JPH04325538A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To provide a very useful thermosetting resin composition which is used as a composition suited for a coating material, an adhesive or a sealant and can give a cured product improved in resistance to thermal yellowing and water resistance. CONSTITUTION:A thermosetting resin composition essentially consisting of a polymer prepared from a monomer represented by 4- methacryloyloxymethyl-1,3-dioxolan-2-one and having at least two 1,3-dioxolan-2- on-4-yl groups in the molecule and a quat. hydroxyalkyl ammonium salt. A cured product improved in resistance to thermal yellowing and water resistance without detriment to acid resistance can be obtained by using the above ammonium salt as a curing catalyst.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to a new and useful thermosetting resin composition. More specifically, 1,3-
A thermosetting product that forms a cured product that contains a dioxolan-2-one-4-yl group-containing polymer and a specific quaternary ammonium salt as essential components, and has particularly excellent resistance to heat yellowing and water resistance. The present invention relates to a synthetic resin composition.

The composition of the present invention has extremely high utility value in various applications such as paints, adhesives, and sealants.

0003

BACKGROUND OF THE INVENTION Conventionally, compositions comprising a hydroxyl group-containing polymer and an amino resin have been used as thermosetting resin compositions for top coating of automobiles.

[0004] However, the cured coating film obtained from such a composition has insufficient acid resistance, and the surface is easily attacked by acid rain accompanying the progress of environmental pollution in recent years. Therefore, the development of new compositions is desired.

In order to solve these problems, the present inventors conducted various studies and found that a polymer containing a 1,3-dioxolan-2-one-4-yl group and a curing catalyst, We have previously filed a patent application based on the discovery that a new composition comprising the essential ingredients provides a cured coating film with particularly excellent acid resistance. (Patent application Hei 2-255304
However, with such new compositions, the heat yellowing resistance of the cured coating film is insufficient, resulting in discoloration due to overbaking, and when a two-coat, one-bake metallic coating film is immersed in boiling water for a long time. It was found that there were problems such as discoloration of the metallic base coat.

[0006]

[Problems to be Solved by the Invention] Therefore, in view of the above-mentioned drawbacks, the present inventors have attempted to obtain a composition that forms a cured coating film that is excellent in heat yellowing resistance and water resistance. With this goal in mind, I began research.

[0007] Therefore, the problem to be solved by the present invention is to provide an extremely useful composition that can form a cured coating film that is not only resistant to acid but also has excellent resistance to heat yellowing and water resistance. It is to obtain.

[0008]

[Means for Solving the Problem] As a result, the present inventors used a polymer having a specific group called 1,3-dioxolan-2-one-4-yl group as a reactive functional group, while By using a quaternary ammonium salt having a specific group called a hydroxyalkyl group as a curing catalyst, a cured coating film with excellent resistance to heat yellowing and water resistance as a 2-coat, 1-bake metallic coating film can be obtained. This discovery led to the completion of the present invention.

That is, the present invention provides that one molecule contains the general formula [I]

0010

[Chemical formula 3]

(However, R1, R2 and R in the formula
3 each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different. ) 1,3-dioxolane-2-
Polymer (A) having at least two on-4-yl groups
and a quaternary ammonium salt (B) having a hydroxyalkyl group as essential components, or

A polymer (A) having at least two 1,3-dioxolan-2-one-4-yl groups represented by the above-mentioned general formula [I] in one molecule, and a hydroxyalkyl group. A quaternary ammonium salt (B) having
A thermosetting compound comprising a compound (C) having a functional group that reacts with a hydroxyl group and/or a 1,3-dioxolan-2-one-4-yl group, which has improved heat yellowing resistance and water resistance, among others. The present invention aims to provide a resin composition.

The configuration of the present invention will be explained in detail below. First, specific examples of the above-mentioned polymer (A) having at least two 1,3-dioxolan-2-one-4-yl groups, which is the base resin component in the present invention, are as follows. Typical examples include vinyl polymers, polyester resins, alkyd resins, polyurethane resins, polyether resins, and polyamide resins having reactive functional groups. Among these, it is particularly desirable to use vinyl polymers, polyester resins and/or alkyd resins.

