JP2023077572A - Heat curable resin composition and cured film - Google Patents

Abstract

To provide a heat curable resin composition designed to facilitate high solidification.SOLUTION: A heat curable resin composition causes at least two kinds of reactions of interesterification reaction and other chemical reactions that proceed thermally. The heat curable resin composition needs a polyol compound (A) and a transesterification catalyst (B), and contains a composition (X) that causes a reaction other than interesterification reaction. The composition (X) has an alkyl ester group.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a thermosetting resin composition and a cured film.

The present inventors are studying a thermosetting resin composition whose curing reaction is transesterification (Patent Documents 1 and 2). Recent studies have revealed that by using the transesterification reaction as the curing reaction, it is possible to secure curing performance equivalent to curing using commonly known melamine resins and polyisocyanate compounds. .

On the other hand, studies have also been made on thermosetting resin compositions whose curing reaction is the Michael addition reaction of compounds having active hydrogen such as malonic acid esters and acetylacetate esters, and α, β unsaturated carbonyl compounds (patent References 3, 4, etc.). Furthermore, a thermosetting resin composition is also known in which an acid-epoxy reaction is used as a curing reaction.

As an attempt to improve the performance of these thermosetting resin compositions, it is also required to make the thermosetting resin composition have a high solid content. A thermosetting resin composition with a high solid content can be used as a paint that can be efficiently thickened when forming a coating film. Furthermore, by reducing the amount of solvent used, the load on the environment can be reduced.

Japanese Patent No. 6398026 International publication 2019/069783 Japanese Patent Publication No. 2018-519436 JP-A-2002-285041

SUMMARY OF THE INVENTION In view of the above, an object of the present invention is to provide a thermosetting resin composition that can easily be made into a high solid.

The present invention is a thermosetting resin composition that undergoes at least two reactions, transesterification and other thermally-progressive chemical reactions, comprising:
A polyol compound (A) and a transesterification catalyst (B) are essential,
A thermosetting resin composition containing a composition (X) that causes a reaction other than transesterification, and the composition (X) has an alkyl ester group.

The composition (X) can essentially include an active hydrogen-containing compound (C), a (meth)acrylate compound (D) and a Michael reaction catalyst (E).
The active hydrogen-containing compound (C) is preferably a malonic acid alkyl ester and/or an acetoacetic ester.
The active hydrogen-containing compound (C) preferably has a molecular weight of 3,000 or less.

The composition (X) can essentially contain an epoxy group-containing compound (F), a carboxylic acid partial ester compound (G), and an acid-epoxy reaction catalyst (H).
The thermosetting resin composition preferably has a solid content of 50% by weight or more.

The present invention also provides a cured film obtained by curing the thermosetting resin composition described above by heating.

ADVANTAGE OF THE INVENTION The thermosetting composition of this invention has the effect that it can be hardened at low temperature, and high solidification can be achieved.

Rigid body pendulum type physical property test data of Example 1. Rigid body pendulum type physical property test data of Comparative Example 1. Rigid body pendulum type physical property test data of Comparative Example 2. Rigid body pendulum type physical property test data of Comparative Example 3. Rigid body pendulum type physical property test data of Example 2. Rigid body pendulum type physical property test data of Comparative Example 4. Rigid body pendulum type physical property test data of Comparative Example 5. Rigid body pendulum type physical property test data of Comparative Example 6. Rigid body pendulum type physical property test data of Example 3. Rigid body pendulum type physical property test data of Example 4. Rigid body pendulum type physical property test data of Example 5. Rigid body pendulum type physical property test data of Example 6. Rigid body pendulum type physical property test data of Example 7. Rigid body pendulum type physical property test data of Example 8. Rigid body pendulum type physical property test data of Example 9. Rigid body pendulum type physical property test data of Example 10. Rigid body pendulum type physical property test data of Comparative Example 7. Rigid body pendulum type physical property test data of Comparative Example 8. Rigid body pendulum type physical property test data of Comparative Example 9. Rigid body pendulum type physical property test data of Comparative Example 10. Rigid body pendulum type physical property test data of Comparative Example 11. Rigid body pendulum type physical property test data of Comparative Example 12. Rigid body pendulum type physical property test data of Example 11. Rigid body pendulum type physical property test data of Example 12. Rigid body pendulum type physical property test data of Example 13. Rigid body pendulum type physical property test data of Comparative Example 13. Rigid body pendulum type physical property test data of Comparative Example 14. Rigid body pendulum type physical property test data of Comparative Example 15. Rigid body pendulum type physical property test data of Comparative Example 16. It is drawing which shows the reading method of hardening start temperature.

The thermosetting compositions of the present invention are thermosetting resin compositions that combine two reactions, transesterification and other thermally-progressive chemical reactions.
The present inventors are studying a thermosetting resin composition that is cured by a transesterification reaction. In addition to this, it is an object of the present invention to obtain a thermosetting resin composition which undergoes yet another reaction.

A particularly preferable point is that the thermosetting resin composition can be made to have a high solid by causing two reactions in this way.
In order to achieve high solids, a thermosetting resin composition containing a large amount of relatively low-molecular-weight components is used so that the composition can be sufficiently polymerized after thermosetting. necessary. In order that the resin after curing has sufficient performance, it is preferable to obtain sufficient polymerization and high crosslink density. Therefore, it is necessary to design a resin composition that can achieve such a purpose.
In the present invention, since two or more reactions are caused, it is easy to achieve a sufficiently high molecular weight as a resin after curing even if a raw material with a relatively low molecular weight is used.

Furthermore, the composition (X) that causes a reaction other than the transesterification reaction has an alkyl ester group. This causes the alkyl ester groups in the composition (X) to react with the polyol compound (A). This results in an overall bonded resin composition after both reactions have proceeded. In other words, the part crosslinked by the transesterification reaction and the part crosslinked by the other reaction do not exist as separate parts, but they become one crosslinked resin as a whole. This is preferable in that a coating film having good performance can be obtained.

In the present invention, "other thermally proceeding chemical reactions" other than transesterification are not particularly limited, but specifically, Michael addition reaction, acid-epoxy reaction, urethanization reaction, Diels Alder reaction, dehydration condensation reaction (ether, ester, amide, melamine, silicone, etc.), thiol-ene reaction, polymerization reaction and the like can be mentioned. These reactions should be easily combined in the same system, furthermore, even if an alkyl ester group is present, the reaction should not be affected, and by-products having poor compatibility with the crosslinked resin should be produced. It is particularly preferable from the viewpoints that the reaction does not occur, the composition can be obtained from inexpensive materials, and the like. Among these, the Michael addition reaction and the acid-epoxy reaction are particularly preferred.
These will be described in detail below.

(if the other thermally proceeding chemical reaction is the Michael addition reaction)
A Michael addition reaction is an addition reaction of a compound having an active hydrogen group that is easily anionized to an unsaturated bond.
Examples of the composition (X) that causes such a reaction include those essentially containing an active hydrogen-containing compound (C), a (meth)acrylic acid ester compound (D) and a Michael reaction catalyst (E). Either one of the active hydrogen-containing compound (C) and the (meth)acrylic acid ester compound (D) may have the alkyl ester group, or both of them may have the alkyl ester group. Among them, the active hydrogen-containing compound (C) preferably has an alkyl ester group.

Active hydrogen-containing compound (C)
The active hydrogen-containing compound (C) is not particularly limited, and examples thereof include dialkyl malonic acid, alkyl acetoacetate, alkyl cyanoacetic acid, and trialkyl methanetricarboxylate. When a dialkyl malonic acid ester or an alkyl acetoacetic acid ester is used, the alkyl group forming the ester group is not particularly limited, and those having 1 to 50 carbon atoms can be used.

