JPH0578551A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To prepare the object compsn. which has an excellent storage stability, gives a coating film excellent in heat resistance, weather resitance, and appearance such as smoothness, and is useful as a high-solid one-component coating compsn. by compounding a specific functional vinyl copolymer and an active ester compd. CONSTITUTION:The objective compsn. contains a vinyl copolymer having at least two 2-oxo-1,3-dioxolan-4-yl groups of formula I (wherein Rl, R2, and R3 are each H or 1-4C alkyl) in the molecule and a compd. having at least two active ester groups in the molecule. An example of the ester compd. is one having an ester group of fomula II (wherein X is a 3-10C alkylene group optionally substd. by 1-10C alkyl, alkoxyl, aryl, or halogen). The compsn. has an excellent storage stability, gives a coating film excellent in heat resistance, weather resistance, and appearance such as smoothness, and is useful as a high-solid one-component coating compsn.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel and useful thermosetting resin composition. More specifically, the present invention provides
A vinyl-based copolymer (A) having a specific reactive group of 2-oxo-1,3-dioxolan-4-yl group and a specific compound (B) having an active ester group, or Alternatively, the copolymer (A) and the compound (B)
And a curing catalyst (C), which is particularly useful as a high solid content one-pack type thermosetting resin composition having excellent storage stability and excellent acid resistance and weather resistance. Resin composition.

The thermosetting resin composition of the present invention is used for paints such as automobile bodies and metal coatings.
Alternatively, it is used in various fields such as adhesives, sealing agents or cast resins.

[0003]

2. Description of the Related Art In recent years, mainly in the automobile industry, there is a strong need for an excellent finished appearance. Moreover, the reduction of the amount of solvent during painting must be promoted from the viewpoint of environmental protection.

[0004] However, the conventional coating used for automobile top coatings, which is composed of a combination of a hydroxyl group-containing acrylic resin and a melamine-based curing agent, has a problem that the appearance thereof deteriorates due to acid rain as it becomes high-solidified.

In view of such problems, development of a new curing type resin has been studied. Among them are 1)
A combination of hydroxyl group-containing resin and polyisocyanate,
2) There is also a system which is a combination of a silanol group-containing resin and an epoxy group-containing resin, or 3) a combination of a hydroxyl group-containing resin and an acid anhydride group-containing resin, and 4) a moisture having a hydrolyzable silyl group. System with curable resin,
And 5) there is a combination of an acid group-containing resin and an epoxy group-containing resin.

However, among the above-mentioned resin systems, the combination of the hydroxyl group-containing resin and the polyisocyanate and the combination of the acid group-containing resin and the epoxy group-containing resin have a short pot life and have major drawbacks in terms of workability. Have and
Further, in the case of a combination of a silanol group-containing resin and an epoxy group-containing resin, or in the case of a hydrolyzable silyl group-containing moisture-curable resin, a change in the degree of crosslinking of the coating film formed by baking with time However, there are various drawbacks such as changes in coating film performance and unsatisfactory appearance.

[0007]

Furthermore, in addition to such long-term storage stability and appearance of the coating film, it is possible to obtain a coating film that can withstand acid rain mainly in the automobile industry. Immediate development of useful curing systems
There is a strong demand.

Therefore, the present inventors have earnestly started research in order to meet the above-mentioned demands. That is, the problem to be solved by the present invention is a high-solids one-pack type coating resin composition having excellent storage stability, and further excellent in coating film appearance such as acid resistance, weather resistance and smoothness. Another object of the present invention is to provide a resin composition for coating which is extremely useful.

[0009]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted intensive studies and studied as a result of focusing on the problems to be solved by the invention as described above, and as a result, 2-oxo-1,3-dioxolane-4 A vinyl-based copolymer (A) having an yl group,
A thermosetting resin composition comprising a compound (B) having a so-called active ester group in a form in which a carboxyl group is blocked with a specific compound, or having a 2-oxo-1,3-dioxolan-4-yl group Vinyl copolymer (A) and compound (B) having this active ester group
By using a thermosetting resin composition composed of a curing catalyst (C) and a curing catalyst (C), the inventors have found that the problems to be solved by the invention described above can be solved satisfactorily. The present invention has been completed.

That is, the present invention has the following essential components:
At least two compounds represented by the general formula [I] in one molecule

[0011]

[Chemical 8]

(However, R1, R2 and R3 in the formula are
Each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different. ) The vinyl copolymer (A) having a 2-oxo-1,3-dioxolan-4-yl group represented by the formula (1) contains a compound (B) having at least two active ester groups in one molecule. An object of the present invention is to provide a thermosetting resin composition,

Alternatively, at least one in one molecule,
A copolymer (A) having a 2-oxo-1,3-dioxolan-4-yl group represented by the above general formula [I] and a compound (B) having two or more active ester groups in one molecule. ) And a curing catalyst (C),
It is intended to provide a thermosetting resin composition.