[0014] Among the vinyl polymers mentioned above, particularly representative ones include acrylic polymers, vinyl ester polymers, α-olefin polymers, and fluoroolefin polymers. It will be done.

1,3 introduced into the polymer (A)
Typical examples of the -dioxolan-2-one-4-yl group include 1,3-dioxolan-2-one-4-yl group, 4-methyl-1,3-dioxolan-2-one-4
-yl group, 5-methyl-1,3-dioxolan-2-one-4-yl group, 4,5-dimethyl-1,3-dioxolan-2-one-4-yl group, 4,5,5- Trimethyl-1,3-dioxolan-2-one-4-yl group, 4-
Ethyl-1,3-dioxolan-2-one-4-yl group or 5-ethyl-1,3-dioxolan-2-one-
Examples include 4-yl group,

4-n-propyl-1,3-dioxolan-2-one-4-yl group, 5-n-propyl-1,3-
Dioxolan-2-one-4-yl group, 4-n-butyl-1,3-dioxolan-2-one-4-yl group, 5-
Examples include n-butyl-1,3-dioxolan-2-one-4-yl group and 4,5-di-n-butyl-1,3-dioxolan-2-one-4-yl group.

Such 1,3-dioxolan-2-one-
To prepare a 4-yl group-containing vinyl polymer,

00
18] ■ Homopolymerizing a vinyl monomer having a 1,3-dioxolan-2-one-4-yl group, or copolymerizing it with another monomer that can be copolymerized with it.

■ A pre-prepared carboxylic anhydride group-containing vinyl polymer is added with a hydroxyl group and 1,3-dioxolan-2-one-4-yl, such as 4-hydroxymethyl-1,3-dioxolan-2-one. Reacting a compound that also has a group, or

■Various methods such as reacting a pre-prepared isocyanate group-containing vinyl polymer with a compound having both a hydroxyl group and a 1,3-dioxolan-2-one-4-yl group as described above. Among these methods, method (2) is the simplest.

[0021] Here, 1,3-dioxolan-2-one-4- used in the preparation by method (2)
To exemplify only particularly representative vinyl monomers containing a yl group, 4-(meth)acryloyloxymethyl-1,3-dioxolan-2-one, 4-methyl-4-(meth) ) Acryloyloxymethyl-1,3-dioxolan-2-one, 4-(meth)acryloyloxymethyl-4,5-dimethyl-1,3-dioxolan-
2-one, 4-ethyl-4-(meth)acryloyloxymethyl-1,3-dioxolan-2-one,
Furthermore,

4-n-propyl-4-(meth)acryloyloxymethyl-1,3-dioxolan-2-one,
4-n-Butyl-4-(meth)acryloyloxymethyl-1,3-dioxolan-2-one, 4-[2-(meth)acryloyloxyethoxymethyl]-1,3-dioxolan-2-one, 4 - (meth)acrylic acid ester monomers such as methyl-4-[2-(meth)acryloyloxyethoxymethyl]-1,3-dioxolan-2-one;

4-Crotonoyloxymethyl-1,3-
Crotonic acid ester monomers such as dioxiran-2-one, 4-methyl-4-crotonoyloxymethyl-1,3-dioxiran-2-one; monovinyl mono-(1
, 3-dioxolan-2-one-4ylmethyl)succinate, monovinyl mono-(1,3-dioxolan-2
vinyl ester monomers such as -one-4ylmethyl)adipate;

or 4-vinyloxymethyl-1,3-
These include vinyl ether monomers such as dioxolan-2-one and 4-methyl-4-vinyloxymethyl-1,3-dioxolan-2-one.

Such 1,3-dioxolan-2-one-
From the 4-yl group-containing vinyl monomer, the polymer (A)
In order to obtain a copolymer, a copolymer of only monomers as described above may be used, but from the viewpoint of the solubility of the polymer in solvents and the flexibility of the cured coating film, copolymers that are copolymerizable may be used. Particularly desirable are copolymers with other monomers.