The alkyl group in the alkyl ester group (that is, R ₈ in the general formula (4) described in detail below) is an alkyl group having 50 or less carbon atoms, more preferably having 1 to 20 carbon atoms. more preferably in the range of 1-10, more preferably in the range of 1-6. Most preferably it is in the range of 1-4. By setting the content within such a range, the curing reaction can be favorably progressed, which is preferable.

Compounds having an active methylene group Many compounds having structures derived from esters are known, but compounds having the above structures are difficult to synthesize because addition reactions between malonic acid esters or acetoacetic esters and vinyl groups readily proceed. Since it is easy and the number of ester groups can be adjusted by selecting the starting raw material, it is particularly preferable in that the curing performance and the performance of the resin after curing can be easily adjusted. Specifically, dimethyl malonate, diethyl malonate, di-n-butyl malonate, methyl acetoacetate, ethyl acetoacetate and the like can be most preferably used.
Further, compounds obtained by reacting these compounds with other compounds may also be used. Examples of such a reaction include a compound obtained by reacting a carboxylic acid group, a compound obtained by reacting only a part of active hydrogens, and the like.
Two or more of these compounds may be used in combination.

The active hydrogen-containing compound (C) preferably has a molecular weight of 3,000 or less. As a result, since a low molecular weight compound is used, the viscosity of the composition can be made low, and high solidification can be efficiently achieved. The molecular weight is more preferably 1,000 or less, even more preferably 500 or less.

Furthermore, since it is a compound with a relatively low molecular weight, it has a low viscosity, so the viscosity of the composition does not increase. Therefore, a high solid state can be achieved.

((Meth) acrylic acid ester compound (D))
The (meth)acrylic acid ester compound is a (meth)acrylic acid ester compound that undergoes a Michael addition reaction with the active hydrogen-containing compound (C) described above.
Such a (meth)acrylic acid ester compound (D) may have only one (meth)acrylic acid ester group represented by the following general formula, or may have two or more. .

Examples of compounds that can be used as such (meth)acrylic acid ester compound (D) include the following.

Examples of (meth)acrylates with a functionality of 1 include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, sec-butyl ( meth)acrylate, t-butyl (meth)acrylate and the like can be mentioned.

Examples of (meth)acrylates with a functionality of 2 include 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol. Di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol Di(meth)acrylate, neopentylglycol di(meth)acrylate, neopentylglycol hydroxypivalate di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate , 1,10-decanediol di(meth)acrylate, glycerol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate (DCP-A), EO adduct diacrylate of bisphenol A (manufactured by Kyoeisha Chemical Co., Ltd. ; light acrylates BP-4EA, BP-10EA) including PO adduct diacrylates of bisphenol A (manufactured by Kyoeisha Chemical; BP-4PA, BP-10PA, etc.). Among them, PO adduct diacrylate of bisphenol A (BP-4PA manufactured by Kyoeisha Chemical Co., Ltd.), dimethylol-tricyclodecane di(meth)acrylate (DCP-A), and the like can be preferably used.

Examples of (meth)acrylates having a functionality of 3 include trimethylolmethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide-modified tri(meth)acrylate, trimethylolpropane propylene oxide-modified tri( meth)acrylate, pentaerythritol tri(meth)acrylate, glycerin propoxytri(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate and the like. Among them, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, and the like can be preferably used.

Examples of (meth)acrylates with 4 functional groups include dipentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethylene oxide-modified tetra(meth)acrylate, and pentaerythritol propylene oxide-modified tetra(meth)acrylate. , ditrimethylolpropane tetra(meth)acrylate and the like. Among them, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and the like can be preferably used.

Examples of (meth)acrylates having 4 or more functional groups include pentaerythritol tetra(meth)acrylate, pentaerythritol ethylene oxide-modified tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, Dipentaerythritol penta(meth)acrylate, ditrimethylolpropane penta(meth)acrylate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane hexa(meth)acrylate, dipenta Examples include polyfunctional (meth)acrylates such as hexa(meth)acrylate of caprolactone-modified erythritol.

The (meth)acrylic acid ester compound (B) may have an alkyl ester group. The alkyl group in the alkyl ester group is an alkyl group having 50 or less carbon atoms, more preferably in the range of 1 to 20 carbon atoms, still more preferably in the range of 1 to 10 carbon atoms, still more preferably , in the range 1-6. Most preferably it is in the range of 1-4. By setting the content within such a range, the curing reaction can be favorably progressed, which is preferable.

(Michael reaction catalyst (E))
Michael addition reactions generally employ a basic compound as a catalyst to form a carbanion from an active hydrogen site.
The compound to be used is not particularly limited, and any compound known as a Michael reaction catalyst can be used.
Specific examples include hydroxides and alkoxides of alkali metals, quaternary ammonium hydroxides, tertiary amines, guanidines, amidines and tertiary phosphines.

(Mixing ratio of (C) to (E))
The content of each component (C) to (E) described above in the composition (X) is preferably as follows. The content of the active hydrogen-containing compound (C) is preferably 10 to 90% by mass with respect to the total mass of (C) to (E). The above lower limit is more preferably 20% by weight, even more preferably 30% by weight. The above upper limit is more preferably 80% by weight, and even more preferably 75% by weight.

The (meth)acrylic acid ester compound (D) is preferably 10 to 60% by mass with respect to the total mass of (C) to (E). The above lower limit is more preferably 15% by weight, and even more preferably 20% by weight. The above upper limit is more preferably 50% by weight, and even more preferably 45% by weight.

The Michael reaction catalyst (E) is preferably 0.05 to 5% by mass with respect to the total mass of (C) to (E). The above lower limit is more preferably 0.1% by weight, and even more preferably 0.15% by weight. The upper limit is more preferably 4% by weight, even more preferably 3% by weight.

(if the other thermally proceeding chemical reaction is an acid-epoxy addition reaction)
An acid-epoxy addition reaction is a reaction that proceeds through a ring-opening reaction between a --COOH group and an epoxy group. Such reactions can also be used in the present invention. In this case, the composition (X) preferably essentially comprises the epoxy group-containing compound (F), the carboxylic acid partial ester compound (G), and the acid-epoxy reaction catalyst (H).

(Epoxy group-containing compound (F))
Epoxy compounds that can be used in the present invention include any known compounds such as trimethylolpropane triglycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate, 3′,4′-epoxy Cyclohexylmethyl, 3,4-epoxycyclohexane carboxylate and the like can be mentioned.

The epoxy group-containing compound (F) preferably has a molecular weight of 3,000 or less. As a result, since a low molecular weight compound is used, the viscosity of the composition can be made low, and high solidification can be efficiently achieved. The molecular weight is more preferably 2,000 or less, even more preferably 1,000 or less.

(Carboxylic acid partial ester compound (G))
The carboxylic acid partial ester compound (G) is a compound obtained by esterifying only a part of a polycarboxylic acid compound having two or more carboxyl groups. Since such a compound has both a carboxyl group and an alkyl ester group in the same molecule, it can contribute to both the acid-epoxy reaction and the transesterification reaction. It is a compound suitable for the purposes of the invention.

Such a compound can be produced by a known reaction such as a method of reacting an acid anhydride of a polycarboxylic acid with an alcohol, or a method of partially esterifying a polycarboxylic acid compound by a known method.

The acid anhydride of the polycarboxylic acid that is the raw material in the above reaction is not particularly limited, and examples thereof include succinic anhydride, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methyl Various dibasic acid anhydrides such as hexahydrophthalic anhydride, benzoic anhydride, and itaconic anhydride can be used. The partial esterification reaction with an acid anhydride and an alcohol is a well-known general reaction. , the reaction conditions, etc. can be carried out according to general conditions.
The alcohol is not particularly limited, and alcohols having 50 or less carbon atoms can be mentioned.
More specifically, known alcohols such as methanol, ethanol, benzyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol and t-butyl alcohol can be used. .