More specifically, the vinyl copolymer having at least two 2-oxo-1,3-dioxolan-4-yl groups represented by the above-mentioned general formula [I] in one molecule. (A) and the general formula [II], respectively.

[0015]

[Chemical 9]

(However, X in the formula has 1 to 10 carbon atoms.
A carbon atom that may or may not be substituted with at least one atomic group selected from the group consisting of an alkyl group, an alkoxyl group, an aryl group, an alkanoyloxy group, an aryloxy group, an aralkyl group and a halogen atom. It represents an alkylene group having a number of 3 to 10. ), A hemiacetal ester group represented by
Alternatively, the general formula [III]

[0017]

[Chemical 10]

(However, X in the formula has 1 to 10 carbon atoms.
The number of carbon atoms, which may or may not be substituted with at least one atomic group selected from the group consisting of an alkyl group, an alkoxyl group, an aryl group, an alkanoyloxy group, an aryloxy group, an aralkyl group and a halogen atom, Represents an alkylene group consisting of 3 to 10, and R4 may or may not be substituted with an alkyl group having 1 to 18 carbon atoms, or a cycloalkyl group, an aralkyl group or an alkoxyl group,
It represents an alkyl group having 1 to 18 carbon atoms. )
A hemiketal ester group represented by

[0019]

[Chemical 11]

(In the formula, R 5 and R 6 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 5
7 is substituted even if it is substituted with at least one atomic group selected from the group consisting of an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group, an aralkyl group, an aryl group, an alkoxyl group, an alkanoyloxy group, and a halogen atom. It represents an alkyl group having 1 to 22 carbon atoms, which may not be included. ) And / or the general formula [V]

[0021]

[Chemical 12]

(However, R8, R9 and R10 in the formula are
Each of them may have the same or different carbon number of 1 to 1.
20 represents an alkyl group, a phenyl group, an alkyl-substituted phenyl group or a phenylalkyl group. And a compound (B) containing a silyl ester group represented by the formula (1), as an essential component,

Further, the compound (A) having such various forms of the 2-oxo-1,3-dioxolan-4-yl group, and the various forms of the hemiacetal ester group and the hemiketal ester described above. (B) having a group and / or a silyl ester group, and a curing catalyst (C)
The present invention is intended to provide a thermosetting resin composition containing, as an essential component.

At least two 2-
Examples of the vinyl-based copolymer (A) having an oxo-1,3-dioxolan-4-yl group (hereinafter, also referred to as a cyclocarbonate group) include, for example, one polymerizable group in one molecule. Compound (a-1) having both a saturated double bond and at least one 2-oxo-1,3-dioxolan-4-yl group, and another polymerizable compound capable of being copolymerized with the compound (a-1) It may be one obtained by copolymerization with an unsaturated monomer by a conventional method, or a 2-oxo-1,3-dioxolan-4-yl group and a hydroxyl group such as glyceryl carbonate. And a compound (a-
It may be obtained by adding 2) to a vinyl-based copolymer having a functional group capable of reacting with the hydroxyl group.

In particular, a compound (a-1) which combines one polymerizable unsaturated double bond and at least one 2-oxo-1,3-dioxolan-4-yl group in one molecule, A simple method is to obtain a copolymerizable other polymerizable unsaturated monomer (a-2) by copolymerization by a conventional method.

Specific examples of the functional groups capable of reacting with the above-mentioned hydroxyl group include, but are not limited to, an isocyanate group, an acid anhydride group and an acid chloride. At least two 2-oxo-1,3-in one molecule
Used in obtaining the vinyl-based copolymer (A) having a dioxolan-4-yl group, one polymerizable unsaturated double bond and at least one 2-oxo-in one molecule are used.
Examples of the compound (a-1) having a 1,3-dioxolan-4-yl group include, for example, general formula [I-2]

[0027]

[Chemical 13]

(In the formula, R1, R2 and R3 are as described above, R11 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is 1 to 6). And an integer such as a compound represented by the formula).

Specifically, 2,3-carbonate propyl (meth) acrylate, 3,4-carbonate butyl (meth) acrylate, 4,5-carbonate pentyl (meth) acrylate and 6,7-carbonate hexyl (meth) Compounds such as acrylate, 2,3-carbonate propyl vinyl ether or methyl-2,3-carbonate propyl crotonate.