Other copolymerizable monomers that can be used in this case include methyl (meth)acrylate, ethyl (meth)acrylate, and ethyl (meth)acrylate.
C such as acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate
1 to C22 alkyl (meth)acrylates,

Cycloalkyl (meth)acrylates such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate;

Aralkyl (meth)acrylates such as benzyl (meth)acrylate and phenethyl (meth)acrylate; crotonic acid esters of methyl crotonate, ethyl crotonate, and n-butyl crotonate;

[
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl pivalate, and vinyl versatate; dimethyl maleate, dibutyl maleate, dimethyl fumarate, dibutyl fumarate, dimethyl itaconate, Dialkyl esters of unsaturated dibasic acids such as dibutyl itaconate;

003
0] Aromatic vinyl monomers such as styrene, p-tert-butylstyrene, α-methylstyrene, vinyltoluene; methyl vinyl ether, ethyl vinyl ether,
Alkyl or cycloalkyl vinyl ethers such as isobutyl vinyl ether and cyclohexyl vinyl ether; α- such as ethylene, propylene, and 1-butene;
Olefins; fluoroolefins such as tetrafluoroethylene, vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene;

[0031]2
- Hydroxyl groups such as hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethoxy allyl ether, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether Monomers having;

Monomers having a carboxyl group such as acrylic acid, methacrylic acid, crotonic acid, monovinyl adipate, monobutyl maleate, monobutyl fumarate, monobutyl itaconate, maleic acid, fumaric acid, itaconic acid; Monomers having a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride;

Monomers having epoxy groups such as glycidyl (meth)acrylate, glycidyl vinyl ether, allylglycidyl ether; 2-trimethylsilyloxyethyl (meth)acrylate, 2-trimethylsilyloxypropyl (meth)acrylate, 4-trimethylsilyloxy Monomers having a silyloxyalkyl group such as butyl (meth)acrylate and 4-trimethylsilyloxybutyl vinyl ether;

N-methylol (meth)acrylamide,
Monomers having a hydroxymethylamino group such as N-methylolcrotonamide; monomers having an N-alkoxymethylamino group such as N-methoxymethyl (meth)acrylamide and N-butoxymethyl (meth)acrylamide ;

Monomers having an isocyanate group such as isocyanatoethyl (meth)acrylate and 2-isopropenyl-α,α-dimethylbenzyl isocyanate; monomers having a cyano group such as (meth)acrylonitrile and crotononitrile; mer; (meth)acrylamide,
Monomers having an amide group such as crotonic acid amide;

Alternatively, monomers having a tertiary amino group such as N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate can be used.

Among such copolymerizable monomers, monomers having specific reactive functional groups such as hydroxyl group, silyloxyalkyl group, carboxyl group, carboxylic acid anhydride group or epoxy group are particularly preferred. It is a particularly effective means to use these functional groups as copolymerization components and introduce these functional groups into the polymer (A), since it is possible to improve curability, crosslinking density, etc.

From the various monomers listed above, 1,3
- In order to obtain a vinyl polymer (A) having a dioxolan-2-one-4-yl group, a 1,3-dioxolan-2-one-4-yl group is introduced into the polymer (A). The amount is per 1000 grams of solid content of the polymer (A),
0.05 to 3.5 mol, more preferably 0.25 to 3.5 mol
This 1,3-dioxolan-2-one-4-yl group-containing monomer may be copolymerized so that the amount is within the range of 2.5 moles.

If the amount of 1,3-dioxolan-2-one-4-yl group introduced is less than 0.05 mol, the curability will be poor, while if it exceeds 3.5 mol, the cured coating will deteriorate. Either case is undesirable because it becomes brittle.

As mentioned above, when various specific functional groups such as hydroxyl group, silyloxyalkyl group, carboxylic acid anhydride group or epoxy group are introduced into the vinyl polymer (A), the functional group Although it varies depending on the type, the amount of these functional groups introduced is generally less than 6 mol, more preferably less than 4 mol, per 1,000 grams of solid content of the polymer (A). , monomers having these functional groups may be copolymerized.

[0041] When introducing such a reactive functional group,
Although only one type of functional group may be introduced, or two or more types may be introduced simultaneously, a hydroxyl group and a carboxylic acid anhydride group, or a carboxyl group and an epoxy group,
At the same time, when introducing the vinyl polymer (A), gelation may occur during the preparation of the vinyl polymer (A), or the polymer (A) may
This should be avoided as it will impair the stability of the system.

