JPH0778159B2 - Thermosetting resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION The present invention relates to a thermosetting resin composition useful as a vehicle for paints, adhesives, printing inks and the like.

A thermosetting resin composition comprising a melamine resin and an acrylic resin, a polyester resin, an epoxy resin having a hydroxyl group is widely used in the coating field. These melamine resin-curing resin compositions contain a proton donor such as paratoluenesulfonic acid as a catalyst for the curing reaction. However, in a system containing a free acid, the resin tends to gel, and it is generally difficult to achieve both low-temperature curability and storage stability of the composition. Therefore, it has been proposed to use a compound obtained by blocking a sulfonic acid with an amine as a catalyst, but its curability and storage stability were not always satisfactory.

Japanese Patent Publication No. 63-33512 discloses a curable resin composition containing a vinyl polymer having an alkoxysilyl bond in its side chain, a polyhydroxy compound, and a curing catalyst. Such In the system, the alkoxysilane of self-condensation reaction _{ROSi - + - SiOR + H 2} O → -Si - O - Si + 2ROH and alkoxy co-condensation reaction between silane and hydroxyl _{ROSi- + HO-C- → -Si -} O _- C _- + it is believed that the curing takes place by the ROH.

Conventionally, as catalysts for these self-condensation and co-condensation reactions, amines such as butylamine, dibutylamine, t-butylamine, ethylenediamine, tetraisopropyl titanate, tetrabutyl titanate, tin octylate, lead octylate, zinc octylate, octyl octylate. Metal-containing compounds such as calcium acidate, dibutyltin diacetate, dibutyltin dioctate and dibutyltin dilaurate, and acidic compounds such as p-toluenesulfonic acid and trichloroacetic acid have been used.

However, as can be understood from the fact that the system containing such a catalyst can be cured at room temperature, it cannot be stably stored for a long period of time with the catalyst contained. Therefore, if long-term storage stability is desired, it is necessary to take measures such as adding a catalyst as a two-part liquid immediately before use, reducing the amount of the catalyst, or blocking with a volatile amine or acid during curing. is there. However, the use of 2 liquids has a problem in workability, and there are restrictions such as that it must be used within the pot life. With other measures, the membrane performance is deteriorated and it is difficult to block completely, so sufficient storage stability is achieved. Are not obtained, and the blocking amine or acid is volatilized to cause coloring and an offensive odor.

JP-A-58-37003 and JP-A-58-37004 disclose sulfonium salt type cationic polymerization initiators that thermally cleave to generate carbonium cations.

Recently, the present inventors newly developed a pyridinium salt cationic polymerization initiator which is also thermally cleaved. Japanese Patent Application Sho 62-25
See 5388.

These initiators were developed for the purpose of utilizing the carbonium cation generated by thermal cleavage in the cationic polymerization reaction.However, the OH compound exists in the reaction system using these initiators. At that time, it was considered that the cation generated by the cleavage reacts with the hydroxyl group to generate a proton, which is used as a crosslinking reaction catalyst for the melamine resin and the alkoxysilane compound.

The sulfonium or pyridinium salt is thermally cleaved,
Since it does not release a proton unless it reacts with the OH group, the crosslinking reaction of the melamine resin or the alkoxysilane compound does not substantially occur below the cleavage temperature. Therefore, a thermosetting resin composition having critical storage stability can be obtained by using such a carbonium cation by thermally cleaving.

SUMMARY OF THE INVENTION (a) A film-forming resin containing at least two hydroxyl groups per molecule, and (b) a solid content weight ratio of 50/5 with respect to the hydroxyl group-containing resin.
A melamine resin in an amount of 0 to 95/5, and (c) a formula of 0.01 to 10% by weight of the total amount of the hydroxyl group-containing resin and the melamine resin in a solid content weight ratio. (Wherein R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, halogen, alkyl, alkoxy, nitro, amino, alkylamino, hydroxy, cyano, alkoxycarbonyl, carbamoyl or alkanoyl, and M is As, Sb , B or P
And X is halogen and n is 4 when M is B.
And 6 in all other cases. And a pyridinium salt and / or a sulfonium salt of the above).