(Acid-epoxy reaction catalyst (H))
The acid-epoxy catalyst (H) is not particularly limited and any known one can be used. Specific examples include quaternary onium salts, tertiary phosphine derivatives, tertiary amine derivatives and the like.
Examples of the quaternary onium salts include tetrabutylammonium bromide, triethylbenzylammonium chloride, tetrabutylphosphonium bromide, and tetraphenylphosphonium bromide.
Examples of the tertiary phosphine include triarylphosphine such as triphenylphosphine, tribenzylphosphine and tritolylphosphine; tricycloalkylphosphine such as tricyclohexylphosphine; trialkylphosphine such as triethylphosphine, tripropylphosphine, tributylphosphine and trioctylphosphine phosphine and the like.
Examples of the tertiary amines include trialkylamines such as triethylamine and tributylamine; dialkylarylamines such as dimethylbenzylamine and diethylbenzylamine; and triethanolamine.
In addition to the acid-epoxy reaction catalyst (H), a polymerization inhibitor such as hydroquinone or phenothiazine may be present to stabilize the reaction system.

The contents of the components (F) to (H) described above in the composition (X) are preferably as follows.
The content of the epoxy group-containing compound (F) is preferably 10 to 90% by mass with respect to the total mass of (F) to (H). The above lower limit is more preferably 20% by weight, even more preferably 30% by weight. The above upper limit is more preferably 80% by weight, even more preferably 70% by weight.

The content of the carboxylic acid partial ester compound (G) is preferably 10 to 90% by mass with respect to the total mass of (F) to (H). The above lower limit is more preferably 20% by weight, even more preferably 30% by weight. The above upper limit is more preferably 80% by weight, even more preferably 70% by weight.

The acid-epoxy reaction catalyst (E) is preferably 0.1 to 10% by mass with respect to the total mass of (C) to (E). The above lower limit is more preferably 0.5% by weight, even more preferably 1% by weight. The upper limit is more preferably 8% by weight, even more preferably 7% by weight.

The above-mentioned composition (X) is, as described above, a composition that causes a thermally proceeding chemical reaction other than the transesterification reaction, and at the same time has an alkyl ester group. That is, a thermally proceeding chemical reaction occurs between the components in composition (X), and the alkyl ester group does not participate in such reaction.

Such an alkyl ester group in the composition (X) forms an ester chain through a transesterification reaction with a hydroxyl group in the thermosetting resin composition of the present invention. Therefore, it is preferable that the composition (X) contains 0.5 to 2 molar equivalents of the alkyl ester groups relative to the hydroxyl groups in the polyol compound (A).

The composition (X) of the present invention includes compositions in which the other thermally proceeding chemical reaction is the Michael addition reaction and compositions in which the other thermally proceeding chemical reaction is the acid-epoxy addition reaction. It does not interfere even if it uses a composition together. That is, it may contain all the components (C) to (H) described above.

(Polyol compound (A))
The polyol compound (A) is a resin having a hydroxyl group. This hydroxyl group causes a transesterification reaction with an ester group to cause a curing reaction.
This polyol compound (A) is not particularly limited as long as it has two or more hydroxyl groups in one molecule and causes a transesterification reaction with an ester group. It may be a resin component such as a polymer, and can be appropriately used depending on the purpose.

When the polyol compound (A) is a resin, various general polyol resins used in the field of thermosetting resins, such as acrylic polyol resins, polyester polyol resins, urethane polyol resins, and carbonate polyol resins, can be used. can be done.
Among them, it is particularly preferable to use acrylic polyol and/or polyester polyol.
As the acrylic polyol and/or polyester polyol used here, resins commonly used in the paint field can be used.
These will be described in detail below.

(A-1) Acrylic polyol The acrylic polyol is obtained by, for example, adding a hydroxyl group vinyl monomer and another polymerizable unsaturated monomer (a ₂ ) copolymerizable with the hydroxyl group vinyl monomer by a known method. It can be produced by copolymerizing with More specifically, polymerization methods such as a solution polymerization method in an organic solvent, an emulsion polymerization method in water, a mini-emulsion polymerization method in water, and an aqueous solution polymerization method can be mentioned.

A hydroxyl group-containing vinyl monomer is a compound having one or more hydroxyl groups and one or more polymerizable unsaturated bonds in one molecule.
As such hydroxyl group-containing vinyl monomers, those described above can be used.

Other polymerizable unsaturated monomers copolymerizable with the hydroxyl group-containing vinyl monomer include, for example, the following monomers (i) to (xix), and any combination thereof.

(i) alkyl or cycloalkyl (meth)acrylates:
For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, tridecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, tricyclodecanyl (meth)acrylate, etc.

(ii) a polymerizable unsaturated monomer having an isobornyl group:
(iii) a polymerizable unsaturated monomer having an adamantyl group such as isobornyl (meth)acrylate:
adamantyl (meth)acrylate, etc.

(iv) a polymerizable unsaturated monomer having a tricyclodecenyl group:
(v) Aromatic ring-containing polymerizable unsaturated monomer such as tricyclodecenyl (meth)acrylate:
Benzyl (meth)acrylate, styrene, α-methylstyrene, vinyltoluene, etc. (vi) A polymerizable unsaturated monomer having an alkoxysilyl group:
vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyltriethoxysilane, etc.

(vii) a polymerizable unsaturated monomer having a fluorinated alkyl group:
perfluoroalkyl (meth)acrylates such as perfluorobutylethyl (meth)acrylate and perfluorooctylethyl (meth)acrylate; fluoroolefins (viii) polymerizable unsaturated monomers having photopolymerizable functional groups such as maleimide groups ( ix) vinyl compounds:
N-vinylpyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate, etc.

(x) a carboxyl group-containing polymerizable unsaturated monomer:
(Meth)acrylic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate, etc. (xi) Nitrogen-containing polymerizable unsaturated monomers:
(Meth)acrylonitrile, (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, methylenebis(meth)acrylamide , ethylene bis (meth) acrylamide, adduct of glycidyl (meth) acrylate and amine compound, etc.

(xii) a polymerizable unsaturated monomer having two or more polymerizable unsaturated groups in one molecule:
Allyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, etc. (xiii) epoxy group-containing polymerizable unsaturated monomers:
Glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxycyclohexylethyl (meth)acrylate, 3,4-epoxycyclohexylpropyl (meth)acrylate , allyl glycidyl ether, etc.

(xiv) a (meth)acrylate having a polyoxyethylene chain terminated with an alkoxy group (xv) a polymerizable unsaturated monomer having a sulfonic acid group:
2-acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth)acrylate, allylsulfonic acid, 4-styrenesulfonic acid, etc.; sodium salts and ammonium salts of these sulfonic acids, etc.

(xvi) a polymerizable unsaturated monomer having a phosphate group:
Acid phosphooxyethyl (meth)acrylate, acid phosphooxypropyl (meth)acrylate, acid phosphooxypoly(oxyethylene) glycol (meth)acrylate, acid phosphooxypoly(oxypropylene) glycol (meth)acrylate, etc.

(xvii) a polymerizable unsaturated monomer having a UV-absorbing functional group:
2-hydroxy-4-(3-methacryloyloxy-2-hydroxypropoxy)benzophenone, 2-hydroxy-4-(3-acryloyloxy-2-hydroxypropoxy)benzophenone, 2,2′-dihydroxy-4-(3- methacryloyloxy-2-hydroxypropoxy)benzophenone, 2,2'-dihydroxy-4-(3-acryloyloxy-2-hydroxypropoxy)benzophenone, 2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2H - Benzotriazole, etc.