Using various monomers as listed above,
To prepare the vinyl polymer (A), any known and commonly used polymerization method such as solution polymerization method or non-aqueous dispersion polymerization method can be applied, but solution radical polymerization method is the simplest method. It is.

Typical examples of solvents used here include hydrocarbon solvents such as toluene, xylene, cyclohexane, n-hexane, and octane;

Ester solvents such as methyl acetate, n-butyl acetate or amyl acetate; or ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone or cyclohexanone; More than one species may be used in combination.

[0045] In addition, particularly representative radical polymerization initiators include known and commonly used initiators such as azo type represented by azobisisobutyronitrile; or peroxide type represented by benzoyl peroxide. belongs to.

Furthermore, if necessary, lauryl mercaptan, octyl mercaptan, 2
-Mercaptoethanol, octyl thioglycolate,
Various known and commonly used chain transfer agents such as 3-mercaptopropionic acid or α-methylstyrene dimer can also be used.

The number average molecular weight of the vinyl polymer thus obtained is suitably within the range of 800 to 50,000, more preferably within the range of 1,500 to 50,000.

[0048] If it is less than 800, by all means,
It becomes difficult to obtain products with the desired performance, and on the other hand,
If it exceeds 50,000, it will inevitably have an adverse effect on workability, so either case is not preferable.

Next, 1,3-dioxolan-2-one-
To prepare polyester resins or alkyd resins having 4-yl groups,

■ 1,3-dioxolane-2 is added to the polyester resin or alkyd resin having isocyanate groups.
Reacting a compound having both an -one-4-yl group and a hydroxyl group, etc.

■ 1,3-dioxolane-2- to the polyester resin or alkyd resin having an acid chloride group
Reacting a compound that has both an on-4-yl group and a hydroxyl group, etc.

■ 1,3-dioxolane-2 is added to the polyester resin or alkyd resin having a carboxylic acid anhydride group.
Reacting a compound having both an -one-4-yl group and a hydroxyl group, etc.

■ Polyester resin or alkyd resin having hydroxyl group and/or carboxyl group, 1,3
-Reacting a compound having both a dioxolan-2-one-4-yl group and an isocyanate group, or,

■ A monomer containing a 1,3-dioxolan-2-one-4-yl group is added to the polyester resin or alkyd resin via a double bond in these resins, or the monomer is contained therein. Various methods can be applied, such as graft polymerization of monomer mixtures.

When preparing these polyester resins or alkyd resins (A) by the various methods listed above, known and commonly used methods can be applied using known and commonly used alcohol components, acid components and oil components. can.

[0056] The polyester resin or alkyd resin is then subjected to the various modifications described above to obtain 1,3
-Dioxolan-2-one-4-yl group-containing various polyester resins or alkyd resins (A) can be obtained.

The amount of 1,3-dioxolan-2-one-4-yl groups introduced into the polyester resin or alkyd resin (A) thus obtained is 0.000 g per 1,000 g of solid content of the resin. 1 to 4 moles, and even
It is preferably within the range of 0.5 to 3 moles.

If it is less than 0.1 mol, the curability will inevitably be poor, and if it exceeds 4 mol, the coating will be hard and brittle, which is not preferable. Next, the compound (C) having a functional group that reacts with the aforementioned hydroxyl group and/or 1,3-dioxolan-2-one-4-yl group, which is used as a component of the composition of the present invention, will be described.

A functional group that is reactive with the hydroxyl group and/or 1,3-dioxolan-2-one-4-yl group introduced into the compound (C), that is, a reactive group introduced into the compound (C). Specific examples of the functional group include carboxyl group, carboxylic anhydride group, hydroxymethylamino group, alkoxymethylamino group, hydroxyl group, silyloxyalkyl group, isocyanate group, blocked isocyanate group, and epoxy group. , is particularly representative.

[0060] The compound (C) preferably has at least two such functional groups in one molecule. Particularly typical examples of the compound (C) include vinyl polymers, polyester resins, and alkyd resins having various reactive functional groups as described above, as well as various amino resins, Examples include polyisocyanate resins, blocked polyisocyanate resins, and epoxy resins, as well as low molecular weight compounds having various reactive functional groups as mentioned above.