In another aspect, the present invention provides: (a) a silicone resin containing at least two alkoxysilyl bonds per molecule; and (b) a solid content of 0.01 to 0.01 of the silicone resin.
10 wt% formula (The symbols in the formulas are the same as the above.) The present invention relates to a thermosetting resin composition containing a pyridinium salt and / or a sulfonium salt.

Alternatively, the present invention provides: (a) a silicone resin containing at least two alkoxysilyl bonds per molecule; and (b) the number of hydroxyl groups per alkoxysilyl bond of the silicone resin is 0.1 to 10. Of a resin containing at least two hydroxyl groups per molecule, and (c) a solid content of 0.01 to 10% by weight of the total amount of the silicone resin and the hydroxyl group-containing resin. (The symbols in the formulas are the same as above.) The present invention relates to a thermosetting resin composition containing a pyridinium salt and / or a sulfonium salt.

Although the composition of the present invention does not substantially cure at the cleavage temperature of the pyridinium salt or the sulfonium salt or lower,
The curing reaction is characterized by the critical progress of the curing reaction by heating above the temperature. Therefore, the storage stability of the composition is far superior to the compositions containing the conventional catalyst.

Detailed discussion I. Systems containing melamine resins Film-forming resins using melamine resins as curing agents are widely used in the paint field.

Examples of these are polyester resin, polylactone resin,
Examples thereof include epoxy resin and acrylic resin. The polyester resin is obtained by a condensation reaction of a polyhydric carboxylic acid or its acid anhydride with a polyhydric alcohol, and a resin having a hydroxy group at the terminal and / or in the middle of the polyester chain can be used. Hydroxyl terminated polylactone resins may also be used.

Examples of the epoxy resin include resins having an epoxy side group at the terminal and a hydroxy group at the middle of the molecular chain, such as bisphenol type epoxy resin and / or novolac type epoxy resin.

The acrylic resin having a hydroxyl group is (meth) acrylic acid 2
A hydroxy group-containing monomer such as hydroxyethyl,
Alkyl (meth) acrylates such as methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; styrene and its derivatives, (meth) acrylonitrile, vinyl acetate It can be obtained by copolymerizing with another monomer such as

Melamine resins are prepared by reacting a triazine compound such as melamine, benzoguanamine or acetoguanamine with formaldehyde and optionally partially or completely etherifying the methylol group of the condensation product with a lower alkanol such as methanol and butanol. can get.

Thermosetting resin compositions obtained by combining a film-forming resin having a hydroxyl group and a melamine resin are well known in the field of coating materials, and the composition of the present invention has the above-mentioned thermocleavable pyridinium salt / sulfonium salt as a catalyst for a curing reaction. It may be the same as the known melamine resin-curable thermosetting composition except that is used.

The ratio of the film-forming resin having a hydroxyl group to the melamine resin may be 50/50 to 95/5 by weight.

The pyridinium salt / sulfonium salt is blended in an amount of 0.01 to 10% by weight, preferably 0.05 to 5.0% by weight, based on the resin solid content. If the blending amount is too small, the curability will be lowered, and if it is excessive, the cured product will be colored and the water resistance will be deteriorated.

The composition may contain additives such as pigments and fillers depending on its use.

II. System utilizing self-condensation or co-condensation reaction of alkoxysilyl group Silicone resin containing alkoxysilyl bond Typical examples of silicone resin containing at least two alkoxysilyl bonds per molecule are as follows. is there.

(1) Alkoxysilyl Group-Containing Acrylic Resin A monomer having an alkoxysilyl group and an ethylenic double bond in the molecule is used as an alkoxy group-containing acrylic polymer or copolymer by homopolymerization or copolymerization with another polymerizable monomer. Make a polymer.

The first class of such monomers is the general formula Is an alkoxysilylalkyl ester of acrylic acid or methacrylic acid. In the formula, R is hydrogen or methyl, x is an integer of 1 or more, R ′ and R ″ are alkyl, n
Is 0, 1 or 2.

Examples of these specific compounds include γ-metacroyloxypropyltrimethoxysilane, γ-metacroyloxypropylmethyldimethoxysilane, γ-metacroyloxypropyldimethylmethoxysilane, γ-metacroyloxypropyltriethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-
Methacryloyloxypropyltripropoxysilane, γ
-Methacryloyloxypropylmethyldipropoxysilane, γ-methacryloyldimethylpropoxysilane, γ
-Methacryloyloxypropyltributoxysilane, γ
-Metacroyloxypropylmethyldibutoxysilane, γ-metacroyloxypropyl dimethylbutoxysilane and the like.

