JP2585198B2 - Thermosetting resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to a thermosetting resin composition using a novel benzylpyridinium sulfonate, which thermally cleaves to release a sulfonic acid, as a heat latent curing catalyst. Such compositions are useful as vehicles for paints, adhesives, printing inks and the like.

[0002] In one-pack type paints using an aromatic sulfonic acid as a proton donor as a curing catalyst, a sulfonic acid blocked with a volatile amine to prevent an early curing reaction such as gelling of the paint during storage. Amine salts have been used. However, in such sulfonic acid amine salts,

[0003]

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Due to the equilibrium as described above, the amount of amine must be reduced in order to exert the effect of sulfonic acid at a relatively low temperature. This increases the amount of unblocked sulfonic acid and reduces the storage stability of the system. When the amount of amine is increased to increase the storage stability, the amount of sulfonic acid in the form of an amine salt increases. Therefore, it is necessary to heat the sulfonic acid to a high temperature in order to exert its effect. As described above, the conventional system using the amine salt of sulfonic acid has a drawback that it is difficult to achieve both control of the curing temperature and storage stability.

JP-B-63-33512 discloses a curable resin composition containing a vinyl polymer having an alkoxysilyl bond in a side chain, a polyhydroxy compound, and a curing catalyst. In such a system, a self-condensation reaction of alkoxysilane ROSi − + − SiOR + H ₂ O → −Si—O—Si + 2ROH and a cocondensation reaction of alkoxysilane with hydroxyl group ROSi− + HO−C− → It is believed that curing occurs with -Si-OC- + ROH.

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

However, such a system containing a catalyst cannot be stably stored for a long period of time while containing a catalyst, as can be understood from the fact that curing at room temperature is also possible. Therefore, when long-term storage stability is desired, it is necessary to take measures such as blending the catalyst immediately before use as a two-part solution, reducing the amount of the catalyst, or blocking with a volatile amine or acid during curing. is there. However, if two liquids are used, there is a problem in workability, and there are restrictions such as the fact that they must be used within the pot life. And the blocking amine or acid volatilizes to cause coloring and off-flavor.

Accordingly, the present invention provides a method using a compound which is stable up to a critical temperature near the curing temperature but is thermally cleaved when the critical temperature is reached, releasing sulfonic acid and exerting its catalytic effect. It is an object to provide a curable resin composition.

SUMMARY OF THE INVENTION The present invention relates to a heat-latent curing catalyst having the formula

[0010]

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The novel benzylpyridinium sulfonates are used. Wherein R ₁ , R ₂ , R ₃ and R ₆ are hydrogen, halogen, alkyl, alkoxy, nitro, amino, alkylamino, cyano, alkoxycarbonyl or carbamoyl; R ₄ and R ₅ are hydrogen, alkyl or halogen And R ₇ is hydrogen or alkyl.

In terms of application, the present invention relates to (a) a silicone resin containing at least two alkoxysilyl bonds per molecule, and (b) 0.01 to 10% by weight of the silicone resin in a solid content ratio. A thermosetting resin composition comprising the benzylpyridinium sulfonate.

In still another aspect, the present invention provides:
(A) a silicone resin containing at least two alkoxysilyl group bonds per molecule, and (b) an amount of 0.1 to 10 hydroxyl groups per alkoxysilyl bond of the silicon resin. A film-forming resin containing at least two hydroxyl groups per molecule;
(C) A thermosetting resin composition comprising the benzylpyridinium sulfonate in an amount of 0.01 to 10% by weight based on the total amount of the silicone resin and the hydroxyl group-containing resin in solid content.