The hydroxyalkyl group-containing quaternary ammonium salt (B) which is the curing catalyst used in the present invention has the general formula [II]

[0062]

[C4]

(However, R1, R2, R3 in the formula
and R4 each represent a monovalent organic group which may be the same or different. ), wherein R1 , R2 , R3 respectively
or R4 has a hydroxyalkyl group in at least one of them.

Ammonium ion (R1) constituting the hydroxyalkyl group-containing quaternary ammonium salt (B)
(R2) (R3) (R4) To exemplify only typical examples of N+, 2-hydroxyethyltrimethylammonium ion, 2-hydroxyethylbenzyldimethylammonium ion, 2-hydroxyethyl-tri-n- Butylammonium ion, 2-hydroxyethylcyclohexyldimethylammonium ion, 2-hydroxypropyltrimethylammonium ion, 2-hydroxypropyltriethylammonium ion, 2-hydroxypropyl-tri-n-butylammonium ion, 2-hydroxypropylbenzyldimethylammonium ion , 3-hydroxypropyltrimethylammonium ion, 3-hydroxypropylbenzyldimethylammonium ion or 3-hydroxypropyldimethyllauryl ammonium ion, etc.

or bis(2-hydroxyethyl)dimethylammonium ion, bis(2-hydroxyethyl)diethylammonium ion, bis(2-hydroxyethyl)di-n-butylammonium ion, bis(2-hydroxyethyl)dimethylammonium ion, bis(2-hydroxyethyl)dimethylammonium ion, bis(2-hydroxyethyl)dimethylammonium ion,
-hydroxypropyl)di-n-butylammonium ion, tris(2-hydroxyethyl)-n-butylammonium ion, 4-hydroxybutylbenzyldimethylammonium ion, 6-hydroxyhexylbenzyldimethylammonium ion, 2-hydroxyethylbenzylpipe Examples include lysinium ion, 2-hydroxyethylbenzylmorpholinium ion, and 4-hydroxybutyl-tri-n-butylammonium ion.

[0066] As the counter anion X- of the ammonium ion constituting the quaternary ammonium salt (B), only representative examples include hydroxide ion, fluoride ion, chloride ion, bromide ion. ions, iodide ions, carboxylate ions, or tetrafluoroborate ions.

Among these, particularly representative carboxylate ions include acetate ion, propanoate ion, butanoate ion, 2-ethylhexanoate ion, benzoate ion, and p-tert ion.
Examples include -butylbenzoate ion, 2,2-dimethylpropanoate ion, 2,2-dimethylbutanoate ion, and 2,2-dimethylpentanoate ion.

Specific examples of the quaternary ammonium salt (B) include those in which the above-mentioned ammonium ion and counter anion are combined, but any combination of compounds can be used.

In order to obtain the composition of the present invention from both components (A) and (B) described above, the ammonium group of component (B) is added to 100 grams of solid content of component (A). is 0.05 to 60 mmol, furthermore, 0.1 to 4
Component (B) may be added so that the amount is within the range of 0 mmol.

If it is less than 0.05 mmol, the curability is poor, and if it exceeds 60 mmol, the water resistance of the cured coating film will be lowered, which is not preferable. (A) in the case where component (C) is further used as one component of the composition of the present invention;
The usage ratio of the component and the (C) component is determined as appropriate depending on the functional group content in the (A) component, as well as the type and functional group content of the (C) component. However, in general, (C) is added to 100 parts by weight of component (A).
) may be blended in an amount of 400 parts by weight or less, more preferably 200 parts by weight or less.

[0071] And, with respect to 100 grams of solid content of the mixture of both components (A) and (C), the ammonium group of component (B) is 0.05 to 60 mmol, more preferably 0.1 to 40 mmol. This (B
) ingredients may be added.

The composition of the present invention thus obtained can be used as a clear composition as it is, or can be used as a colored composition by adding a pigment to it.

The composition of the present invention may also contain various known and commonly used additives, such as leveling agents, ultraviolet absorbers, pigment dispersants, etc., if necessary.

When the composition of the present invention is used, for example, as a paint, various known and commonly used methods can be employed, such as brush coating, spray coating, or roll coating.

[0075] Furthermore, the curing conditions are 100 to 240
It can be selected as appropriate from a wide range of baking temperatures such as 0.degree. C. and baking times from 30 seconds to 90 minutes. The thus obtained thermosetting resin composition of the present invention forms a cured product that is excellent in acid resistance, heat yellowing resistance, and water resistance, and is extremely useful.