(xviii) UV stable polymerizable unsaturated monomers:
4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4-(meth ) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl- 4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2, 2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine and the like

(xix) a polymerizable unsaturated monomer having a carbonyl group:
Acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formyl styrene, vinyl alkyl ketone having about 4 to about 7 carbon atoms (eg, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone), etc.

ｎ_１：１～１０
（式中、Ｒ_４、Ｒ_５，Ｒ_６は、同一又は異なって、水素、アルキル基、カルボキシル基、アルキルエステル基又は下記Ｒ_７－［ＣＯＯＲ_８］ｎ_１で表される構造。
Ｒ_７は、主鎖の原子数が５０以下であり、主鎖中にエステル基、エーテル基、アミド基、ウレタンからなる群より選択される１又は２以上の官能基を有していてもよく、側鎖を有していてもよい脂肪族、脂環族又は芳香族アルキレン基。
Ｒ_８は、炭素数５０以下のアルキル基。）
等を挙げることができる。 The acrylic polyol may have an alkyl ester group that contributes to the transesterification reaction.
Examples of alkyl ester groups that contribute to such transesterification include:
A compound represented by the following general formula (4)

_n1 : 1 to 10
(wherein R ₄ , R ₅ and R ₆ are the same or different and are hydrogen, an alkyl group, a carboxyl group, an alkyl ester group or a structure represented by R ₇ -[COOR ₈ ] _n1 below.
R ₇ has a main chain of 50 or less atoms, and may have one or more functional groups selected from the group consisting of an ester group, an ether group, an amide group and a urethane in the main chain. , an optionally branched aliphatic, alicyclic or aromatic alkylene group.
_R8 is an alkyl group having 50 or less carbon atoms. )
etc. can be mentioned.

(Meth)acrylic acid esters, which are widely used in thermosetting resin compositions, are generally resistant to transesterification reactions. The compounds represented by the general formula described above are particularly suitable for use because they readily undergo transesterification reactions.

The compound represented by the general formula (1) is not particularly limited, and those disclosed in International Publication No. 2921/172397 can be used. Moreover, among these, it is particularly preferable to use methoxycarbonylmethyl (meth)acrylate.

As used herein, "polymerizable unsaturated group" means an unsaturated group capable of undergoing radical polymerization or ion polymerization. Examples of the polymerizable unsaturated group include a vinyl group and a (meth)acryloyl group.

The ratio of the hydroxyl group-containing monomer in producing the above acrylic polyol is preferably 0.5 to 50% by weight based on the total amount of the monomer components. Within this range, a suitable cross-linking reaction can be caused, and excellent physical properties of the coating film can be obtained.
The above lower limit is more preferably 1.0% by weight, even more preferably 5% by weight. The above upper limit is more preferably 50% by weight, even more preferably 40% by weight.

The hydroxyl value of the acrylic polyol is preferably 1 to 250 mgKOH/g from the viewpoint of the water resistance of the coating film to be formed. The above lower limit is more preferably 2 mgKOH/g, even more preferably 5 mgKOH/g. The above upper limit is more preferably 230 mgKOH/g, even more preferably 220 mgKOH/g.

A commercially available product can also be used as such an acrylic polyol. Commercially available products are not particularly limited, and for example, Acrydic A-801-P, A-817, A-837, A-848-RN, A-814, 57-773, A-829 manufactured by DIC Corporation. , 55-129, 49-394-IM, A-875-55, A-870, A-871, A-859-B, 52-668-BA, WZU-591, WXU-880, BL-616, CL -1000, CL-408 and the like.

(C-2) Polyester polyol A polyester polyol can usually be produced by an esterification reaction or a transesterification reaction between an acid component and an alcohol component.
Examples of the acid component include compounds commonly used as acid components in the production of polyester resins. Examples of the acid component include aliphatic polybasic acids, alicyclic polybasic acids, aromatic polybasic acids, and anhydrides and esters thereof.

The aliphatic polybasic acids and their anhydrides and esters generally include aliphatic compounds having two or more carboxyl groups in one molecule, acid anhydrides of the aliphatic compounds and esters of the aliphatic compounds. fatty acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, octadecanedioic acid, citric acid, butanetetracarboxylic acid, etc. anhydrides of the above aliphatic polycarboxylic acids; esters of lower alkyls having about 1 to about 4 carbon atoms of the above aliphatic polycarboxylic acids, and any combination thereof.
The aliphatic polybasic acid is preferably adipic acid and/or adipic anhydride from the viewpoint of the smoothness of the resulting coating film.

The above alicyclic polybasic acids, and their anhydrides and esters are generally compounds having one or more alicyclic structures and two or more carboxyl groups in one molecule, and acid anhydrides of the above compounds. and esters of the above compounds. Alicyclic structures are primarily 4- to 6-membered ring structures. Examples of the above alicyclic polybasic acids and their anhydrides and esters include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-cyclohexene-1 ,2-dicarboxylic acid, 3-methyl-1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, etc. Anhydrides of the above alicyclic polycarboxylic acids; esters of lower alkyls having about 1 to about 4 carbon atoms of the above alicyclic polycarboxylic acids, and any of them A combination is mentioned.

As the alicyclic polybasic acid, and anhydrides and esters thereof, from the viewpoint of the smoothness of the resulting coating film, 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic anhydride, 1, 3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic anhydride are preferred, and 1,2-cyclohexanedicarboxylic acid and/or Or 1,2-cyclohexanedicarboxylic anhydride is more preferable.

The aromatic polybasic acids, and anhydrides and esters thereof are generally aromatic compounds having two or more carboxyl groups in one molecule, acid anhydrides of the aromatic compounds and esters of the aromatic compounds. aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, trimellitic acid, and pyromellitic acid; anhydrides of acids; esters of lower alkyls having about 1 to about 4 carbon atoms of the above aromatic polycarboxylic acids, and any combination thereof.
Phthalic acid, phthalic anhydride, isophthalic acid, trimellitic acid, and trimellitic anhydride are preferable as the aromatic polybasic acids and their anhydrides and esters.

As the acid component, an acid component other than the aliphatic polybasic acid, alicyclic polybasic acid, and aromatic polybasic acid, such as coconut oil fatty acid, cottonseed oil fatty acid, hemp seed oil fatty acid, rice bran oil fatty acid, and fish oil fatty acid. , tall oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid; lauric acid, myristic acid, palmitic acid, stearic acid, olein acids, linoleic acid, linolenic acid, benzoic acid, p-tert-butylbenzoic acid, cyclohexanoic acid, monocarboxylic acids such as 10-phenyloctadecanoic acid; lactic acid, 3-hydroxybutanoic acid, 3-hydroxy-4-ethoxybenzoic acid and the like, and any combination thereof.

Examples of the alcohol component include polyhydric alcohols having two or more hydroxyl groups in one molecule, such as ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4 -butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,2-butanediol, 2-butyl -2-ethyl-1,3-propanediol, 1,2-pentanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyltrimethylene glycol, tetra methylene glycol, 3-methyl-4,3-pentanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,5 -hexanediol, 1,4-hexanediol, 2,5-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, neopentyl glycol hydroxypivalate, hydrogenated bisphenol A, water Dihydric alcohols such as added bisphenol F and dimethylolpropionic acid; polylactone diols obtained by adding lactone compounds such as ε-caprolactone to the above dihydric alcohols; ester diol compounds such as bis(hydroxyethyl) terephthalate; alkylene oxides of bisphenol A Polyether diol compounds such as adducts, polyethylene glycol, polypropylene glycol, and polybutylene glycol; glycerin, trimethylolethane, trimethylolpropane, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol , tris(2-hydroxyethyl)isocyanuric acid, sorbitol, mannitol, and other trihydric or higher alcohols; polylactone polyol compounds obtained by adding lactone compounds such as ε-caprolactone to the above trihydric or higher alcohols; fatty acid esters of glycerin compounds and the like.