The amount of the compound (a-1) used is appropriately in the range of 1 to 50 parts by weight, preferably 5 to 35 parts by weight. If the amount is less than 1 part by weight, the crosslinking will be insufficient at the time of forming the coating film, and sufficient coating film performance cannot be exhibited. On the other hand, if the amount exceeds 50 parts by weight, a hard and brittle coating film will be obtained. Is also not preferable.

The other polymerizable unsaturated monomer (a-2) copolymerizable with the unsaturated monomer (a-1) having a cyclocarbonate group is not particularly limited. Although not limited, it is recommended to copolymerize with an unsaturated monomer having a hydroxyl group and / or a carboxyl group as a functional group, respectively, because the effect of the present invention can be further enhanced. .

Typical examples of such a hydroxyl group-containing unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate. , Various hydroxyalkyl (meth) acrylates such as 4-hydroxydibutyl (meth) acrylate; 2-hydroxyethyl vinyl ether,
Various hydroxyalkyl vinyl ethers such as 4-hydroxybutyl vinyl ether;

Or, an allyl compound such as allyl alcohol or hydroxyethyl allyl ether; and a hydroxyl group-containing unsaturated monomer in which ε-caprolactone is added to the above-mentioned monomer.

The introduction of a hydroxyl group causes a reaction with a cyclocarbonate group to induce an increase in crosslink density,
Eventually, solvent resistance and weather resistance are improved. Further, a carboxyl group-containing unsaturated monomer can also be used.

Use of such a carboxyl group-containing unsaturated monomer is particularly effective because the compatibility with the carboxyl group- and / or acid anhydride group-containing compound (C) is significantly improved.

As the carboxyl group-containing unsaturated monomer used in the present invention, only representative ones are exemplified, and α, β such as (meth) acrylic acid, maleic acid, fumaric acid or itaconic acid is used. -Unsaturated mono-
Or dicarboxylic acids; or an ester compound of α, β-ethylenically unsaturated dicarboxylic acid such as monoethyl maleate, monobutyl maleate, monobutyl fumarate or monoethyl itaconate and a monohydric alcohol having 1 to 4 carbon atoms Further, a carboxyl group-containing unsaturated form obtained by adding various acid anhydrides such as phthalic anhydride to various hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl (meth) acrylate Such as monomers.

Other copolymerizable vinyl monomers (a
As only -2), only typical ones are listed. Alkyl (meth) acrylate having an alkyl group having 1 to 22 carbon atoms, 2-ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate or ( Various (meth) acrylates containing no reactive functional group such as (meth) acrylonitrile; Various (methyl) glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate or methylglycidyl (meth) acrylate;

In addition to basic nitrogen atom-containing compounds such as (meth) acrylamide or N-alkoxymethylated (meth) acrylamide, phosphoric acid group-containing (meth) acrylate or hydrolyzable silyl group-containing (meth) acrylate. , Various reactive functional group-containing (meth) acrylates;

Alternatively, various aromatic vinyl monomers such as styrene, tert-butylstyrene, α-methylstyrene or vinyltoluene; or various aromatic vinyl monomers such as vinyl fluoride, tetrafluoroethylene or hexafluoropropylene. Such as fluorine-containing vinyl monomers.

The vinyl copolymer (A) may be prepared by a conventional method such as a solution polymerization method or a non-aqueous dispersion polymerization method. Among them, the solution radical method is the most preferable. It's simple.

As the solvents to be used here, only typical ones are exemplified by toluene, xylene, cyclohexane, n-hexane, octane, "Solvesso 100" or "Solvesso 150" (manufactured by Exxon Chemical Co., Ltd.). Aromatic hydrocarbon solvents), various hydrocarbon solvents;

Various ester solvents such as methyl acetate, butyl acetate, amyl acetate, ethyl ethoxy propionate or ethoxy propionate acetate; or various ester solvents such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone or cyclohexanone. Examples of the ketone solvent include, but it goes without saying that these may be used alone or in combination of two or more kinds.

Further, only typical examples of the radical polymerization initiator are azo type initiators such as azobisisobutyronitrile and peroxide type initiators such as benzoylperoxide. And so on.

If necessary, various chain transfer agents such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid or α-methylstyrene dimer may be used as a molecular weight modifier. You can

The vinyl copolymer (A) thus obtained
The number average molecular weight of is within the range of 800 to 50,000, but from the viewpoint of coating film performance or coating workability,
Appropriate.

Next, the active ester group-containing compound (B) blocked with the above-mentioned specific compound means a compound having at least two hemiacetal ester groups, hemiketal ester groups and / or silyl ester groups per molecule. A compound having a group is referred to, and only typical examples of the compound (B) are exemplified. An acrylic polymer, a vinyl ester polymer, an α-olefin polymer, and a fluoroolefin polymer. Examples thereof include a combined or chlorinated olefin-based polymer, a polyester-based or low-molecular polycarboxylic acid ester, and the like.