[0076]

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

Reference example 1 [1,3-dioxolane-2
Preparation example of vinyl polymer (A) having -on-4-yl group] In a four-necked flask equipped with a thermometer, cooling tube, stirrer and nitrogen gas introduction tube, 500 parts of xylene and n-butanol were added. 300 parts of 4-methacryloyloxymethyl-1,3-dioxolan-2-one, 200 parts of methyl methacrylate, 200 parts of styrene, and n-butyl methacrylate were charged and heated to 120°C. A mixture consisting of 300 parts of xylene and 20 parts of xylene
0 parts, 10 parts of azobisisobutyronitrile (AIBN)
and 20 parts of tert-butylperoxy-2-ethylhexanoate (TBPO) were added dropwise at the same temperature over 5 hours, and then the same temperature was maintained for 7 hours to continue the reaction. Continued, non-volatile content is 50.4%
, the Gardner viscosity (hereinafter abbreviated as viscosity) at 25°C is M-N, and the number average molecular weight is 11,00.
A solution of the desired polymer having a value of 0 was obtained. Hereinafter, this will be abbreviated as polymer (A-1).

Reference Example 2 (same as above) In a reactor similar to Reference Example 1, 150 parts of 4-ethyl-4-acryloyloxyethyl-1,3-dioxolan-2-one, 150 parts of styrene, and isobutyl methacrylate were added. 450 parts of 2-ethylhexyl methacrylate, 50 parts of 4-acryloyloxymethyl-1,3-dioxolan-2-one and 50 parts of 2-hydroxyethyl metharylate.
00 parts, 500 parts of toluene, 20 parts of n-butanol
0 parts of TBPO, 12 parts of TBPO, and 5 parts of AIBN were charged and heated to 90° C. for 30 minutes, and then
It took 30 minutes to raise the temperature to 115℃, and at the same temperature,
800 parts of the remaining monomer mixture and 3 parts of isobutyl acetate.
A mixture consisting of 00 parts, 12 parts of TBPO, and 5 parts of AIBN was added dropwise over 4 hours, and even after the addition was completed, the reaction was continued by maintaining the same temperature for 10 hours.
A solution of the desired polymer having a nonvolatile content of 50.6%, a viscosity of Y, and a number average molecular weight of 12,000 was obtained. Hereinafter, this will be abbreviated as polymer (A-2).

Reference Example 3 (same as above) 20% of 4-methyl-4-methacryloyloxymethyl-1,3-dioxolan-2-one as a monomer mixture
0 parts, 220 parts of methyl methacrylate, 2 parts of styrene
Polymerization was carried out in the same manner as in Reference Example 2, except that a mixture consisting of 00 parts of n-butyl methacrylate, 250 parts of n-butyl methacrylate, and 130 parts of methacrylic acid was used, and the nonvolatile content was 50.9% and the viscosity was Z. and the number average molecular weight is 12
,000 of the target polymer was obtained. Hereinafter, this will be abbreviated as polymer (A-3).

Reference example 4 [1,3-dioxolane-2
Preparation example of polyester resin (A) having -one-4-yl group] In a four-necked flask equipped with a thermometer, nitrogen gas introduction tube, rectification tube, and stirrer, 35 parts of trimethylolpropane,
274 parts of neopentyl glycol, 14 parts of adipic acid
5 parts of isophthalic acid, 246 parts of isophthalic acid, and 0.2 parts of dibutyltin oxide were charged, and the temperature was raised to 150°C, and then the temperature was gradually raised to 240°C over a period of 5 hours.

One hour after the temperature reached 240°C, the rectifying tube was replaced with a decanter, 18 parts of xylene was charged, and the reaction was continued at the same temperature for an additional 6 hours. Then,
After cooling, 244 parts of xylene, 81 parts of methyl isobutyl ketone, and 82 parts of cellosolve acetate were added to obtain a solution of 1,036 parts of polyester resin intermediate.

