JPH04139255A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermosetting resin composition having excellent storing stability, curing property, resistance to acid and smoothness, containing a cyclic ureidocarbonyl group-containing vinyl polymer, an active hydrogen-containing compound and a ring-opening catalyst for the cyclic ureidocarbonyl group. CONSTITUTION:The objective thermosetting resin composition is composed of (A) A1: a vinyl polymer having at least two cyclic ureidocarbonyl groups [preferably group expressed by the formula ((n) is integer of 2-12)] in a molecule and a compound having at least two active hydrogen groups (preferably OH, COOH and/or NH2) in a molecule in an amount of 100 pts.wt. as total solid components, or A2: 100 pts.wt., as total solid components, of a vinyl polymer having at least two cyclic ureidocarbonyl groups and active hydrogen groups in a molecule and (B) 0.01-10 pts.wt. quaternary ammonium salt (preferably quaternary ammonium fluoride) as a ring-opening catalyst of said cyclic ureidocarbonyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a new and useful thermosetting resin composition. More specifically, it is based on a vinyl polymer having a specific group called a cyclic ureido carbonyl group.
The present invention relates to an extremely useful one-component thermosetting resin composition having excellent storage stability and curability, as well as excellent acid resistance and smoothness.

The thermosetting resin composition of the present invention is used in various fields such as coatings for automobile bodies and metal coatings, as well as adhesives, sealants, and casting resins. .

[Conventional technology]

In recent years, there has been a movement, mainly in the automobile industry, to place more emphasis on the appearance of paint.

However, conventional acrylic polyol/melamine resin-based As far as paints are concerned, it is no longer possible to satisfy these required performances.

In line with this trend, various curing paints such as combinations of isocyanate prepolymers and polyols have been developed and studied, but such isocyanate prepolymers/polyols have short pot lives. (There is a major, almost fatal, flaw in the work.

[Problem to be solved by the invention] Furthermore, in addition to achieving long-term storage stability, the smoothness of the layer can be improved by eliminating volatile components during coating film formation, mainly in the automobile industry. The current situation is that there is a strong demand for the urgent development of a curing system that can improve the performance.

To this end, the inventors of the present invention have undertaken earnest research to eliminate or resolve the various drawbacks or problems in the prior art as described above, and in addition, in order to meet the various demands as described above.

Therefore, the problem to be solved by the present invention is to find a one-component thermosetting resin composition that has good storage stability and excellent curability, and also has good acid resistance and smoothness. An object of the present invention is to provide an extremely useful thermosetting resin composition having excellent properties such as:

[Means to solve the problem]

Therefore, the inventors of the present invention focused on the problems to be solved by the invention as described above, and as a result of repeated studies,
A curing system based on a vinyl polymer having a specific group called a cyclic ureido carboxyl group has excellent storage stability and curing properties, and therefore a one-component thermosetting composition with excellent workability. They further discovered that it has excellent acid resistance and smoothness, and completed the present invention.

That is, the present invention includes a vinyl polymer (A-1) having at least two cyclic ureido carbonyl groups in one molecule, especially a group represented by the formula - as essential components; Compounds having at least two active hydrogen groups, especially hydroxyl, carboxyl and/or amino groups (
B) and the above-mentioned ring-opening catalyst (C) for cyclic ureido carbonyl groups, or a thermosetting resin composition comprising at least two cyclic ureido carbonyl groups in one molecule, especially a ring-opening catalyst (C) for cyclic ureido carbonyl groups; A vinyl polymer (A-2) having both a group represented by the general formula (1) such as the above and at least two active hydrogen groups, especially a hydroxyl group, a carboxyl group and/or an amino group, It is an object of the present invention to provide a thermosetting resin composition comprising the above ring-opening catalyst for a cyclic ureido carbonyl group.

That is, in the thermosetting resin composition of the present invention, the cyclic ureido carbonyl group in the vinyl polymer is ring-opened at a temperature in the range of 80 to 200°C in the presence of a specific catalyst as described below. At the same time, it uses a novel type of base resin as an essential component, which reacts rapidly with active hydrogen groups and thereby provides a strong cured product that is insoluble in organic solvents, and furthermore, the cyclic ureido carbonyl group It also contains a ring-opening catalyst as an essential component, and is particularly capable of providing a cured product with excellent storage stability and curability, as well as excellent acid resistance and smoothness. Therefore, the present invention provides an extremely useful one-component thermosetting resin composition.