Further, as the alcohol component, alcohol components other than the polyhydric alcohol, for example, monoalcohols such as methanol, ethanol, propyl alcohol, butyl alcohol, stearyl alcohol, 2-phenoxyethanol; propylene oxide, butylene oxide, "Cardura E10" ( and an alcohol compound obtained by reacting a monoepoxy compound such as Glycidyl Ester of Synthetic Highly Branched Saturated Fatty Acid (trade name, manufactured by HEXION Specialty Chemicals, Inc.) with an acid.

The polyester polyol is not particularly limited and can be produced according to a normal method. For example, the acid component and the alcohol component are heated in a nitrogen stream at about 150 to about 250° C. for about 5 to about 10 hours to carry out an esterification reaction or a transesterification reaction between the acid component and the alcohol component. Thereby, a polyester polyol can be produced.

The polyol of the present invention may be a combination of both the polyacrylic polyol and the polyester polyol described above.

(C-3) Low-molecular-weight polyol The polyol is not limited to the resins described above, and a low-molecular-weight polyol (specifically, a molecular weight of 2,000 or less) can also be used.
Examples of low-molecular-weight polyols include ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3- Butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,2-butanediol, 1,1,1-trimethylolpropane, 2-butyl-2-ethyl- 1,3-propanediol, 1,2-pentanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyltrimethylene glycol, tetramethylene glycol, 3- methyl-4,3-pentanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1 , 4-hexanediol, 2,5-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, neopentyl glycol hydroxypivalate, hydrogenated bisphenol A, hydrogenated bisphenol F, di dihydric alcohols such as methylolpropionic acid; polylactone diols obtained by adding lactone compounds such as ε-caprolactone to the above dihydric alcohols; ester diol compounds such as bis(hydroxyethyl) terephthalate; alkylene oxide adducts of bisphenol A; polyethylene glycol , Polyether diol compounds such as polypropylene glycol, polybutylene glycol; glycerin, trimethylolethane, trimethylolpropane, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, tris (2 hydroxyethyl)isocyanuric acid, sorbitol, trihydric or higher alcohols such as mannitol, and the like.

(Transesterification catalyst (E))
Since the thermosetting resin composition of the present invention uses the ester reaction as part of the curing reaction, it is necessary to mix the ester exchange catalyst (E). As such a transesterification catalyst (E), any known one can be used, but since it is used in combination with the Michael reaction catalyst (D) described above, by combining these , it is necessary to select and use a combination that does not lower the activity of the catalyst.

In general, the Michael reaction catalyst (D) is often a basic compound, so if an acidic compound is used as the transesterification catalyst (E), the combined use of these compounds may reduce the catalytic activity. I don't like it.

From the viewpoint described above, the transesterification catalyst (E) is preferably a metal compound.
The metal compound catalyst can obtain transesterification reactivity by selecting the metal species, using it in combination with other compounds, or the like. Furthermore, it is preferable in that necessary performance can be appropriately obtained depending on the combination with the resin composition.

The metal compound catalyst is preferably a compound (E-1) containing at least one metal element selected from the group consisting of zinc, tin, titanium, aluminum, zirconium and iron. Such compounds are preferred in that they have suitable transesterification reactivity. Among these, zinc and zirconium are preferable because they have particularly excellent transesterification reactivity.

Among the compounds described above, the zirconium compound has extremely excellent transesterification ability, and is particularly preferable in that the above-described thermosetting resin composition can be easily obtained by using it. is.
The use of a zirconium compound as a transesterification catalyst is also preferable in that a very high transesterification ability can be obtained even when the compound (E-2) described in detail below is not used in combination.

Examples of the metal compound catalyst include zinc acetate, zinc acrylate, zinc acetylacetonate, zinc trifluoromethanesulfonate, zinc oxide, aluminum isopropylate, iron chloride, zinc dithiocarbamate, tetraisopropyl titanate, dibutyltin dilaurate, dibutyl Various metal compounds such as tin dioctate, monobutyl stannate, zirconium butoxide, zirconium acetylacetonate, zirconia, and the like can be mentioned.
Furthermore, a zinc cluster catalyst (for example, ZnTAC24 (trade name) manufactured by Tokyo Chemical Industry Co., Ltd.) can also be used.
Furthermore, two or more of the above compounds may be used in combination.

As the metal compound catalyst, a metal salt compound is particularly preferable, and the use of a metal acetylacetonate as an anion component is preferable because it tends to provide a better transesterification ability than a metal compound of the same kind. For example, zinc acetylacetonate and zirconium acetylacetonate can be used particularly preferably. In particular, zirconium acetylacetonate exhibits extremely good catalytic performance.

When zinc oxide is used, it is preferable to use one dispersed in acetylacetone. It is believed that zinc acetylacetonate is produced by dispersing zinc oxide in acetylacetone.
The zinc oxide and acetylacetone are preferably contained in a ratio of 1:0.5 to 1:10 (weight ratio). A particularly favorable result can be obtained by blending in such a ratio.
The above lower limit is more preferably 1:0.8, even more preferably 1:1. The above upper limit is more preferably 1:5, even more preferably 1:3.

When the above metal compounds are used as catalysts, they may further include organophosphorus compounds, urea, alkylated ureas, thioureas, alkylated thioureas, sulfoxide compounds, quaternary ammonium compounds, quaternary phosphonium compounds, and pyridine and quinoline. , isoquinoline, phenanthroline, and imidazole compounds. It is more preferable to use at least one compound (E-2) selected from the group consisting of derivatives thereof, since the catalytic performance is improved.
It is particularly preferable to use a metal compound activated by using these compounds in combination, since the curing initiation temperature and gel fraction described above can be obtained.

Although the mechanism by which such an effect is obtained is not clear, it is presumed that the compound (B-2) is coordinated with the metal compound to improve the catalytic activity.
Therefore, as the compound (B-2), it is preferable to select a compound capable of coordinating with the metal compound.

In the thermosetting resin composition of the present invention, the total amount of the polyol compound (A), the transesterification catalyst (B), and the composition (X) that causes a reaction other than the transesterification reaction is is preferably contained in a proportion of 10 to 90% by mass.
The above lower limit is more preferably 20% by weight, even more preferably 30% by weight.
The above upper limit is more preferably 80% by weight, and even more preferably 75% by weight.

The thermosetting resin composition of the present invention contains the polyol compound (A), the transesterification catalyst (B), the transesterification catalyst (B ) in a proportion of 0.1 to 10% by mass.
The above lower limit is more preferably 0.5% by weight, even more preferably 1% by weight.
The upper limit is more preferably 8% by weight, even more preferably 7% by weight.

In the thermosetting resin composition of the present invention, the total amount of the polyol compound (A), the transesterification catalyst (B), and the composition (X) that causes a reaction other than the transesterification reaction, the composition (X) is preferably contained in a proportion of 10 to 90% by mass.
The above lower limit is more preferably 15% by weight, and even more preferably 20% by weight.
The above upper limit is more preferably 80% by weight, even more preferably 70% by weight.