Meanwhile, in a four-necked flask equipped with a thermometer, nitrogen gas inlet tube, reflux condenser, and stirrer, 254 parts of isophorone diisocyanate, 122 parts of xylene, 52 parts of methyl isobutyl ketone, and cellosolve were added. 52 parts of acetate and 0.02 parts of dibutyltin dilaurate were charged and the temperature was raised to 80°C.

Next, at the same temperature, 135 parts of 4-hydroxymethyl-1,3-dioxolan-2-one was added dropwise over 1 hour, and after keeping at the same temperature for 1 hour, the previously prepared 1 of the solution of the polyester resin intermediate kept
036 parts were added.

After continuing the reaction at the same temperature for 4 hours, the temperature was lowered and 33 parts of n-butanol was added to obtain a non-volatile content of 60.3%, a viscosity of XY, and an acid value of A solution of a target polymer having a hydroxyl value of 2 or less and a hydroxyl value of 2 or less was obtained. Hereinafter, this will be abbreviated as polymer (A-4).

Reference Example 5 (same as above) 104 parts of trimethylolpropane, 207 parts of 1,6-hexanediol, 41 parts of hexahydrophthalic anhydride
The reaction was carried out in the same manner as in Reference Example 4, except that 1 part and 0.2 part of dibutyltin oxide were used.
108 parts of a polyester resin intermediate were obtained.

Next, 128 parts of 1,3-di(isocyanatomethyl)cyclohexane, 189 parts of 4-hydroxymethyl-1,3-dioxolan-2-one,
0.05 parts of dibutyltin dilaurate, 12 parts of xylene
2 parts of methyl isobutyl ketone and 52 parts of cellosolve acetate were added, the reaction was carried out at 80°C for 5 hours, the temperature was lowered, 33 parts of n-butanol was added, and the non-volatile content was 60.0 parts. %, viscosity is V, acid value is 27
A solution of the desired polymer having a hydroxyl value of 2 or less was obtained. Hereinafter, this will be abbreviated as polymer (A-5).

Reference Example 6 [Preparation example of vinyl polymer (C) containing carboxyl group] Using 300 parts of acrylic acid, 300 parts of styrene and 400 parts of n-butyl methacrylate as a monomer mixture, And, except for changing to use 15 parts of AIBN and 70 parts of TBPO as the initiator, the non-volatile content was 50.2%, and
A solution of the desired polymer having a viscosity of 0 was obtained. Hereinafter, this will be abbreviated as polymer (C-1).

Reference Example 7 [Example of Preparation of Polyester Resin (C) Containing a Carboxyl Group] In a reactor similar to Reference Example 1, "Plaxel 308" was placed.
500 parts of [polycaprolactone polyol manufactured by Daicel Chemical Co., Ltd.], 87 parts of phthalic anhydride, 1 part of xylene
After charging 50 parts of butyl acetate and 50 parts of butyl acetate, the temperature was raised to 120° C. under a nitrogen atmosphere.

A reaction was carried out for 2 hours at the same temperature to obtain a solution of a carboxyl group-containing polyester resin with a nonvolatile content of 80% and a viscosity of Q. Hereinafter, this will be referred to as a polymer (C
-2).

Reference Example 8 [Example of Preparation of Vinyl Polymer (C) Containing Carboxylic Anhydride Group] 500 parts of xylene and 300 parts of butyl acetate were charged into the same reactor as in Reference Example 1, and heated to 120°C. At elevated temperature, 100 parts of maleic anhydride, 200 parts of methyl methacrylate, 200 parts of styrene, 300 parts of n-butyl methacrylate, 200 parts of n-butyl acrylate, 10 parts of AIBN, 20 parts of TBPO, and A mixture of 200 parts of butyl acetate was added dropwise over 5 hours at the same temperature.

After completion of the dropwise addition, the same temperature was maintained for 7 hours to continue the reaction, and the nonvolatile content was 50.5%, the viscosity was L,
In addition, a solution of the target polymer having a number average molecular weight of 10,000 was obtained. Hereinafter, this will be abbreviated as polymer (C-3).

Examples 1 to 8 Components (A), (B) 0, and (C) were blended in the ratios listed in Table 1, and then xylene/n-butanol = 70/30 (weight ratio) A clear paint was obtained by diluting it with a mixed solvent to a viscosity that could be sprayed.

Various performances of each paint were evaluated. The results are summarized in Table 2.