To prepare the compound (B), for example, vinyl monomers having various hemiacetal ester groups, hemiketal ester groups or silyl ester groups as represented by the above-mentioned general formula are used. Homopolymerization, or a method of copolymerization, or a method of converting the carboxyl group of a carboxyl group-containing compound prepared in advance into a hemiacetal ester group, a hemiketal ester group or a silyl ester group, etc. Can be adopted.

Among them, the vinyl-based monomers having a hemiacetal ester group used in the case of the above method include, for example, a carboxyl group-containing monomer represented by the general formula [VI].

[0049]

[Chemical 14]

(However, Y in the formula is at least one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aryl group, an alkanoyloxy group, an aryloxy group, an aralkyl group and a halogen atom. May be substituted with an atomic group or may not be substituted,
It represents an alkylene group having 2 to 9 carbon atoms, and Z represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aralkyl group or a halogen atom. ) Or a compound of the general formula [VI
I]

[0051]

Embedded image Compounds obtained by subjecting a compound represented by R 5 —CH═CH—OR 6 (wherein R 5 and R 6 are as described above) to an addition reaction. And so on.

As the above-mentioned addition reaction product, that is, as the above-mentioned vinyl monomer containing a hemiacetal ester group, among others, among the compounds which are particularly representative as the compound obtained by the reaction with methacrylic acid, only the examples are shown. Then, 2-methacryloyloxytetrahydrofuran,
2-methacryloyloxy-5-methyltetrahydrofuran, 2-methacryloyloxy-5-phenyltetrahydrofuran, 6,6-chloro, methacryloyloxy-2,3-dihydropyran and the like, carbon of X in the above-mentioned general formula [II]. As the number, 1 to 10 is preferable, and 2 to 6 is preferable.

Next, as the above-mentioned vinyl monomers containing a hemiacetal ester group, among others, an addition reaction product with (meth) acrylic acid, that is, a particularly representative one as a (meth) acrylic acid ester. Only by way of example, 1-ethoxyethyl (meth) acrylate, 1
-Propyloxyethyl (meth) acrylate, 1-butoxyethyl (meth) acrylate, 1- (2-ethylhexyloxy) ethyl (meth) acrylate, 1-lauryloxyethyl (meth) acrylate, 1-cyclohexyloxyethyl (meth) Acrylate, 1-benzyloxyethyl (meth) acrylate, 1- (2-chloroethyloxyethyl)-(meth) acrylate, 1
-Butoxypropyl (meth) acrylate or 1-butoxypentyl (meth) acrylate.

R5 in the above formula [VII] is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. As R6, an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms is suitable.

On the other hand, the hemiketal ester group-containing vinyl monomers represented by the above-mentioned general formula [III] are, for example, those obtained by adding the carboxyl group-containing monomer to the general formula [VII].
I]

[0056]

[Chemical 16]

(Wherein R 4, Y and Z in the formula are all as described above), and is prepared by addition reaction. As such an addition reaction product, that is, as a hemiketal ester group-containing vinyl-based monomer represented by the above-mentioned general formula [III], particularly, a compound obtained by a reaction with (meth) acrylic acid is particularly representative. 1- (meth) acryloyloxy-1-ethyloxycyclopentane, 1- (meth) acryloyloxy-1-butoxycyclopentane, 1- (meth) acryloyloxy-1 -Methoxycyclohexane, 1-
(Meth) acryloyloxy-1-ethoxycyclohexane, 1- (meth) acryloyloxy-1-butoxycyclohexane, 1- (meth) acryloyloxy-1
-C18, such as octyloxycyclooctane
1-alkoxy-1-methacryloyloxycycloalkanes up to

Alternatively, 1- (meth) acryloyloxy-1-ethoxy-3-methylcyclopentane, 1-
(Meth) acryloyloxy-1-methoxy-3-methyl-cyclohexane, 1- (meth) acryloyloxy-1-butoxy-3,6-dichlorocyclooctane, 1
-(Meth) acryloyloxy-1-octyloxy-
So-called substituent-containing 1-alkoxy-1 having a substituent at a position other than 1 such as 4-methoxycyclooctane
-Methacryloyloxycycloalkanes and the like.

The number of carbon atoms of X in the above-mentioned general formula [II] is in the range of 1 to 10, preferably 2 to 6.
Within the range, it is appropriate. On the other hand, the general formula [I
The hemiketal ester group-containing vinyl-based monomers represented by the formula [I] include, for example, carboxyl group-containing monomers represented by the general formula:

[0060]

Embedded image R5—CH═CR12—OR6 (wherein R5, R6 and R12 in the formula are all as defined above), which is prepared by addition reaction Is.