Here, the above vinyl polymer having at least two cyclic ureido carbonyl groups in one molecule (A-1
) specifically refers to those having at least two cyclic ureido carbonyl groups in one molecule as shown in the general formula (I) as shown above, and such vinyl polymers (
Particularly typical examples of A-1) include acrylic polymers, vinyl ester polymers, α-olefin polymers, and fluoroolefin polymers.

The vinyl polymer (A-1> is, for example, one α,β-ethylenically unsaturated double bond (hereinafter also referred to as an unsaturated bond) and at least one cyclic ureido carbonyl in one molecule. It may be a polymer of a compound having both groups, a copolymer with other polymerizable monomers, or a copolymer containing an acid chloride group with a cyclic urea added thereto. It may be obtained by adding a cyclic urea to an isocyanate group-containing monomer such as an isocyanate ethyl (meth)acrylate copolymer, or it may be obtained by adding a cyclic urea to an isocyanate group-containing monomer such as an isocyanate ethyl (meth)acrylate copolymer. A diisocyanate compound such as hexamethylene diisocyanate is added to the combination, and further,
It may be obtained by adding a cyclic urea, but in particular, one unsaturated bond and at least one
Copolymerization of a compound having two cyclic ureido carbonyl groups with another polymerizable monomer is recommended because it is simple and convenient.

First, only particularly representative compounds having both one unsaturated bond and at least one cyclic ureido carbonyl group in one molecule are used in preparing the vinyl polymer (A-1). Just to give an example,
- represented by the formula, for example, N-(meth)acryloylethyleneurea, N-(meth)acryloylpropyleneurea,
N-(meth)acryloyltetramethylene urea, N-(
meth)acryloylpentamethylene urea, N-(meth)
Acryloylhexamethyleneurea, N-(meth)acryloylhexamethyleneurea, N-(meth)acryloyloctamethyleneurea, N-(meth)acryloylnonamethyleneurea, N-(meth)acryloyldecamethyleneurea, ) acryloyl undecamethylene urea or N-(meth)acryloyl dodecamethylene urea;
or 2-(ethyleneureidocarbamide)ethyl(meth)acrylate, 2-(propyleneureidocarbamide)ethyl(meth)acrylate, 2-(tetramethyleneureidocarbamide)ethyl/(meth)acrylate, 2-(octamethyleneureidocarbamide) ethyl(
meth)acrylate, 2-(alkyleneureidocarbamide)alkylene(meth)acrylates such as 2-(ethyleneureidocarbamide)propyl(meth)acrylate or 2-(propyleneureidocarbamide)propyl(meth)acrylate; ,
For example, N-(2-vinyloxycarbonylacetyl)ethyleneurea, N-(3-vinyloxycarbonylpropanoyl)propyleneurea, N-(4-
(vinyloxycarbonylbutanoyl) tetramethylene urea, N-(5-vinyloxycarbonylpentanoyl)
Tetramethyleneurea, N-(6-vinyloxycarbonylhexanoyl)offmethyleneurea, N-(7-pinyloxycarbonylhebutanoyl)ethyleneurea, N-
(8-vinyloxycarbonyloctanoyl)propyleneurea, N-(13-vinyloxycarbonyltridecanoyl)tetramethyleneurea, N-(5-vinyloxycarbonylpentanoyl)ethyleneurea or N-(
N-(ω-vinyloxycarbonylalkanoyl)alkyleneurea such as 5-vinyloxycarbonylpentanoyl)propyleneurea, and the like.