The thermosetting resin composition of the present invention may further contain a solvent. Here, the solvent is a volatile component that does not correspond to the essential components (A) to (E) described above, and means a solvent that is commonly used in the chemical field.
When the above solvent is used, a high solid type composition containing 48% by weight or less of volatile components can be obtained. Moreover, it can be a composition that does not contain a solvent. The amount of the volatile component used is more preferably 46% by weight or less, and most preferably 45% by weight or less.

The thermosetting resin composition of the present invention preferably has a solvent content of 50% by weight or less and a viscosity at 25° C. of 500 mPa·s or less. This makes it possible to obtain an appropriate viscosity that enables good coating even though the amount of solvent used is small. The viscosity is more preferably 400 mPa·s or less, most preferably 200 mPa·s or less.

When the thermosetting resin composition of the present invention contains the active hydrogen-containing compound (C) described above, the active hydrogen-containing compound (C) is used as a reaction solvent to synthesize the polyol compound (A). may be performed. That is, since the polyol compound (A) is preferably used in a solution state, a resin polymerized by solution polymerization is usually used. When the active hydrogen-containing compound (C) is used as the reaction solvent in this case, there is no need to use a general-purpose solvent that volatilizes during use, which is preferable for making the composition highly solid.

When synthesizing such a polyol compound (A), the polyol compound (A) is particularly preferably an acrylic polyol. This is because the active hydrogen-containing compound (C) is not incorporated into the acrylic polyol in the synthesis of the acrylic polyol.

Synthesis of the polyol compound (A) using the active hydrogen-containing compound (C) as a solvent is not particularly limited, and can be carried out according to general synthesis methods and synthesis conditions.

In the thermosetting composition of the present invention, in addition to the resin component described above, other cross-linking agents commonly used in the fields of paints and adhesives may be used in combination. The cross-linking agent that can be used is not particularly limited, and examples thereof include isocyanate compounds, blocked isocyanate compounds, melamine resins, epoxy resins, silane compounds, and the like. In addition, vinyl ether, an anionic polymerizable monomer, a cationically polymerizable monomer, a radically polymerizable monomer, etc. may be used in combination. A curing agent for accelerating the reaction of these cross-linking agents used in combination may also be used.

In addition, the thermosetting resin composition of the present invention may also contain a compound having an alkyl ester group that does not correspond to each component described above. As noted above, the transesterification reaction dominates the curing reaction in the present invention. Therefore, compounds that are involved in such transesterification reactions and that do not correspond to the components (A) to (H) described above can also be used in combination. Such compounds are not particularly limited, and among the compounds and resins described in International Publication 2020/204089, International Publication 2021/172307, etc., those that do not correspond to the components (A) to (H) described above. can be mentioned.

The above-mentioned other cross-linking agents are not essential, and even if the thermosetting resin composition of the present invention does not contain them, they are preferable in that good curability can be obtained.

When the cross-linking agent is a polyisocyanate compound and/or a melamine resin, the blending amount with respect to the total amount of the resin component (A) and the cross-linking agent (that is, (amount of cross-linking agent)/(amount of cross-linking agent + amount of resin component) is The amount is preferably 0.01 to 50% by weight, which is preferable in that the curing reaction by the transesterification reaction and the curing reaction by the other curing agent can be caused at the same time.
The above lower limit is more preferably 0.01% by weight, even more preferably 1% by weight. The above upper limit is more preferably 30% by weight, even more preferably 20% by weight.

The thermosetting resin composition of the present invention can be suitably used in fields such as thermosetting coatings and thermosetting adhesives. Furthermore, it can also be used as an air-drying curable resin composition.

In the thermosetting resin composition of the present invention, a photocurable component may be used in combination so that two curing systems of photoreaction and thermal reaction are used in combination. When setting it as such a composition, you may use a photoinitiator together. The thermosetting resin composition of the present invention preferably does not contain a photopolymerization initiator unless it is such a combined photoreaction system.

The thermosetting resin composition of the present invention preferably has a curing initiation temperature of 120° C. or lower as measured by the method described in the examples of this specification. Since curing can be started at a low temperature in this way, it is preferable in that the amount of energy used during curing can be reduced. It can also be used as an air-drying thermosetting resin composition. The curing initiation temperature is more preferably 110° C. or lower, even more preferably 100° C. or lower.

The thermosetting resin composition of the present invention preferably has a gel fraction of 80% or more when cured at 120° C. for 30 minutes. By having such curing performance, it is possible to obtain sufficient low-temperature curing, and it is preferable in that physical properties of the resin after curing can be improved.

When used as a thermosetting paint, additives commonly used in the paint field may be used in combination with the above components. For example, leveling agents, antifoaming agents, coloring pigments, extender pigments, luster pigments, pigment dispersants, rheology control agents, UV absorbers, and any combination thereof may be used in combination.

When a pigment is used, it is preferably contained in a total amount of 1 to 500% by weight based on 100% by weight of the total solid content of the resin component. The above lower limit is more preferably 3% by weight, more preferably 5 parts by weight. The above upper limit is more preferably 400% by weight, still more preferably 300% by weight.

Examples of the coloring pigments include titanium oxide, zinc white, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigments, phthalocyanine pigments, quinacridone pigments, isoindoline pigments, threne pigments, and perylene pigments. , dioxazine-based pigments, diketopyrrolopyrrole-based pigments, and any combination thereof.

Examples of the extender pigment include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, alumina white, etc. Barium sulfate and/or talc are preferred, and barium sulfate is more preferred.

Examples of the luster pigment include aluminum (including evaporated aluminum), copper, zinc, brass, nickel, aluminum oxide, mica, titanium oxide or iron oxide-coated aluminum oxide, titanium oxide or iron oxide-coated mica, glass flakes, holographic pigments, etc., and any combination thereof. The aluminum pigments include non-leafing aluminum and leafing aluminum.

The color pigment is preferably added to the thermosetting resin composition in a state of being dispersed by a pigment dispersing resin. The amount of the coloring pigment may vary depending on the type of pigment, etc., but in general, it is preferably about 0.1 to about 300 parts by weight per 100 parts by weight of the solid content of the resin component contained in the pigment dispersion resin. and more preferably in the range of about 1 to about 150 parts by weight.

The thermosetting paint may optionally contain an organic solvent, a thickener, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a plasticizer, a surface control agent, an anti-settling agent, a dispersant, an anti-color separation agent, and a rheology control agent. It may further contain paint additives such as agents, leveling agents, substrate wetting agents, and slip agents.

Examples of the thickener include inorganic thickeners such as silicates, metal silicates, montmorillonite, and colloidal alumina; copolymers of (meth)acrylic acid and (meth)acrylic acid ester; Polyacrylic acid-based thickeners such as sodium acrylate; each molecule has a hydrophilic portion and a hydrophobic portion, and in an aqueous medium, the hydrophobic portion adsorbs to the surface of the pigment or emulsion particles in the paint. , Associative thickeners exhibiting a thickening action due to the association of the above hydrophobic moieties, etc.; Fibrin derivative-based thickeners such as carboxymethyl cellulose, methyl cellulose, and hydroxyethyl cellulose; Casein, sodium caseinate, ammonium caseinate, etc. protein-based thickeners; alginic acid-based thickeners such as sodium alginate; polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl benzyl ether copolymers and other polyvinyl-based thickeners; Polyether thickeners such as ether dialkyl ethers and polyether epoxy modified products; maleic anhydride copolymer thickeners such as vinyl methyl ether-maleic anhydride copolymer partial esters; polyamides such as polyamide amine salts system thickeners, etc., as well as any combination thereof.

The polyacrylic acid-based thickener is commercially available, for example, Rohm and Haas "ACRYSOLASE-60", "ACRYSOLTT-615", "ACRYSOLRM-5" (trade names), San Nopco Co. "SN Thickener 613", "SN Thickener 618", "SN Thickener 630", "SN Thickener 634", and "SN Thickener 636" (these are trade names).