Such addition reaction products, that is, compounds obtained by reaction with (meth) acrylic acid as vinyl monomers containing a hemiketal ester group represented by the above-mentioned general formula [III], As a typical example, only 1- (meth) acryloyloxy-1-methyl-1-propyloxyethane or 1- (meth) acryloyloxy-1-methyl 1-butoxyethane is used. is there.

Next, the silyl ester group-containing vinyl monomer represented by the above general formula [V] is, for example, the general formula [IX]

[0063]

[Chemical 18]

(However, R8, R9 and R10 in the formula are
It represents an alkyl group or an aryl group having 1 to 10 carbon atoms. ) And a carboxyl group-containing unsaturated compound can be prepared by dehydrochlorination reaction.

As the compounds obtained by the reaction with (meth) acrylic acid, only typical ones will be given. Methacryloyloxytrimethylsilane, methacryloyloxytriethylsilane, methacryloyloxytert-butyldimethylsilane, methacryloyloxytriethyl. Examples thereof include silane, methacryloyloxytriphenylsilane and methacryloyloxytripropylsilane.

The various monomers as listed above are the hemiacetal ester group, the hemiketal ester group and // the general formula [II], [III], [IV] or [V], respectively. Or, for preparing silyl ester group-containing vinyl polymers, among the ester group-containing vinyl monomers, only a methacrylic acid derivative, but in addition to these, acrylic acid, Unsaturated monocarboxylic acids such as crotonic acid or carboxylethyl (meth) acrylate;

Monovinyl esters of various saturated dicarboxylic acids such as succinic acid, adipic acid or sebacic acid, maleic acid, fumaric acid or itaconic acid,
Various unsaturated dicarboxylic acids; Half esters of the above-listed unsaturated dicarboxylic acids with monohydric alcohols;

Alternatively, a carboxyl group such as an addition reaction product of a hydroxyl group-containing monomer represented by 2-hydroxyethyl (meth) acrylate with various acid anhydrides such as succinic anhydride or phthalic anhydride. As for the various compounds such as the contained monomers, as described above, [VI], [VII] or [VII], respectively.
[I], various monomers in a form obtained by subjecting various compounds to addition reaction,
Of course, it can be used.

It may be one obtained by copolymerizing the carboxyl group-containing unsaturated monomer with another copolymerizable unsaturated monomer as described above. Examples of the unsaturated monomer capable of copolymerizing with the unsaturated monomer containing a carboxyl group include other unsaturated monomers capable of copolymerizing with the unsaturated monomer containing a cyclocarbonate group (a-1) described above. What was illustrated as a saturated monomer (a-2) can be used.

Similarly, vinyl copolymers containing a hemiacetal ester group, a hemiketal ester group and / or a silyl ester group can also be used in combination with the monomers containing the above groups and the unsaturated compounds containing the cyclocarbonate groups described above. Similar unsaturated monomers that can be copolymerized with the monomers can be used.

Next, other than the vinyl-based copolymer used as the active ester group-containing compound, there is a carboxyl group-containing polyester resin.
The carboxyl group-containing polyester resin refers to those obtained by reacting an acid component in excess with polyvalent alcohol, or those obtained by reacting a hydroxyl group-containing polyester resin with an acid anhydride compound. To do.

Compounds containing a hemiacetal ester group, a hemiketal ester group and / or a silyl ester group can be prepared by using the above-mentioned general formulas [VI], [VII] and [VII].
I] and / or [IX] addition reaction.

Specific examples of the polyester resin include phthalic acid, hexahydrophthalic acid, isophthalic acid,
Various polyvalent carboxylic acids typified by adipic acid, maleic acid or dimer acid, and various polyhydric alcohols such as ethylene glycol, propylene glycol, neopentyl glycol or trimethylolpropane. −
Can be obtained by condensation with a known method.

Further, it is obtained by adding various acid anhydride group-containing compounds such as trimellitic acid to the hydroxyl group in the polyester resin, and the reaction is carried out under the condition that polyvalent carboxylic acid becomes excessive. Can also be obtained.

Next, a low molecular compound containing a hemiacetal ester group, a hemiketal ester group and / or a silyl ester group can also be used. Examples of the carboxyl group-containing low molecular weight compound as a precursor thereof include adipic acid, phthalic acid, isophthalic acid, dimer acid, etc., but two or more carboxyl groups are contained in one molecule. The compound is not particularly limited as long as it is a compound.