The second class is the adducts of (meth) acrylic acid with epoxy group-containing alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane or δ- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

The third class is hydroxyalkyl esters of (meth) acrylic acid such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate, and the general formula OCN ( CH ₂ ) _x Si (R ′) _n (OR ″) _3-n compounds such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ- It is an adduct with isocyanate propylmethyldiethoxysilane and the like.

The final class is (meth) acrylic acid glycidyl ester and amino group-containing alkoxysilanes such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyl. Dimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, γ
-Aminopropyldimethylethoxysilane, γ-aminopropylmethyldiethoxysilane and the like are adducts.

Examples of monomers copolymerizable with the alkoxysilyl group-containing acrylic monomer include various (meth) acrylic acid esters, styrene, (meth) acrylic acid, (meth) acrylonitrile, (meth) acrylamide, vinyl chloride, vinyl acetate, and the like. .

(2) Silicon modified epoxy resin The amino group-containing alkoxysilane compound mentioned immediately before is
Similarly, it can be used to produce an alkoxysilyl group-containing modified epoxy resin by addition reaction with an epoxy group.

(3) Silicon Modified Polyester Resin A polyester resin having a free carboxy group is modified with the same epoxy group-containing alkoxysilane used for the addition reaction with (meth) acrylic acid to produce an acrylic monomer containing an alkoxysilyl group. , A silicone-modified polyester resin can be used.

A polyester resin having a free hydroxyl group can be modified with the same isocyanate group-containing alkoxysilane that undergoes an addition reaction with (meth) acrylic acid hydroxyalkyl ester to produce an alkoxysilyl group-containing acrylic monomer, and can be made into a silicone-modified polyester resin. .

Hydroxyl Group-Containing Resin As the resin containing at least two hydroxyl groups per molecule, a hydroxyl group-containing polyester resin, a hydroxyl group-terminated polylactone resin, an epoxy resin and a hydroxyl group-containing acrylic resin are typical examples.

The polyester resin is obtained by a condensation reaction of a polyhydric carboxylic acid or its acid anhydride with a polyhydric alcohol, and a resin having a hydroxy group at the terminal and / or in the middle of the polyester chain can be used. Hydroxyl terminated polylactone resins may also be used.

Examples of the epoxy resin include resins having an epoxy side group at the terminal and a hydroxy group at the middle of the molecular chain, such as bisphenol type epoxy resin and / or novolac type epoxy resin.

The acrylic resin having a hydroxyl group is (meth) acrylic acid 2
A hydroxy group-containing monomer such as hydroxyethyl,
Alkyl (meth) acrylates such as methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; styrene and its derivatives, (meth) acrylonitrile, vinyl acetate It can be obtained by copolymerizing with another monomer such as ## STR1 ## by a conventional method.

Thermosetting Resin Composition The thermosetting resin composition of the present invention utilizing the self-condensation reaction of alkoxysilyl groups contains the silicone resin and the pyridinium salt / sulfonium salt as essential components.

In the thermosetting resin composition of the present invention which utilizes a co-condensation reaction of an alkoxysilyl group and a hydroxyl group, the number of hydroxyl groups is one per alkoxysilyl bond of the silicone resin.
The hydroxyl group-containing resin in an amount of 0.1 to 10 and the pyridinium salt / sulfonium salt are essential components.

In any case, the pyridinium salt / sulfonium salt is 0.01 to 10% by weight, preferably 0.05 to 10% by weight based on the resin solid content.
~ 5.0 wt% is compounded. If the blending amount is too small, the curability will be lowered, and if it is excessive, the cured product will be colored and the water resistance will be deteriorated.

The composition may contain additives such as pigments and fillers and a solvent, depending on its use.

The composition of the present invention does not cure below the cleavage temperature of the pyridinium salt / sulfonium salt, and therefore has good storage stability, but it cures when heated above the cleavage temperature. Although the curing time depends on the temperature, it is generally within 1 hour.

The invention is illustrated by the following examples. “Parts” and “%” in the examples are by weight.