The vinyl polymer (A-1) is a homopolymer of the various cyclic ureido carbonyl group-containing vinyl monomers listed above, or a copolymer with other copolymerizable vinyl monomers. Examples of other vinyl monomers that can be copolymerized include (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid. Carboxyl group-containing monomers such as methyl (meth)acrylate, ethyl (meth)acrylate
Acrylate, alkyl (meth)acrylates of 01-C2□ such as butyl (meth)acrylate or stearyl (meth)acrylate; glycidyl (meth)
Various (meth)acrylates containing reactive polar groups such as acryle-I., 2-phosphonooxyethyl (meth)acrylate or N,N-dimethylaminoethyl (meth)acrylate; styrene, p-tert-butylstyrene , aromatic vinyl monomers such as α-methylstyrene or vinyltoluene; (meth)acrylamides such as (meth)acrylamide or N-alkoxymethyl (meth)acrylamide; vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, various haloolefins such as chlorotrifluoroethylene, hexafluoropropylene, vinyl chloride or vinylidene chloride;
α-olefins such as ethylene, propylene, isobutylene or 1-butene; or carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate or vinyl persate; and furthermore, ethyl vinyl ether, n -alkyl or cycloalkyl vinyl ethers such as -butyl vinyl ether, isobutyl vinyl ether or cyclohexyl vinyl ether.

To prepare the vinyl polymer (A-1) using the various monomers listed above, a solution polymerization method, a non-aqueous dispersion polymerization method, an emulsion polymerization method, a suspension polymerization method, or a bulk polymerization method can be used. Any known and commonly used polymerization method can be applied, but solution radical polymerization is particularly recommended because it is simple and convenient.

By making full use of this solution radical polymerization method, the polymer (A-
1) Various hydrocarbons such as toluene, xylene, cyclohexane, n-hexane or octane; methyl acetate,
These include esters such as butyl acetate or amyl acetate; or ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl amyl ketone, or cyclohexanone, and it goes without saying that these may be used alone or in combination of two or more. .

In addition, particularly representative polymerization initiators include azo type represented by azobisisobutyronitrile; or peroxide type represented by benzoyl peroxide, and if necessary, molecule! As regulators, it is also possible to use known and customary chain transfer agents such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid or α-methylstyrene dimer.

The content of the cyclic ureido carbonyl group introduced into the vinyl polymer (A-1) obtained in this way is curable,
From the viewpoint of coating film properties and ease of handling of the polymer (A1), the solid content of the polymer (A-1) is 1.0.
0.01 to 5.3 equivalents per 00g, preferably 0.01 to 5.3 equivalents per 00g.
A range of 1 to 5.3 equivalents is suitable.

In addition, the number average molecular weight of the polymer is 500 to 1
00,000, preferably 800 to 50,000. If it is less than 500, it will be difficult to obtain the desired performance, and on the other hand,
If it is too high (more than 100,000), it will inevitably have a negative effect on workability, so either case is not preferable.

On the other hand, the above-mentioned vinyl polymer (A-2) having at least two cyclic ureido carbonyl groups and active hydrogen groups in one molecule means at least two cyclic ureido carbonyl groups in one molecule, In particular, a specific group represented by the general formula [1] as shown above and at least 2
The vinyl polymer (A-2) is particularly representative of vinyl polymers (A-2), which have at least one active hydrogen group, especially a hydroxyl group, a carboxyl group, and/or a primary or secondary amino group. Examples include acrylic polymers, vinyl ester polymers, α-olefin polymers, and fluoroolefin polymers.

The vinyl polymer (A-2) has one unsaturated bond and at least one cyclic ureido carbonyl group in one molecule, such as the various cyclic ureido carbonyl group-containing vinyl monomers listed above. and an active hydrogen group-containing polymerizable monomer such as hydroxyethyl (meth)acrylate, or by copolymerization with other polymerizable monomers, or It may be obtained by reacting a limited amount of a diisocyanate compound such as hexamethylene diisocyanate with an active hydrogen group-containing polymer such as a hydroxyl group-containing vinyl polymer, and then subjecting it to an addition reaction with a cyclic urea. Preparation by copolymerization is the simplest and recommended.

For preparation by such a copolymerization method, various cyclic ureides such as those represented by the general formula (If) or CI[[) used in the preparation of the vinyl polymer (A-1) described above can be used. A carbonyl group-containing vinyl monomer and an active hydrogen group-containing polymerizable monomer are essential components,
If necessary, other copolymerizable monomers such as those listed above may be used, and the polymerization method described above may be applied.