The addition reaction can be obtained in exactly the same manner as described above. Further, the curing catalyst (C) will be described. The catalyst (C) is an important component for the decarbonation reaction from the cyclocarbonate group, but only representative ones will be exemplified. If it stays, tetramethylammonium fluoride, trimethylbenzylammonium hydroxide, 2
Various quaternary ammonium salts such as hydroxypyridine or trimethylbenzylammonium methoxide; acid catalysts such as phosphoric acid, p-toluenesulfonic acid or dimethylsulfate; or carbonates such as calcium carbonate.

The amount of the cyclocarbonate group-decomposing catalyst used is the above-mentioned vinyl copolymer (A).
In the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the solid content of the above is suitable.

When the amount used is less than 0.01 parts by weight during baking for about 20 minutes in the temperature range of 120 to 160 ° C., the crosslinking reaction cannot proceed sufficiently, while 5 parts by weight is required. If it exceeds the range, problems occur in the storage stability of the coating material and the water resistance of the cured coating film deteriorates.

Further, a hemiacetal ester group,
Only representative ones acting as a catalyst for deprotecting a hemiketal ester group or a silyl ester group are given as examples, and methanesulfonic acid, propanesulfonic acid, toluenesulfonic acid, naphthalenedisulfonic acid, and trifluene are given. Various organic sulfonic acids such as foromethanesulfonic acid or trichloromethanesulfonic acid, various organic phosphoric acids such as methylphosphoric acid, isopropylphosphoric acid or diisopropylphosphoric acid and their esters; 1,8-diazabicyclo [5.4. 0] Undecen-7 (DBU), 1,5-
Various organic tertiary amines such as diazabicyclo [4.3.0] nonene-5 (DBN) or 1,4-diazabicyclo [2.2.2] octane (DABCO);

Various metal carboxylic acids such as acetic acid, butyric acid, 2,2-dimethylpentanoic acid or benzoic acid, various metal carboxylic acids such as tin octylate, magnesium naphthenate, zinc octylate or calcium octylate; Imidazole, N-methylimidazole, 1,2-
Various imidazoles, such as dimethyl-imidazole or 2,4-dimethylimidazole;

Various salts obtained from each of the above acids;
Various types such as tetramethylammonium salt, tetraethylammonium salt, trimethyl (2-hydroxypropyl) ammonium salt, tetrabutylammonium salt, tetrakis (hydroxymethyl) ammonium salt, cyclohexyltrimethylammonium salt or O-trifluoromethylphenyltrimethylammonium salt. Quaternary ammonium salts of

Alternatively, a tetramethylphosphonium salt,
Tetraethylphosphonium salt, tetrapropylphosphonium salt, tetrabutylphosphonium salt, trimethyl (2
Various phosphonium salts such as -hydroxypropyl) phosphonium salt, triphenylammonium salt or benzyltriphenylphosphonium salt.

Next, it can also be used to accelerate the reaction between the epoxy group and the carboxyl group, and as such a component, in order to accelerate the esterification reaction, it is usually used.
Preference is given to using the basic catalyst used.

As the basic catalyst, the above-mentioned quaternary ammonium salt, quaternary phosphonium salt and the like, and further, the tertiary organic phosphorus compound typified by triphenylphosphine and the like are particularly representative.

When the amount of the component (C) used exceeds 30 mmol (0.03 mol) and becomes too large, the storage stability of the thermosetting resin composition is inevitably lowered. Moreover, the water resistance of the cured product is significantly reduced, which is not preferable.

The thus obtained thermosetting resin composition of the present invention contains the presence or absence of the curing catalyst (C) component, the vinyl copolymer (A) and the active ester group-containing (B) component. 100 to 100 depending on the content of the reactive functional group.
By baking at a temperature range of about 250 ° C. for about 30 seconds to 1 hour, it is possible to provide a sufficiently cured cured coating film having excellent acid resistance and the like.

If desired, the resin composition for laminated coatings of the present invention thus obtained may also contain various known and conventional additives such as a leveling agent and an ultraviolet absorber.

The thermosetting resin composition of the present invention may also be an organic solvent solution type, an organic solvent dispersion type, a solventless liquid type or a solventless solid type, or a powder type (powder type) depending on its application. It can be used in any form such as body).

Further, the thermosetting resin composition of the present invention comprises
It can be used as it is as a clear composition, and can be further used as a coloring composition, especially an enamel composition in the form of being mixed with a pigment.

[0090]

EXAMPLES Next, the present invention will be explained more concretely by reference examples, examples and comparative examples. In the following, all parts and% are based on weight unless otherwise specified.