I. Production Example Synthesis of Polyester Resin Production Example 1 36 parts of hexahydrophthalic acid in a reaction vessel equipped with a heating device, a stirrer, a reflux device, a water separator, a rectification column and a thermometer,
42 parts of trimethylol propane, neopentyl glycol
Charge 50 parts and 56 parts of 1,6-hexanediol and heat. When the raw material melts and stirring becomes possible, start stirring and raise the temperature to 210 ° C. The temperature is raised from 210 ° C to 230 ° C over a period of 2 hours at a constant temperature, and the condensed water produced is distilled out of the system.

When it reaches 230 ℃, keep the temperature as it is and cool it when the acid value reaches 1.0. After cooling, add 153 parts isophthalic acid,
Reheat to 190 ° C. The temperature is raised from 190 ° C to 210 ° C over a period of 3 hours at a constant rate, and the condensation water produced is distilled out of the system. When 210 ° C is reached, add 3 parts xylene to the reaction vessel,
Switch to condensation in the presence of solvent and cool to an acid value of 5.0.

After cooling, 190 parts of xylene was added to obtain a polyester resin solution [A].

Synthesis of acrylic resin Production example 2 90 parts of Solvesso 100 was charged into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, N2 gas inlet pipe and dropping funnel, and the temperature was raised to 160 ° C while introducing N2 gas. After heating, 23.2 parts of 2-hydroxyethyl methacrylate, 35.65 parts of n-butyl acrylate, 40.15 parts of methyl methacrylate, methacrylic acid
A mixture of 1.0 part and 10 parts of tert-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate using a dropping funnel.

1 hour after the end of the dropping of the mixture, 10 parts of xylene and te
A mixture of 1 part of rt-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate over 30 minutes. After completion of the dropping, the mixture was aged for 2 hours and then cooled to obtain an acrylic resin [A].

Synthesis of Silicon Resin Production Example 3 45 parts of xylene was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a N2 gas introducing pipe and a dropping funnel, and N2 was added.
After heating to 130 ° C. while introducing gas, 50 parts of γ-methacryloyloxypropyltrimethoxysilane and tert-
A mixture of 4 parts of butylperoxy-2-ethylhexanoate was added dropwise at a constant rate over 3 hours from a dropping funnel.

After keeping the mixture for 30 minutes after the dropwise addition, the inside of the reaction system was cooled to 90 ° C., and a mixture of 1 part of tert-butylperoxy-2-ethylhexanoate and 5 parts of xylene was kept at the temperature for 1 hour from the dropping funnel. At constant speed.

After completion of dropping, the mixture was aged at 90 ° C. for 2 hours and then cooled to obtain a silicone resin solution [A].

Production Example 4 45 parts of xylene was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a N2 gas introducing pipe and a dropping funnel, and N2 was added.
After heating to 130 ° C while introducing gas, 50 parts of γ-methacryloyloxypropylmethyldimethoxysilane and te
A mixture of 4 parts of rt-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate over 3 hours from a dropping funnel.

After keeping the mixture for 30 minutes after the dropwise addition, the inside of the reaction system was cooled to 90 ° C., and a mixture of 1 part of tert-butylperoxy-2-ethylhexanoate and 5 parts of xylene was kept at the temperature for 1 hour from the dropping funnel. At constant speed.

After completion of dropping, the mixture was aged at 90 ° C. for 2 hours and then cooled to obtain a silicone resin solution [B].

Production Example 5 45 parts of xylene was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a N2 gas introducing pipe and a dropping funnel, and N2 was added.
After heating to 130 ° C while introducing gas, 50 parts of γ-methacryloyloxypropyldimethylmethoxysilane and te
A mixture of 4 parts of rt-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate over 3 hours from a dropping funnel.

After keeping the mixture for 30 minutes after the dropwise addition, the inside of the reaction system was cooled to 90 ° C., and a mixture of 1 part of tert-butylperoxy-2-ethylhexanoate and 5 parts of xylene was kept at the temperature for 1 hour from the dropping funnel. At constant speed.

After completion of dropping, the mixture was aged at 90 ° C. for 2 hours and then cooled to obtain a silicone resin solution [C].

