (1-methylheptyl) (yield: 72%). The obtained heat-latent acid catalyst was dissolved in 238 parts by weight of xylene and diluted to 10% by weight in terms of p-toluenesulfonic acid. 2) Acid catalyst B: 10 wt% of equimolar salt of zinc chloride and pyridine
% Dimethyl sulfoxide solution The pyridine salt of zinc chloride is treated with dimethyl sulfoxide in 10%.
Solution diluted to weight percent. 3) Modaflow: Leveling agent manufactured by Monsanto

(3) Preparation of test piece Cathodic electrodeposition paint Aqua No. 4
200 [trade name, manufactured by NOF CORPORATION] with a dry film thickness of 20 μm
And baked at 175 ° C for 25 minutes.
Further, a test plate was prepared by applying an intermediate coating paint Epico No. 1500CP sealer (trade name, manufactured by Nippon Oil & Fat Co., Ltd.) by air spraying so as to have a dry film thickness of 40 μm and baking at 140 ° C. for 30 minutes. Next, bell coat No6
000 silver metallic base coat paint [trade name,
Nippon Oil & Fats Co., Ltd.] by air spray at intervals of 1 minute and 30 seconds and 2 stages to a dry film thickness of 15 μm, set at 20 ° C. for 3 minutes, and apply the clear paint of (2) above. (Ford Cup No4, 25 at 20 ° C
Seconds), paint each paint diluted with air spray, 140 ℃
For 30 minutes to prepare a test piece.

[0049]

[Table 3]

Note 1) It was determined by drying a coating material diluted with Ford Cup No. 4 for 25 seconds (20 ° C.) at 105 ° C. for 3 hours. 2) 2 ml of 40 wt% sulfuric acid is spotted on the test piece,
After being left at 20 ° C. for 48 hours, abnormality of the coating film was visually determined. 3) Impact deformation tester [JIS Z-5400 (1979)
6.13.3 Method B], the test piece was put in a shooting mold having a radius of 6.35 mm, and the damage of the coating film when a 500 g weight was dropped from a height of 40 cm was visually determined. 4) Measured at 20 ° C. with an M-type micro hardness tester manufactured by Shimadzu Corporation. The higher the value, the harder it is. 5) Sunshine weather meter (JIS B-775)
After exposure for 3000 hours using 3), the abnormality of the coating film was visually determined.

The coating film performance is shown in Table 3. In each case, a uniform and glossy coating film was obtained, and excellent storage stability and
It showed acid resistance, impact resistance, hardness and weather resistance. However, in Comparative Application Example 1, since a compound having two vinyl ether groups per molecule was not used as a blocking agent for the latent carboxyl compound, the coating solid content and Knoop hardness were lower than in Application Example 1.

[0052]

The thermosetting composition of the present invention cures at a relatively low temperature to give a cured product having excellent chemical performance, physical performance and weather resistance, and further discharges volatile substances to the outside during curing. Low, and also excellent in storage stability,
Available as one-pack type paints, inks, adhesives,
It is suitably used for molded articles and the like. Further, the latent carboxyl compound of the present invention is suitably used for providing a thermosetting composition having the above-mentioned coating properties and coating properties.

Claims (5)

(57) [Claims] (A) a polycarboxyl compound having two or more carboxyl groups per molecule, and having an acid equivalent of 1,000 g / mol or less and a number average molecular weight of 4000 or less;
A compound having one vinyl ether group per molecule,
(C) A non-gel-like latent carboxyl compound having an acid value of less than 10 mgKOH / g obtained by reacting a compound having two vinyl ether groups per molecule. 2. A half-esterified product of a polyol having two or more hydroxyl groups per molecule and an acid anhydride, or a polyisocyanate compound having two or more isocyanate groups per molecule and a hydroxycarboxylic acid. Adducts with acids or amino acids,
The latent carboxyl compound according to claim 1, which is a polyester resin or an acrylic resin. 3. The non-gel-like latent carboxyl compound according to claim 1 as the component (A) and two or more reactive functional groups capable of forming a chemical bond by heating with a carboxyl group as the component (B) in one molecule. A thermosetting composition comprising, as a component (C), a heat-latent acid catalyst which is active when cured by heating. 4. The reactive functional group of the component (B) is an epoxy group,
Silanol group, alkoxysilane group, hydroxyl group,
At least one selected from an amino group, an imino group, an isocyanate group, a blocked isocyanate group, a cyclocarbonate group, a vinyl ether group, a vinyl thioether group, an aminomethylol group, an alkylated aminomethylol group, an acetal group and a ketal group The thermosetting composition according to claim 3. 5. A compound obtained by neutralizing a protonic acid or a Lewis acid with a Lewis base, a mixture of a Lewis acid and a trialkyl phosphate, a sulfonate, a phosphate and an onium. The thermosetting composition according to claim 3, wherein the thermosetting composition is at least one selected from compounds.