Reference Example 1 [Preparation Example of Cyclocarbonate Group-Containing Vinyl Copolymer (A)] In a four-necked flask equipped with a thermometer, a cooling tube, a stirrer and a nitrogen gas introducing tube, 500 parts of xylene and n were added. -Preparing 300 parts of butanol and heating to 120 ° C, 300 parts of 2,3-carbonate propyl methacrylate, 200 parts of methyl methacrylate, 200 parts of styrene and 300 parts of n-butyl methacrylate.
And xylene, 200 parts of xylene, 10 parts of azobisisobutyronitrile (AIBN) and tert.
-Butylperoxy-2-ethylhexanoate 20
Part of the mixture was added dropwise at the same temperature over 5 hours, and after the completion of the addition, the mixture was kept at the same temperature for 7 hours to cause a reaction, the nonvolatile content was 50.4%, and the Gardner viscosity at 25 ° C. (hereinafter, A resin solution having a viscosity of 1) and a number average molecular weight of 11,000 was obtained. Hereinafter, this is abbreviated as resin (A-1).

Reference Example 2 (Preparation Example of Vinyl Copolymer Containing Cyclocarbonate Group and Hemiacetal Ester Group) As a monomer mixture, 250 parts of 2,3-carbonate butyl acrylate, 150 parts of styrene, and isobutyl methacrylate were used. Of 75 parts, 150 parts of 2-ethylhexyl methacrylate, 50 parts of 2,3-carbonate propyl acrylate and 325 parts of 1-ethoxyethyl methacrylate were used in the same manner as in Reference Example 1 except that a mixture was used. , Nonvolatile content 50.6
%, And a resin having a viscosity of Q was obtained. Hereinafter, this is abbreviated as resin (A-2).

Reference Example 3 (Preparation Example of Vinyl Copolymer Containing Cyclocarbonate Group and Silyl Ester Group) As monomers for copolymerization, 249 parts of 2,3-carbonate propyl methacrylate, 89 parts of styrene and trimethyl were used. Nonvolatile matter was 49.8% and viscosity was H in the same manner as in Reference Example 1 except that 200 parts of methacryloyloxysilane, 150 parts of n-butyl methacrylate and 312 parts of n-butyl acrylate were used. A solution of the target polymer was obtained. Hereinafter, this is abbreviated as resin (A-3).

Reference Example 4 (Preparation Example of Cyclocarbonate Group-Containing Vinyl Copolymer) As a monomer mixture, 321 parts of 4,5-carbonate pentyl methacrylate, 150 parts of styrene, 250 parts of 2-ethylhexyl methacrylate, A resin solution having a nonvolatile content of 50.1% and a viscosity of F was obtained in the same manner as in Reference Example 1 except that 279 parts of butyl acrylate was used. Hereinafter, this is a resin (A-
4) is abbreviated.

Reference Example 5 [Preparation example of vinyl copolymer containing hemiketal ester group] As a monomer mixture, 328 parts of 1,1-methoxy-methacryloyloxycyclobutane, 300 parts of styrene and n-butyl methacrylate were used. 372 parts were used as the initiator, 15 parts of AIBN and ter, respectively.
A solution of a resin having a nonvolatile content of 50.2% and a viscosity of O was obtained in the same manner as in Reference Example 1 except that 70 parts of t-butylper-2-ethylhexanoate was used. . Hereinafter, this is abbreviated as resin (B-1).

Reference Example 6 [Preparation example of silyl ester group-containing polyester resin (B)] 500 parts of "Placcel 308" (caprolactone polymerized polyol manufactured by Daicel Chemical Industries, Ltd.) and 87 parts of phthalic anhydride were further added. After charging 100 parts of xylene and 50 parts of butyl acetate, the reaction was carried out at 120 ° C. for 2 hours to obtain a resin solution having a nonvolatile content of 80% and a viscosity of Q.

Then, to 1,000 parts of this resin solution, 66 parts of trimethylchlorosilane and 64 parts of triethylamine were added, the reaction was carried out while cooling, and the reaction product was filtered to obtain the desired resin. A solution was obtained. Hereinafter, this is abbreviated as resin (B-2).

Reference Example 7 (Preparation Example of Vinyl Copolymer Containing Cyclocarbonate Group and Carboxyl Group) 178 parts of methacrylic acid was used instead of 325 parts of 1-ethoxyethyl methacrylate, and xylene 500 initially charged. The same operation as in Reference Example 2 was performed except that 353 parts of xylene was charged instead of the parts.
A resin solution having a nonvolatile content of 50.5% and a viscosity of Y was obtained. Hereinafter, this is abbreviated as a resin solution (A'-1).

Examples 1 to 5 Using the respective resins obtained in Reference Examples 1 to 7,
The resin composition of the present invention was obtained according to the composition ratio shown in the table.