Production Example 6 45 parts of xylene was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, an N2 gas introducing pipe and a dropping funnel, and N2 was added.
After heating to 130 ° C. while introducing gas, 50 parts of γ-methacryloyloxypropyltriethoxysilane and tert-
A mixture of 4 parts of butylperoxy-2-ethylhexanoate was added dropwise at a constant rate over 3 hours from a dropping funnel.

After keeping the mixture for 30 minutes after the dropwise addition, the inside of the reaction system was cooled to 90 ° C., and a mixture of 1 part of tert-butylperoxy-2-ethylhexanoate and 5 parts of xylene was kept at the temperature for 1 hour from the dropping funnel. At constant speed.

After completion of dropping, the mixture was aged at 90 ° C. for 2 hours and then cooled to obtain a silicone resin solution [D].

Production Example 7 45 parts of xylene was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a N2 gas introducing pipe and a dropping funnel, and N2 was added.
After heating to 130 ° C while introducing gas, a mixture of 25 parts of γ-methacryloyloxypropyltriethoxysilane, 25 parts of methyl methacrylate and 4 parts of tert-butylperoxy-2-ethylhexanoate is added dropwise to the funnel. It was added dropwise at a constant speed in 3 hours.

After keeping the mixture for 30 minutes after the dropwise addition, the inside of the reaction system was cooled to 90 ° C., and a mixture of 1 part of tert-butylperoxy-2-ethylhexanoate and 5 parts of xylene was kept at the temperature for 1 hour from the dropping funnel. At constant speed.

After completion of dropping, the mixture was aged at 90 ° C. for 2 hours and then cooled to obtain a silicone resin solution [E].

Production Example 8 100 parts of polyester resin solution [A] was charged into a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, heated to 100 ° C., and then 0.2 parts of dibutyltin dilaurate was added to KBM-9007.
10 parts of structural formula OCN (CH ₂ ) ₃ Si (OCH ₃ ) ₃ (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise at a constant rate over 30 minutes from a dropping funnel. After aging for 1 hour, a cooled silicone resin solution [F] was obtained. In the IR spectrum of the obtained resin solution, the absorption due to the NCO group at 1720 cm ^-1 had disappeared.

Production Example 9 A reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser was charged with 100 parts of bisphenol A diglycidyl ether, and the temperature was 150 ° C.
Γ-aminopropyltrimethoxysilane 10 after heating to
0 part of the dropping funnel was dropped at a constant speed in 1 hour. After aging for 1 hour, a cooled silicone resin solution [G] was obtained.

II. Melamine resin curing system Example 1 Cymel 303 to 70 parts of Praxel 308 (trifunctional polycaprolactone polyol manufactured by Daicel, molecular weight 860)
(Mitsui Toatsu Co., Ltd. melamine resin) 30 parts and 4-methylbenzyl-4-cyanopyridinium-hexafluoroantimonate 2 parts were added and mixed, coated on a tin plate and baked at 140 ° C. to obtain a cured coating film. The curing reactivity and the storage stability test of the mixed solution were conducted under the conditions shown in Table 1, and the results shown in Table 1 were obtained.

Example 2 Cymel 303 to 70 parts of Praxel 308 (trifunctional polycaprolactone polyol manufactured by Daicel, molecular weight 860)
(Mitsui Toatsu Co., Ltd. melamine resin) (30 parts) and 4-chlorobenzyl-2-methylpyridinium-hexafluoroantimonate (2 parts) were added and mixed, and the mixture was applied to a tin plate and baked at 140 ° C to obtain a cured coating film. The following investigation was performed in the same manner as in Example 1.

Example 3 Cymel 303 to 50 parts of Praxel 308 (trifunctional polycaprolactone polyol manufactured by Daicel, molecular weight 860)
(Mitsui Toatsu Co., Ltd. melamine resin) 50 parts and 2,4-dichlorobenzyl-2-methylpyridinium-hexafluorophosphate 2 parts were added and mixed, and applied on a tin plate.
A baked coating film was obtained by baking at ℃. The following investigation was performed in the same manner as in Example 1.