Typical examples of active hydrogen group-containing polymerizable monomers used in preparing the vinyl polymer (A-2) include 2-hydroxyethyl (meth)acrylate and 4-hydroxyethyl (meth)acrylate. - hydroxyalkyl (meth)acrylates such as hydroxybutyl (meth)acrylate; hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether or 4-hydroxybutyl vinyl ether; or allyl compounds such as allyl alcohol or hydroxyethyl vinyl ether. hydroxyl group-containing monomers, (meth)acrylic acid, crotonic acid, maleic acid, itaconic acid or fumaric acid, as well as monoalkyl esters of unsaturated dibasic acids such as maleic acid, fumaric acid or itaconic acid. Carboxyl group-containing monomers such as N
- Monomers containing primary or secondary amino groups such as methylaminoethyl (meth)acrylate, N-ethylaminoethyl (meth)acrylate, aminoethyl crotonate or N-methylaminoethyl crotonate.

The amounts of the cyclic ureido carbonyl group and active hydrogen group introduced into the vinyl polymer (A-2) are 0.01 to 1,000 g per 1,000 g of solid content of the polymer (A-2). 6.0 equivalents and 0.01 to 6.0 equivalents, preferably 0.1 to 3.5 equivalents and 0.1 to 6.0 equivalents
A range of 3.5 equivalents is appropriate.

In addition, the number average molecular weight of the polymer (A-2) is:
500-100,000, preferably 800-50
．． A value within the range of 000 is appropriate.

Furthermore, the equivalent ratio of the cyclic ureido carbonyl group to the active hydrogen group in the vinyl polymer (A-2) is 1.
:0.2-1:5, preferably 1:0.4-1:2.
A value within the range of 5 is appropriate.

Next, the above-mentioned compound (B) having at least two active hydrogen groups in one molecule includes a hydroxyl group, a carboxyl group,
Active hydrogen groups such as primary amino groups or secondary amino groups,
It refers to low molecular weight compounds or resins having at least two molecules in one molecule.

Particularly representative examples of the compound (B) include low molecular weight polyols such as ethylene glycol, propylene glycol, tetramethylene glycol, 1,6-hexanediol or glycerin; polyester polyols; or hydroxyl group-containing polymers such as hydroxyl group-containing vinyl polymers; low molecular weight polyamines such as ethylene diamine, diethylene triamine, or hexamethylene diamine; polyamide polyamines obtained by reacting dimer acid with polyamines, or primary polymers in the side chains. or high molecular weight polyamines such as vinyl polymers having secondary amine groups; adipic acid;
An ester bond-containing polycarboxylic acid obtained by the addition reaction of cepatic acid, trimellitic acid, or the above-mentioned low molecular weight polyols with a polyhydric carboxylic acid anhydride such as succinic anhydride or trimellitic anhydride. low molecular weight polycarboxylic acids; or carboxyl group-containing resins such as carboxyl group-containing polyester resins or vinyl polymers having carboxyl groups in the side chains; These include polymers and vinyl polymers having both a hydroxyl group and a carboxyl group.

Next, the above-mentioned cyclic ureido carbonyl group and the above-mentioned ring-opening catalyst for the cyclic ureido carbonyl group (C
) refers to a catalyst for efficiently ring-opening a cyclic ureidocarbonyl group, especially a group represented by the above general formula, such as tetramethylammonium salt, tetraethylammonium salt, tetraethylammonium salt, etc. Such as propylammonium salt, tetrabutylammonium salt, trimethyl(2-hydroxypropyl)ammonium salt, tetrakis(hydroxymethyl)ammonium salt, benzyltrimethylammonium salt, cyclohexyltrimethylammonium salt or 0-trifluoromethylphenyltrimethylammonium salt. It is a quaternary ammonium salt and is an important component that can open the cyclic ureido carbonyl group and at the same time expose a reactive polar group that has high reactivity with active hydrogen groups.

Typical examples of counteranions for such quaternary ammonium salts include halogens such as fluoride, chloride, bromide, or iodide; acetate, butyrate, benzoate, dimethylbenzoate, or p-tert-butylbenzoate; or halide oxides or bicarbonates, among which fluoride is preferred.