In addition, the associative thickener is commercially available, for example, "UH-420", "UH-450", "UH-462", "UH-472", "UH-540" manufactured by ADEKA, “UH-752”, “UH-756VF”, “UH-814N” (the above are product names), “ACRYSOLRM-8W”, “ACRYSOLRM-825”, “ACRYSOLRM-2020NPR”, “ACRYSOLRM” manufactured by Rohm and Haas -12W", "ACRYSOLSCT-275" (the above are product names), "SN Thickener 612", "SN Thickener 621N", "SN Thickener 625N", "SN Thickener 627N", "SN Thickener 660T" manufactured by San Nopco ( above, product names) and the like.

As the pigment dispersing resin, it is preferable to use an acrylic pigment dispersing resin. More specifically, for example, an acrylic resin obtained by polymerizing a polymerizable unsaturated monomer with a polymerization initiator in the presence of a hydrophilic organic solvent can be mentioned.

Examples of the polymerizable unsaturated monomer include the compounds exemplified in the synthesis of the resin described above, and can be used in combination as appropriate.
The pigment dispersion resin is preferably a resin that can be dissolved or dispersed in water. has an acid value of 10-80 mg KOH/g, and more preferably 20-60 mg KOH/g.

The thermosetting resin composition of the present invention preferably contains a pigment dispersion resin in a solid content of 5 to 70% by mass, more preferably 7 to 70% by mass, based on the total solid mass of the resin and the pigment dispersion resin. It is preferable to contain 61% by mass. The above range is preferable from the viewpoint of the storage stability of the thermosetting resin composition, and the finish, water resistance, medium sandability, etc. of the colored coating film formed using the colored coating composition of the present invention.

The thermosetting resin composition of the present invention can also be an aqueous composition. There are no particular restrictions on the method for making the composition aqueous, and the composition can be made aqueous by a general method using the components described above. Even in the case of aqueous conversion, the transesterification reaction can be favorably progressed by using the transesterification catalyst of the present invention.

The article to be coated to which the above thermosetting resin composition can be applied is not particularly limited, and examples include outer panel parts of automobile bodies such as passenger cars, trucks, motorcycles and buses; automobile parts; mobile phones and audio equipment. , building materials, furniture, adhesives, film and glass coating agents, and the like. In addition, precoated metals and metal cans that form a coating film by curing at high temperature for a short period of time can also be used. Furthermore, use in electrodeposition coatings, adhesives, particle boards and the like can also be mentioned.

The thermosetting resin composition can also be used as an electrodeposition coating composition. Electrodeposition paints include cationic electrodeposition paints and anionic electrodeposition paints, and any of these may be used.

The object to be coated may be a metal surface such as the metal material and a vehicle body molded from the metal material, which has been subjected to surface treatment such as phosphate treatment, chromate treatment, and composite oxide treatment. It may be an article to be coated having a coating film.
Examples of the article to be coated having the above-mentioned coating film include those obtained by subjecting a base material to surface treatment as desired and forming an undercoat coating film thereon. In particular, a vehicle body having an undercoat film formed with an electrodeposition paint is preferred, and a vehicle body having an undercoat film formed with a cationic electrodeposition paint is more preferred.

The object to be coated may be the plastic material, or a plastic surface such as an automobile part molded from the plastic material, and optionally subjected to surface treatment, primer coating, or the like. Alternatively, the plastic material and the metal material may be combined.

The method of coating the thermosetting resin composition is not particularly limited, and examples thereof include air spray coating, airless spray coating, rotary atomization coating, curtain coat coating, etc. Air spray coating, rotary atomization coating, etc. is preferred. If desired, static electricity may be applied during coating. A wet coating film can be formed from the aqueous coating composition by the coating method.

The wet coating film can be cured by heating. The curing can be performed by a known heating means, for example, a drying oven such as a hot air oven, an electric oven, an infrared induction heating oven. The wet coating is preferably applied at a temperature ranging from about 80 to about 180°C, more preferably from about 100 to about 170°C, and even more preferably from about 120 to about 160°C for preferably about 10 to about 60 minutes, And more preferably, it can be cured by heating for about 15 to about 40 minutes. It is also preferable in that it can be applied to low-temperature curing at 80 to 140°C.

The thermosetting resin composition of the present invention can also be used in a wet-on-wet multilayer coating film forming method. In this case, after applying a paint made of the thermosetting resin composition of the present invention, another paint composition is applied thereon without curing, and these two layers of paint films are baked at the same time. A method of forming a multilayer coating film, etc. can be mentioned. Moreover, in such a coating method, a multi-layer coating film having three or more layers may be formed in which at least one layer is formed from the thermosetting resin composition of the present invention.

When the thermosetting resin composition of the present invention is used to form such a multilayer coating film, the coating used in combination may be water-based or solvent-based. Furthermore, the curing system may be a curing system by transesterification as described above, or may be other curing systems such as melamine curing and isocyanate curing.

When the thermosetting resin composition of the present invention is used in the field of coatings, it is required to have sufficient curing properties such as smoothness, water resistance, and acid resistance. On the other hand, when used in the field of adhesives, pressure-sensitive adhesives, etc., high curing performance required for paints is not required. The thermosetting resin composition of the present invention can be of a level that can be used as a paint, but even a composition that does not reach such a level can be used in the fields of adhesives, pressure sensitive adhesives, etc. may be used.

A cured film is obtained by three-dimensionally crosslinking the thermosetting resin composition of the present invention. Such a cured film has sufficient performance that it can be used as a paint or adhesive.
The cured film also includes a cured film formed by the method for forming a multilayer coating film described above.

The present invention will be described in more detail below based on examples. In addition, the present invention is not limited to the following examples. In addition, a part represents a weight part in a sentence.

Synthesis Example 1 Ester Compound A
40 parts of trimethylolpropane triacrylate, 55 parts of dimethyl malonate, 56 parts of potassium carbonate, 1.5 parts of 18-crown 6-ether and 95 parts of tetrahydrofuran were mixed and stirred at 50° C. for 3 hours. After completion of the reaction, cyclohexane and water were added and washed with water. The organic layer was neutralized with a saturated aqueous solution of ammonium chloride, washed with water twice, and the obtained organic layer was concentrated under reduced pressure to obtain an ester compound A.

Synthesis Example 2 Monomer A
90 parts of methyl chloroacetate, 130 parts of potassium carbonate and 250 parts of dimethylformamide were mixed, and 78 parts of methacrylic acid was added dropwise to the mixture at 30-40°C. After completion of dropping, 8 parts of triethylamine was added and stirred at 50°C for 4 hours. After completion of the reaction, it was washed with 500 parts of water. 300 parts of toluene was added to the organic layer and washed with 300 parts of water four times. The resulting organic layer was distilled under reduced pressure to obtain Monomer A.

Synthesis Example 3 Polymer Solution A
n-butyl methacrylate (Kyoeisha Chemical Co., Ltd. product: Light Ester NB) 28 parts, 2-hydroxyethyl methacrylate 35 parts, styrene 7 parts as a monomer mixture, 1,1,3,3-tetramethylbutyl as an initiator 3.5 parts of peroxy-2-ethylhexanoate (Perocta O, NOF Corporation) was dissolved in methyl acetoacetate to prepare an initiator solution. 30 parts of methyl acetoacetate was placed in a stirrable flask, and the monomer solution and the initiator solution were added dropwise while blanketing with nitrogen. The polymerization temperature at this time was 100°C. The dropwise addition was carried out in 2 hours, followed by aging at 100° C. for 4 hours to obtain a polymer solution A. The weight average molecular weight was 17,000 and the dispersity was 2.8.