Example 4 Polyester Resin A To 90 parts of solid content, 10 parts of Cymel 303 (melamine resin manufactured by Mitsui Toatsu Co., Ltd.) and 0.1 part of 2-methylbenzyl-2-methylpyridinium-hexafluorophosphate were added and mixed, and applied on a tin plate. Then, it was baked at 140 ° C. to obtain a cured coating film. The following investigation was performed in the same manner as in Example 1.

Example 5 Polyester Resin A 40 parts solid content of Uban 20SE (melamine resin manufactured by Mitsui Toatsu) as solid content of 60 parts and
2,4-Dimethylbenzyl-2-chloropyridinium-tetrafluoroborate (2 parts) was added and mixed, coated on a tin plate and baked at 140 ° C. to obtain a cured coating film. The following investigation was performed in the same manner as in Example 1.

Example 6 Polyester Resin A 30 parts of Uban 20SE (melamine resin manufactured by Mitsui Toatsu Co., Ltd.) as solid content of solid content of 70 and 7 parts of 4-methoxybenzyl-3-chloropyridinium-tetrafluoroborate were added and mixed, It was applied to a tin plate and baked at 140 ° C to obtain a cured coating film. The following investigation was performed in the same manner as in Example 1.

Example 7 Acrylic Resin A To 90 parts of solid content, 10 parts of Cymel 303 (melamine resin manufactured by Mitsui Toatsu Co., Ltd.) and 2 parts of benzyl-2-methylpyridinium-hexafluoroantimonate were added and mixed, and the mixture was coated on a tin plate and 140 ° C. And baked to obtain a cured coating film. The following investigation was performed in the same manner as in Example 1.

Example 8 Acrylic resin A 40 parts by weight of Uban 20SE (melamine resin manufactured by Mitsui Toatsu Co., Ltd.) as solid content of 60 and 2-
2 parts of chlorobenzyl-2-cyanopyridinium-hexafluorophosphate were added and mixed, and the mixture was applied to a tin plate and baked at 140 ° C to obtain a cured coating film. The following investigation was performed in the same manner as in Example 1.

Example 9 Acrylic resin A 30 parts of Uban 20SE (melamine resin manufactured by Mitsui Toatsu) as solid content of 70 parts and 4-
0.5 part of methoxybenzyl-4-chloropyridinium-hexafluoroantimonate was added and mixed, coated on a tin plate and baked at 140 ° C. to obtain a cured coating film. Example 1 below
The same examination was carried out.

Comparative Example 1 Cymel 303 to 70 parts of Praxel 308 (Daicel's trifunctional polycaprolactone polyol, molecular weight 860)
(Mitsui Toatsu Co., Ltd. melamine resin) 30 parts and p-toluenesulphonic acid triethylamine salt 2 parts were added and mixed, and the mixture was coated on a tin plate and baked at 140 ° C. to obtain a cured coating film. The curing reactivity and the storage stability test of the mixed solution were conducted under the conditions shown in Table 1, and the results shown in Table 1 were obtained.

Comparative Example 2 Polyester Resin A 10 parts of Cymel 303 (melamine resin manufactured by Mitsui Toatsu Co., Ltd.) and 2 parts of pyridine salt of p-dodecylbenzenesulphonic acid were mixed with 90 solids, mixed, coated on a tin plate and baked at 140 ° C. Then, a cured coating film was obtained. The following investigation was performed in the same manner as in Example 1.

Comparative Example 3 Acrylic resin A 40 parts solid content of Uban 20SE (melamine resin manufactured by Mitsui Toatsu) as solid content of 60 parts and p-
Toluenesulphonic acid pyridine salt (2 parts) was added and mixed, and the mixture was coated on a tin plate and baked at 140 ° C to obtain a cured coating film. The following investigation was performed in the same manner as in Example 1.

III. Cocondensation system of alkoxysilyl group and hydroxyl group Example 10 100 parts of acrylic resin [A], 30 parts of silicone resin [A].
2.62 parts of 7 parts, 5 parts of methanol and 2.62 parts of benzyl-4'-cyanopyridinium-hexafluoroantimonate were mixed, and the mixture was uniformly applied on a steel plate and set for 2 hours, then baked at 140 ° C for 30 minutes. A cured coating film was obtained. The curing reaction of the coating film and the storage stability test of the mixed solution were performed under the conditions shown in Table 2, and the results shown in Table 2 were obtained.