[0094]

[Table 1]

[0095]

[Table 2]

Comparative Examples 1 to 3 (A), (C) and a hydroxyalkyl group-free quaternary ammonium salt were blended in the ratios shown in Table 1, and xylene/n-butanol = 70/30. Various control clear paints were prepared by diluting them to a spray viscosity with a mixed solvent of (weight ratio).

[0097] Using each of the control clear paints thus obtained, coating films were prepared in the same manner as in Examples 1 to 8, and then heat yellowing resistance and water resistance were evaluated. The results are summarized in Table 2.

Among these various performances, first, heat yellowing resistance was evaluated by spray painting the above various clear paints on a tin plate on which a white acrylic-melamine coating had been formed in advance, and A cured clear coating film having a film thickness of 50 microns (μm) was obtained by baking for a minute.

The difference in degree of yellowing (Δb value) between the clear coating film thus obtained and the white coating film was measured, and this was used as a measure of heat resistance to yellowing. The smaller the Δb value, the better the heat yellowing resistance.

[0100] Next, water resistance was evaluated using "Acrydic 47-712" [acrylic resin containing acid groups manufactured by Dainippon Ink & Chemicals Co., Ltd.] and "Super Beckamine L-
117-60" (butyl etherified methylol melamine resin manufactured by the same company) (solid content weight ratio = 80/2
0), add "Alpaste 7160NS" [aluminum paste made by Toyo Aluminum] so that the PWC is 15%, and further add toluene/xylene/cellosolve acetate/butyl acetate = 60/20/5/15.
A metallic base paint was prepared by diluting it to a spray viscosity with a mixed solvent (weight ratio).

[0101] This metallic base paint was applied to a steel plate treated with zinc phosphate, and the various clear paints described above were applied thereon, and then baked at 140°C for 20 minutes.
A two-coat, one-bake metallic coating was obtained.

[0102] The coating film thus obtained was placed in boiling water for 2 hours.
The difference between the color after soaking for a time and the color before soaking (
ΔE value) was calculated and used as a measure of water resistance. The smaller the ΔE value, the better the water resistance.

[0103] These respective Δb values and ΔE values are
It is also listed in Table 2.

[0104]

[Table 3]

[0105]

[Table 4]

[0106]

Effects of the Invention The thermosetting resin composition of the present invention obtained as described above has not only excellent acid resistance but also particularly excellent resistance to heat yellowing and water resistance, and is suitable for coatings only. It is extremely useful as an adhesive or a sealant.

Claims (7)

[Claims] Claim 1: General formula: [Formula 1] (In the formula, R1, R2 and R3 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different.) ) A polymer (A) having at least two 1,3-dioxolan-2-one-4-yl groups in one molecule.
and a quaternary ammonium salt (B) having a hydroxyalkyl group as essential components. Claim 2: General formula: [Formula 2] (wherein R1, R2 and R3 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different. ) A polymer (A) having at least two 1,3-dioxolan-2-one-4-yl groups in one molecule.
, a quaternary ammonium salt (B) having a hydroxyalkyl group, and a compound (C) having a functional group that reacts with a hydroxyl group and/or a 1,3-dioxolan-2-one-4-yl group as essential components. A thermosetting resin composition comprising: 3. The above polymer (A) contains at least one group selected from the group consisting of hydroxyl group, silyloxyalkyl group, carboxyl group, carboxylic acid anhydride group, and epoxy group.
The thermosetting resin composition according to claim 1 or 2, which also has a type of functional group. 4. The thermosetting resin according to claim 1 or 2, wherein the polymer (A) is at least one selected from the group consisting of vinyl polymers, polyester resins, and alkyd resins. Composition. 5. The thermosetting resin composition according to claim 4, wherein the vinyl polymer is an acrylic polymer. 6. The thermosetting resin composition according to claim 4, wherein the vinyl polymer is a fluoroolefin polymer. 7. The compound (C) having a functional group that reacts with the hydroxyl group and/or 1,3-dioxolan-2-one-4-yl group is a carboxyl group, a carboxylic acid anhydride group, or a hydroxymethylamino group. , an alkoxymethylamino group, a hydroxyl group, a silyloxyalkyl group, an isocyanate group, a blocked isocyanate group, and an epoxy group. Resin composition.