To prepare the thermosetting resin composition of the present invention from the component (A-1) or (A-2), component (B), and component (C) listed above, respectively, First, (A-1
) component and (B) component, the equivalent ratio of the cyclic ureido carbonyl group in component (A-1) to the active hydrogen group in component (B) is 1:0.2 to 1:5, preferably , 1:0.4~
Blend in a ratio of 1:2.5, and (A-
Component (C) should be blended in a ratio of 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, to a total of 100 parts by weight of the solid content of both components 1) and (B). Bye.

Next, in order to prepare from component (A-2) and component (C), the solid content of component (A-2) is 100 parts by weight or 0.
They may be blended in a proportion of 0.01 to 5 parts by weight.

The amount of the catalyst (C) used greatly influences the crosslinking reaction between the cyclic ureido carbonyl group and the active hydrogen group, and therefore greatly affects the curability.
If the amount is less than 1 part by weight, the crosslinking reaction will not proceed sufficiently, while if it is too much, exceeding 10 parts by weight, the storage stability of the thermosetting resin composition will be extremely reduced. However, since the water resistance of the cured product is also significantly reduced, either case is unfavorable.

It is also effective to use a known and commonly used urethanization catalyst in combination with the quaternary ammonium salt catalyst.

Particularly representative examples of such urethanation catalysts include dibutyltin dioctoate, dibutyltin dilaurate, stannous oleate, and stannous octoate.
Organotin compounds such as tin or their analogues; phosphinic acid; triethylamine, triethylenediamine, 1,
8-diazabicyclo(5,4,0]-7-undecene,
and tertiary organo(di)amines such as 1,5-diazabicyclo[4,3,O)-5-nonene or N-ethylmorpholine or analogs thereof.

The thermosetting resin composition of the present invention thus obtained can be used in any form, such as an organic solvent solution type, an organic solution dispersion type, a solvent-free liquid type, or a solvent-free solid type, depending on the use. .

Further, the composition of the present invention can be used as it is as a clear composition, or can be used as a colored composition with a pigment added thereto.

In addition, leveling agents, ultraviolet absorbers,
Various known and commonly used additives such as combination inhibitors or pigment dispersants may also be incorporated.

〔Example〕

Next, the present invention will be specifically explained using reference examples, examples, comparative examples, applied examples, and comparative applied examples. In the following, all parts and percentages are based on weight unless otherwise specified.

Reference Example 1 [Preparation example of vinyl polymer containing cyclic ureido carbonyl group (A-1)] 500 parts of butyl acetate and 50 parts of styrene were placed in a four-flow flask equipped with a thermometer, a cooling tube, a stirrer, and a nitrogen gas introduction tube. 238 parts of butyl methacrylate, 50 parts of lauryl methacrylate, 162 parts of N-methacryloyloxytetraethylene urea, 15 parts of azobisisobutyronitrile and tert-butyl peroxyoctoate manufactured by Nippon Oil & Fats Corporation. ], the temperature was raised to 80°C, and the temperature was maintained at the same temperature for 15 hours.

Next, add 5 parts of “Perbutyl O” and heat to 1.80°C.
The reaction was continued by holding for 6 hours, and the nonvolatile content was 50.8
%, the Gardner viscosity (hereinafter abbreviated as viscosity) at 25°C is B-C", and the number average molecular weight is 6.0
A solution of target resin No. 40 was obtained.

Hereinafter, this will be abbreviated as resin (A-1-1), and this example is an example of the preparation of a vinyl polymer containing a tetramethylene ureido carbonyl group.

Reference Example 2 (same as above) This example is an example of the preparation of a trimethylene ureido carbonyl group-containing vinyl polymer.

The amount of butyl acetate used was 1,000 parts, and the monomer mixture was changed to use 100 parts of styrene, 501 parts of butyl methacrylate, 100 parts of lauryl methacrylate, and 299 parts of N-methacryloyltrimethylene urea. Other than that, the same procedure as in Reference Example 2 was carried out, and the nonvolatile content was 50.0%, and the number average molecular weight was 11.5%.
A target resin named 00 was obtained.

Hereinafter, this will be abbreviated as resin (A-1-2).