Synthesis Example 4 Polymer Solution B
n-butyl methacrylate (Kyoeisha Chemical Co., Ltd. product: Light Ester NB) 28 parts, 2-hydroxyethyl methacrylate 35 parts, styrene 7 parts as a monomer mixture, 1,1,3,3-tetramethylbutyl as an initiator 3.5 parts of peroxy-2-ethylhexanoate (Perocta O, NOF Corporation) was dissolved in dimethyl malonate to prepare an initiator solution. 30 parts of dimethyl malonate was placed in a stirrable flask, and the monomer solution and the initiator solution were added dropwise while blanketing with nitrogen. The polymerization temperature at this time was 100°C. The dropwise addition was carried out in 2 hours, followed by aging at 100° C. for 4 hours to obtain a polymer solution B. The weight average molecular weight was 24,000 and the dispersity was 3.3.

Synthesis Example 5 Polymer Solution C
20 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd.: Light Ester NB), 15 parts of monomer A, 10 parts of 2-hydroxyethyl methacrylate, 25 parts of 4-hydroxybutyl acrylate, 30 parts of styrene as a monomer mixture, and an initiator 5 parts of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (NOF Corporation, Perocta O) was dissolved in methyl acetoacetate to prepare an initiator solution. A stirrable flask was charged with 43 parts of methyl acetoacetate, and the monomer solution and initiator solution were added dropwise while blanketing with nitrogen. The polymerization temperature at this time was 100°C. The dropwise addition was carried out in 2 hours, followed by aging at 100° C. for 4 hours to obtain a polymer solution C. The weight average molecular weight was 14,000 and the dispersity was 4.1.

Synthesis Example 6 Polymer solution D
20 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd.: Light Ester NB), 15 parts of monomer A, 10 parts of 2-hydroxyethyl methacrylate, 25 parts of 4-hydroxybutyl acrylate, 30 parts of styrene as a monomer mixture, and an initiator 5 parts of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (NOF Corporation, Perocta O) was dissolved in dimethyl malonate to prepare an initiator solution. A stirrable flask was charged with 43 parts of dimethyl malonate, and the monomer solution and initiator solution were added dropwise while blanketing with nitrogen. The polymerization temperature at this time was 100°C. The dropwise addition was carried out in 2 hours, followed by aging at 100° C. for 4 hours to obtain a polymer solution D. The weight average molecular weight was 21,000 and the dispersity was 3.8.

Synthesis Example 7 Polymer solution E
n-butyl methacrylate (Kyoeisha Chemical Co., Ltd. product: Light Ester NB) 28 parts, 2-hydroxyethyl methacrylate 35 parts, styrene 7 parts as a monomer mixture, 1,1,3,3-tetramethylbutyl as an initiator 3.5 parts of peroxy-2-ethylhexanoate (Perocta O, NOF Corporation) was dissolved in butyl acetate to prepare an initiator solution. 30 parts of butyl acetate was placed in a stirrable flask, and the monomer solution and the initiator solution were added dropwise while the flask was sealed with nitrogen. The polymerization temperature at this time was 100°C. The dropwise addition was carried out in 2 hours, followed by aging at 100° C. for 4 hours to obtain a polymer solution E. The weight average molecular weight was 16,000 and the dispersity was 2.3.

Synthesis Example 8 Polymer Solution F
40 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd. product: Light Ester NB), 50 parts of 4-hydroxybutyl acrylate, 10 parts of styrene as a monomer mixture, and 1,1,3,3-tetramethylbutyl as an initiator 5 parts of peroxy-2-ethylhexanoate (Perocta O, NOF Corporation) was dissolved in butyl acetate to prepare an initiator solution. 100 parts of butyl acetate was placed in a stirrable flask, and the monomer solution and the initiator solution were added dropwise while the flask was sealed with nitrogen. The polymerization temperature at this time was 100°C. The dropwise addition was carried out in 2 hours, and then aging was carried out at 100° C. for 4 hours to obtain a polymer solution F. The weight average molecular weight was 11,000 and the dispersity was 2.2.

In addition, the coating film evaluation method in the above table was performed by the following methods.
State of Coating Film After baking, the surface state of the coating film was observed by touch and visually.
◎ : Glossy, smooth surface ○ : Slightly visible citrus skin △ : Citron skin, armpits are visible, no gloss × : No gloss, uneven surface, citron skin, armpits Severe - : Sufficient hardening is not recognized

Xylene Rubbing After baking, the painted plate was rubbed 10 times with gauze impregnated with xylene. After drying the xylene, the surface condition was visually observed.
◎: No change 〇: Slightly scratched △: Slightly dissolved ×: Surface whitened and dissolved

Gel fraction The coating films obtained in Examples were dissolved in refluxing acetone for 30 minutes by the Soxhlet extraction method, and the residual weight % of the coating film was measured as the gel fraction.
A gel fraction of 0 to 40% was evaluated as "X" as being unusable.
A gel fraction of 40 to 60% was evaluated as Δ assuming that a certain degree of curing was observed.
A gel fraction of 60 to 80% was evaluated as ◯, which is regarded as practically usable.
A gel fraction of 80 to 100% was evaluated as excellent in performance.

Rigid pendulum type physical property test Using a rigid pendulum type physical property tester (model number RPT-3000W) manufactured by A&D, the temperature was raised to 180°C at a heating rate of 3°C/min, and changes in period and logarithmic decrement at that time were measured. asked. In particular, it was used to confirm the cured state of the coating film.
Pendulum: FRB-100
Film thickness (WET): 100 μm

The curing start temperature refers to the temperature at which the cycle starts to decrease when a rigid body pendulum test is performed at a temperature rising condition of 3 ° C./min, and is a value obtained by measuring the curing start point as shown in FIG. .

In the examples, the weight average molecular weight and the polydispersity are values of polystyrene equivalent molecular weight measured by gel permeation chromatography (GPC). GPC KF-804L (manufactured by Showa Denko KK) was used as the column, and tetrahydrofuran was used as the solvent.

From the results in Tables 1 to 3, it is clear that the thermosetting resin composition of the present invention has good curing performance while achieving high solids. Furthermore, in the thermosetting resin compositions in Tables 1 and 2 using the Michael addition reaction, thermosetting resin compositions having a low curing initiation temperature can be obtained.

INDUSTRIAL APPLICABILITY The thermosetting resin composition of the present invention is a highly versatile thermosetting resin composition that can be made high solid and adaptable to various curing conditions.

Claims (7)

A thermosetting resin composition that undergoes at least two reactions, transesterification and other thermally-progressive chemical reactions,
A polyol compound (A) and a transesterification catalyst (B) are essential,
A thermosetting resin composition comprising a composition (X) that causes a reaction other than transesterification, wherein the composition (X) has an alkyl ester group. Composition (X) is a thermosetting resin composition essentially comprising an active hydrogen-containing compound (C), a (meth)acrylate compound (D) and a Michael reaction catalyst (E). 3. The thermosetting resin composition according to claim 2, wherein the active hydrogen-containing compound (C) is an alkyl malonic acid ester and/or an acetoacetic ester. 4. The thermosetting resin composition according to claim 2, wherein the active hydrogen-containing compound (C) has a molecular weight of 3,000 or less. 2. The thermosetting resin composition according to claim 1, wherein the composition (X) essentially comprises an epoxy group-containing compound (F), a carboxylic acid partial ester compound (G), and an acid-epoxy reaction catalyst (H). The thermosetting resin composition according to any one of claims 1 to 5, which has a solid content of 50% by weight or more. A cured film obtained by thermally curing the thermosetting resin composition according to any one of claims 1 to 6.

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