Example 11 100 parts of acrylic resin [A] and 28.
9 parts, methanol 5 parts and 2-chlorobenzyl-4-
Cyanopyridinium-hexafluoroantimonate
Mix 2.58 parts and apply the mixture evenly onto the steel plate. 2
After setting the time, it was baked at 140 ° C. for 30 minutes to obtain a cured coating film. The following investigation was performed in the same manner as in Example 10.

Example 12 100 parts of acrylic resin [A] and 26.
9 parts, methanol 5 parts and 2,4-dichlorobenzyl-
2.54 parts of 4'-cyanopyridinium-hexafluoroantimonate was mixed, and the mixed solution was uniformly applied on a steel plate and set for 2 hours, and then baked at 140 ° C for 30 minutes to obtain a cured coating film. The following investigation was performed in the same manner as in Example 10.

Example 13 100 parts of acrylic resin [A] and 36.
2 parts, methanol 5 parts and 2-methylbenzyl-2 '
-Cyanopyridinium-hexafluoroantimonate was mixed in 2.72 parts, the mixed solution was uniformly applied on a steel plate and set for 2 hours, and then baked at 140 ° C for 30 minutes,
A cured coating film was obtained. The following investigation was performed in the same manner as in Example 10.

Example 14 100 parts of acrylic resin [A] and 43.
4 parts, 5 parts methanol and 4-nitrobenzyl-2 '
2.87 parts of -methylpyridinium-hexafluoroantimonate was mixed, and the mixed solution was uniformly applied on a steel plate and set for 2 hours, and then baked at 140 ° C for 30 minutes,
A cured coating film was obtained. The following investigation was performed in the same manner as in Example 10.

Example 15 100 parts of polyester resin [A], silicone resin [F]
30 parts, methanol 5 parts and 2-methylbenzyl-
2.87 parts of 4'-fluoropyridinium-hexafluorophosphate were mixed, the mixed solution was uniformly applied on a steel plate and set for 2 hours, and then baked at 140 ° C for 30 minutes to obtain a cured coating film. The following investigation was performed in the same manner as in Example 10.

Example 16 100 parts of polyester resin [A], silicone resin [G]
18 parts, 5 parts methanol and 4-methoxybenzyl-
2.87 parts of pyridinium-hexafluorophosphate were mixed, the mixed solution was uniformly applied on a steel plate and set for 2 hours, and then baked at 140 ° C. for 30 minutes to obtain a cured coating film. The following investigation was performed in the same manner as in Example 10.

Comparative Example 4 100 parts of acrylic resin [A] and 30 parts of silicone resin [A].
After mixing 9 parts and 5 parts of methanol, apply the mixture evenly on a steel plate and set for 2 hours, then 140 ° C
And baked for 30 minutes to obtain a cured coating film. The same examination as in Example 10 was performed below.

Comparative Example 5 100 parts of acrylic resin [A] and 30 parts of silicone resin [A].
9 parts, 2.62 parts of dodecyl bunsen sulfonic acid and 5 parts of methanol were mixed, and the mixed solution was uniformly applied on a steel plate and set for 2 hours, and then baked at 140 ° C. for 30 minutes to obtain a cured coating film. The same examination as in Example 10 was performed below.

IV. Alkoxysilyl Group Self-Condensation System Example 17 100 parts of a silicon resin solution [A], 5 parts of methanol and 2 parts of 2-chlorobenzyl-4′-cyanopyridinium-hexafluoroantimonate were mixed, and a mixed solution thereof was mixed. Is evenly applied on the steel plate, and after setting for 2 hours,
It was baked at 140 ° C. for 30 minutes to obtain a cured film. Example 10 below
The same examination was carried out.

Example 18 A cured film was obtained in the same manner as in Example 17, except that the silicone resin solution [C] was used instead of the silicone resin solution [A]. The same examination as in Example 10 was performed below.

Example 19 A cured film was obtained in the same manner as in Example 17, except that the silicone resin solution [F] was used instead of the silicone resin solution [A]. The same examination as in Example 10 was performed below.