Reference Example 3 (Same as above) This example is an example of the preparation of an octamethylene ureido carbonyl group-containing vinyl polymer.

1,000 parts of butyl acetate, 10 parts of styrene and 376 parts of methyl methacrylate as a monomer mixture.
The procedure was repeated in the same manner as in Reference Example 1, except that 80 parts of lauryl methacrylate and 424 parts of N-methacryloyl octamethylene urea were used.
6% and a number average molecular weight of 12.100 was obtained. Hereinafter, this will be abbreviated as resin (A-1-3).

Reference Example 4 [Preparation example of active hydrogen group-containing compound (B)] This example is an example of the preparation of a hydroxyl group-containing vinyl copolymer.

In a reaction vessel similar to Reference Example 1, 280 parts of xylene, 140 parts of styrene, 772.8 parts of butyl acrylate, 159.6 parts of lauryl methacrylate, 324.8 parts of 2-hydroxyethyl methacrylate, and 8 parts of phosphonoxy 2.8 parts of ethyl methacrylate and 28 parts of azobisisobutyronitrile were charged, the temperature was raised to 110°C, the reaction was carried out at the same temperature for 18 hours, and then xylene was added until the non-volatile content was 39. 7% and the viscosity is F-
A solution of the target resin G was obtained. Hereinafter, this will be abbreviated as active hydrogen group-containing compound (B-1).

Reference example 5 (same as above) This example is an example of the preparation of a hydroxyl group-containing polyester resin.

That is, a mixture consisting of 134 parts of trimethylolpropane, 342 parts of ε-caprolactone, and 1 part of tetraisopropyl titanate was heated to 160 parts under a nitrogen atmosphere.
The reaction was carried out for 10 hours at "C" to obtain a desired resin having a number average molecular weight of 500. Hereinafter, this will be abbreviated as active hydrogen group-containing compound (B-2).

Reference Example 6 [Preparation example of vinyl polymer (A2) having both a cyclic ureido carbonyl group and an active hydrogen group] 1,000 parts of butyl acetate, 100 parts of styrene and butyl methacrylate as a monomer mixture 523
100 parts of lauryl methacrylate, 162 parts of N-methacryloyltetramethylene urea, and 115 parts of 2-hydroxyethyl methacrylate.
Non-volatile content is 50.0% and number average molecular weight is 8.6
A solution of the target resin 00 was obtained. Hereinafter, this resin (A
This example, abbreviated as -2-1), is an example of the preparation of a vinyl copolymer having both a tetramethylene ureido carbonyl group and a hydroxyl group.

Reference Example 7 (same as above) This example is an example of the preparation of a vinyl copolymer having both an octamethylene ureido carbonyl group and a hydroxyl group.

Butyl acetate is 1,000 parts, and the monomer composition is 100 parts of styrene, 472 parts of butyl methacrylate,
In the same manner as in Reference Example 1, except that 10 parts of lauryl methacrylate, 212 parts of N-methacryloyl octamethylene urea and 116 parts of 2-hydroxyethyl methacrylate, and 10 parts of azobisisobutyronitrile, A solution of the target resin with a nonvolatile content of 51.0% and a number average molecular weight of is, ooo was obtained. Hereinafter, this will be abbreviated as resin (A-2-2).

Reference Example 8 [Example of Preparation of Vinyl Polymer (A-1) Containing a Cyclic Ureido Carbonyl Group] This example is an example of the preparation of a fluororesin containing a tetramethylene ureido carbonyl group.

First, in a stainless steel autoclave sufficiently purged with nitrogen, 116 parts of ethyl vinyl ether, 15 parts of "Beoba 9" (vinyl ester of branched fatty acid C1 manufactured by Shell, Netherlands), N-(5-vinyl (oxycarbonylpentanoyl) tetramethylene urea 13
4 parts, 33 parts of methyl ethyl ketone, and 15 parts of 2,2'-azobis(2,4-dimethylvaleronitrile).

Then, 2 of the liquefied and collected chlorotrifluoroethylene
35 parts were press-injected and the reaction was carried out at 60°C for 15 hours with stirring, after which unreacted chlorotrifluoroethylene was purged and the non-volatile content was 58.5% and the number average molecular weight was 14. ,000 of the target resin solution was obtained. Hereinafter, this will be abbreviated as resin (A-1-4).