Furthermore, a cured coating film was prepared using these various resin compositions, and various performances and various performances were compared and examined. The results are summarized in Table 2.

[0101]

[Table 1]

[Footnote of Table 1 (1)] Curing catalyst (C-1) ... Trifluoromethanesulfonic acid curing catalyst (C-2) ... Di-n-butyltin dilaurate curing catalyst (C-3) ……… Trimethylbenzylammonium hydroxide

[0103]

[Table 2]

[Footnote in Table 1 (2)] Comparative contrast paint: Acrylic resin / melamine resin paint is "Acridic 52-748" [hydroxyl group-containing acrylic manufactured by Dainippon Ink and Chemicals, Inc.] Resin] and "Super Beckamine L-117-60"
(Butyl etherified melamine resin manufactured by the same company), and
Compounded at a ratio of 0:30 (solid content weight ratio) L-117-60 ... "Super Beckamine L-1
17-60 "abbreviation

[0105]

[Table 3]

[0106]

[Table 4]

[Footnotes in Table 2] Storage stability ……………… Stability immediately after preparation of the resin composition (paint) (that is, initial stability) and after storage at 50 ° C. for 1 month. The values in the table represent the "seconds" of the Ford Cup # 4 Gloss ………………………… 60 degree specular reflectance (%) Impact resistance Sex …………………… 1/2 inch with notch; 5
00g / cm Xylene rubbing …… Evaluation when rubbing is 10 times Acid resistance ………………………………………………………………………………………………………………………………………………………… ………… By immersing it in a 5% sodium hydroxide solution at room temperature and visually observing the coated surface condition. Weather resistance ……………………
Accelerated weathering test for 000 hours

[0108]

As described in detail above, the thermosetting resin composition of the present invention comprises a vinyl carbonate containing a cyclocarbonate group, a hemiacetal ester group and a hemiketal ester group, respectively, as active ingredients. And / or a compound having a specific structure, which is protected by a silyl ester group, and thus has excellent storage stability, excellent solubility, and high coating nonvolatile content. It is extremely useful because it gives a coating film having excellent solvent resistance and the like.

Therefore, the thermosetting resin composition of the present invention is widely used as a coating material for automobile bodies, metal coatings, etc., or in various application fields such as adhesives, sealing agents or casting resins. It is used.

Claims (4)

[Claims] 1. At least two compounds of the general formula [I] in one molecule: (However, R1, R2, and R3 in the formula are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) 2- It is characterized by containing a vinyl-based copolymer (A) having an oxo-1,3-dioxolan-4-yl group and a compound (B) having at least two active ester groups in one molecule. , A thermosetting resin composition. 2. At least one compound of the general formula [I] (However, R1, R2, and R3 in the formula are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) 2- Containing a copolymer (A) having an oxo-1,3-dioxolan-4-yl group, a compound (B) having two or more active ester groups in one molecule, and a curing catalyst (C). A thermosetting resin composition characterized by the above. 3. At least two compounds represented by the general formula [I]: (However, R1, R2, and R3 in the formula are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) 2- The thermosetting resin composition according to claim 1 or 2, wherein the vinyl copolymer (A) having an oxo-1,3-dioxolan-4-yl group also has an active ester group. 4. The above-mentioned active ester group is represented by the general formula [I
I] (However, X in the formula is at least one atomic group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aryl group, an alkanoyloxy group, an aryloxy group, an aralkyl group, and a halogen atom. With 3 carbon atoms, which may or may not be substituted with
It represents an alkylene group consisting of 10 to 10. ), The general formula [III] (However, X in the formula is at least one atomic group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aryl group, an alkanoyloxy group, an aryloxy group, an aralkyl group, and a halogen atom. Represents an alkylene group having 3 to 10 carbon atoms, which is very good even if it is substituted with
Is optionally substituted with an alkyl group having 1 to 18 carbon atoms, or a cycloalkyl group, an aralkyl group or an alkoxyl group, having 1 to 1 carbon atoms
8 represents an alkyl group. ) Or the general formula [IV] (However, R5 and R6 in the formula, which may be the same or different, each have a hydrogen atom or a carbon number of 1-10.
And R7 is at least selected from the group consisting of an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group, an aralkyl group, an aryl group, an alkoxyl group, an alkanoyloxy group, and a halogen atom. It represents an alkyl group having 1 to 22 carbon atoms, which may or may not be substituted with one kind of atomic group. ) Having the structure shown in, or
General formula [V] (However, R8, R9 and R10 in the formula may represent the same or different alkyl groups each having 1 to 20 carbon atoms, or a phenyl group, an alkyl-substituted phenyl group or a phenylalkyl group. The thermosetting resin composition according to claim 1, which has a structure represented by the formula (1).