Comparative Example 6 100 parts of silicon resin [A] and 5 parts of methanol were mixed, the mixed solution was uniformly applied on a steel plate and set for 2 hours, and then baked at 140 ° C. for 30 minutes to obtain a cured coating film. It was

Comparative Example 7 100 parts of silicone resin [A], 2 parts of dodecylbenzelsulfonic acid and 5 parts of methanol were mixed, and the following Comparative Example 3
A cured film was obtained in the same manner as in. The same examination as in Example 10 was performed below.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 67/00 LPK 83/06 LRT (72) Inventor Koichi Tsutsui 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka No. Japan Paint Co., Ltd. (56) Reference JP-A-1-96169 (JP, A) JP 51-18975 (JP, B1)

Claims (7)

[Claims] 1. A film-forming resin containing (a) at least two hydroxyl groups per molecule, and (b) a solid content weight ratio of 50/5 to the hydroxyl group-containing resin.
A melamine resin in an amount of 0 to 95/5, and (c) a formula of 0.01 to 10% by weight of the total amount of the hydroxyl group-containing resin and the melamine resin in the solid content weight ratio. (Wherein R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, halogen, alkyl, alkoxy, nitro, amino, alkylamino, hydroxy, cyano, alkoxycarbonyl, carbamoyl or alkanoyl, and M is As, Sb , B or P
And X is halogen and n is 4 when M is B.
And 6 in all other cases. 2.) A thermosetting resin composition, which comprises a pyridium salt and / or a sulfonium salt. 2. The thermosetting resin composition according to claim 1, wherein the hydroxyl group-containing resin is a hydroxyl group-containing polyester resin, a hydroxyl group-terminated polylactone resin, an epoxy resin, or a hydroxyl group-containing acrylic resin. 3. A silicone resin containing (a) at least two alkoxysilyl bonds per molecule, and (b) a solid content ratio of 0.01 to 10% by weight of the silicone resin. (Wherein R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, halogen, alkyl, alkoxy, nitro, amino, alkylamino, hydroxy, cyano, alkoxycarbonyl, carbamoyl or alkanoyl, and M is As, Sb , B or P
And X is halogen and n is 4 when M is B.
And 6 in all other cases. 2.) A thermosetting resin composition, which comprises a pyridium salt and / or a sulfonium salt. 4. The silicone resin is an acrylic polymer or copolymer containing at least one constituent monomer component having the alkoxysilane bond and an ethylenic double bond in the molecule, and a polyester resin having a carboxyl group. A silicone-modified polyester resin obtained by reacting with an epoxy group-containing alkoxysilane, a silicon-modified polyester resin obtained by reacting a hydroxyl group-containing polyester resin with an isocyanate group-containing alkoxysilane, or an epoxy resin containing an amino group-containing alkoxysilane The thermosetting resin composition according to item 3, which is a silicon-modified epoxy resin obtained by reacting 5. A silicone resin containing at least two alkoxysilyl bonds per molecule; (b) 0.1 to 10 hydroxyl groups per alkoxysilyl bond in the silicone resin. Of a resin containing at least two hydroxyl groups per molecule, and (c) a solid content ratio of 0.01 to 10% by weight based on the total amount of the silicone resin and the hydroxyl group-containing resin. (Wherein R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, halogen, alkyl, alkoxy, nitro, amino, alkylamino, hydroxy, cyano, alkoxycarbonyl, carbamoyl or alkanoyl, and M is As, Sb , B or P
And X is halogen and n is 4 when M is B.
And 6 in all other cases. 2.) A thermosetting resin composition, which comprises a pyridium salt and / or a sulfonium salt. 6. The silicone resin is an acrylic polymer or copolymer having at least one constituent monomer component having the alkoxysilane bond and an ethylenic double bond in the molecule, and a polyester resin having a carboxyl group. A silicone-modified polyester resin obtained by reacting with an epoxy group-containing alkoxysilane, a silicon-modified polyester resin obtained by reacting a hydroxyl group-containing polyester resin with an isocyanate group-containing alkoxysilane, or an epoxy resin with an amino group-containing alkoxysilane The thermosetting resin composition according to item 5, which is a silicone-modified epoxy resin obtained by reacting with. 7. The thermosetting resin composition according to claim 5, wherein the hydroxyl group-containing resin is a hydroxyl group-containing polyester resin, a hydroxyl group-terminated polylactone resin, an epoxy resin, or a hydroxyl group-containing acrylic resin.