Examples 1 to 5 Cyclic ureido carbonyl group-containing vinyl polymers (A-1) and (A-2) obtained in Reference Examples 1 to 7, respectively
, an active hydrogen group-containing compound, and a ring-opening catalyst (C) for a cyclic ureido carbonyl group according to the compounding composition ratios shown in Table 1 to prepare various thermosetting resin compositions.

Among them, in the case of Example 4, 2,2-dimethyl 3-
Hydroxypropyl-2,2-dimethyl-3hydroxypropionate [hereinafter referred to as active hydrogen group-containing compound (B-3
). ] were used as low molecular weight diols.

Further, the ring-opening catalyst (C) in the same table is as follows.

(C-1)...Tetrabutylammonium fluoride (C-2)...Tetrabutylammonium acetate (C-3)...Benzyltrimethylammonium fluoride Comparative Examples 1 to 4 As shown in Table 1 Various comparative thermosetting resin compositions were prepared according to the blending composition ratio.

However, in Comparative Example 3, the conventional commercial product "Acridic 52-748J [Dainippon Ink & Chemicals Co., Ltd.]
acrylic resin] and “Super Beckamine L-11
A control acrylic resin/melamine resin mixture was prepared by blending 7-60'' (melamine resin manufactured by the same company) at a solid content weight ratio of 70/30.

In addition, in Comparative Example 4, conventional commercial products ``Acridic A-800J (acrylic polyol manufactured by the same company) and ``Burnock 0N-950J (polyisocyanate manufactured by the same company) were mixed at 100% 30 to prepare a control acrylic polyol/polyisocyanate resin mixture.

Example 6 1,000 of the resin (A-1-4) obtained in Reference Example 8
1,1 of "Fluoride 704J (hydroxyl group-containing fluoroolefin polymer manufactured by Dainippon Ink & Chemicals, non-volatile content = 60%, solid content hydroxyl value = 48)"
A thermosetting resin composition was prepared by mixing 30 parts of the ring-opening catalyst (C-1) with 38 parts of the ring-opening catalyst (C-1).

Hereinafter, this will be abbreviated as a resin composition (RC-6).

Application Examples 1 to 6 and Comparative Application Examples 1 to 4 Each thermosetting resin composition obtained in each Example and Comparative Example was separately applied to a zinc phosphate treated steel plate, and then the results shown in Table 2 were applied. A cured coating film having a thickness of 40 .mu.m was obtained by baking according to the procedure shown, and then various coating film performances were evaluated for the items shown in the same table. The results are summarized in the same table.

[Effects of the Invention] As described above, the thermosetting resin composition of the present invention not only has excellent storage stability and curability, but also has excellent acid resistance and smoothness. It is extremely useful.

Claims (1)

[Claims] 1. A vinyl polymer (A-1) having at least two cyclic ureido carbonyl groups in one molecule, and a compound (B) having at least two active hydrogen groups in one molecule. , a thermosetting resin composition comprising the above-mentioned ring-opening catalyst (C) for a cyclic ureido carbonyl group. 2. Vinyl polymer having at least two cyclic ureido carbonyl groups and active hydrogen groups in one molecule (A-2
) and the ring-opening catalyst for the cyclic ureido carbonyl group described above (
C) A thermosetting resin composition. 3. The above-mentioned cyclic ureido carbonyl group has the general formula ▲ Numerical formula, chemical formula, table, etc. ▼... [I] [However, n in the formula shall be an integer from 2 to 12. ] The composition according to claim 1 or 2, which is represented by the following. 4. The composition according to claim 1 or 2, wherein the active hydrogen group is a hydroxyl group, a carboxyl group, and/or an amino group. 5. Ring-opening catalyst for the cyclic ureido carbonyl group described above (C
4. A composition according to any one of claims 1 to 3, wherein ) is a quaternary ammonium salt. 6. Ring-opening catalyst for the cyclic ureido carbonyl group (C
) is a quaternary ammonium fluoride.
, 2, 3 or 5.