The benzylpyridinium sulfonate compound is stable until the critical temperature is reached, and therefore does not exhibit the catalytic effect of sulfonic acid. However, when the critical temperature is reached, the bond between the benzyl group and the nitrogen atom is broken to generate a benzyl cation, which reacts with the OH group or water in the system to provide a proton, and the sulfonic acid is supplied only there. You. Therefore, in the system containing the above-mentioned benzylpyridinium sulfonate compound as a catalyst, a substantial curing reaction does not occur below the cleavage temperature of the compound, but a critical storage reaction in which the curing reaction proceeds only when heated above the cleavage temperature. It has stability.

Detailed Discussion I. Synthesis of benzylpyridinium sulfonate

[0016]

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The quaternary ammonium salt of the formula is

[0018]

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The pyridine of the formula

[0020]

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(Wherein X is a halogen), which is quaternized with a benzyl halide, and the resulting pyridinium halide halide anion is reacted with the corresponding alkali metal salt of benzenesulfonic acid. .

Wherein R ₁ , R ₂ , R ₃ and R ₆ are hydrogen, halogen,
Selected from alkyl, alkoxy, nitro, amino, alkylamino, cyano, alkoxycarbonyl or carbamoyl. R ₄ and R ₅ are selected from hydrogen, alkyl or halogen. R ₇ is hydrogen or alkyl having up to 20 carbon atoms.

The pyridinium sulfonate of the formula (I) is
Cleavage occurs when the temperature rises to generate the corresponding carbonium cation, which reacts with the OH group or moisture in the system to provide a proton to the sulfonate anion, and sulfonic acid, which functions as an acid catalyst, is supplied for the first time. Is done.

The cleavage temperature of the quaternary ammonium of the formula (I) can be controlled by selecting the type and position of the substituent on the α-position of the benzyl group and the benzene and pyridine rings.

II. A typical example of a silicone resin containing at least two alkoxysilyl bonds per molecule of a silicone resin containing an alkoxysilyl bond using a self-condensation or co-condensation reaction of an alkoxysilyl group is as follows.

(1) Acrylic tree containing alkoxysilyl group
A monomer having an alkoxysilyl group and an ethylenic double bond in a fat molecule forms an alkoxy group-containing acrylic polymer or copolymer by homopolymerization or copolymerization with another polymerizable monomer.

A first class of such monomers is represented by the general formula

[0028]

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An alkoxysilylalkyl ester of acrylic acid or methacrylic acid represented by the formula: In the formula
R is hydrogen or methyl, x is an integer of 1 or more, R ', R "is alkyl, and n is 0, 1 or 2.

Examples of these specific compounds include γ-
Methacryloyloxypropyltrimethoxysilane, γ-
Methacryloyloxypropylmethyldimethoxysilane,
γ-methacryloyloxypropyldimethylmethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropyltripropoxysilane, γ-methacryloyloxypropylmethyldipropoxy Examples include silane, γ-methacryloyldimethylpropoxysilane, γ-methacryloyloxypropyltributoxysilane, γ-methacryloyloxypropylmethyldibutoxysilane, and γ-methacryloyloxypropyldimethylbutoxysilane.

The second class is an adduct of (meth) acrylic acid with an epoxy group-containing alkoxysilane such as γ-glycidoxypropyltrimethoxysilane or δ- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. It is.

The third class is (meth) acrylic acid 2-
Hydroxyalkyl esters of (meth) acrylic acid such as hydroxyethyl, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate,
Compounds of the general formula OCN (CH ₂ ) _x Si (R ′) _n (OR ″) _3-n , for example γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropyltriethoxy It is an adduct with silane, γ-isocyanatopropylmethyldiethoxysilane and the like.

The last class consists of glycidyl (meth) acrylate and alkoxysilanes containing amino groups, for example γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-. Aminopropylmethyldimethoxysilane, N
-(2-aminoethyl) -3-aminopropyltrimethoxysilane, γ-aminopropyldimethylethoxysilane, adduct with γ-aminopropylmethyldiethoxysilane and the like.

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

(2) The amino group-containing alkoxysilane compound listed immediately before the silicon-modified epoxy resin is as follows:
Similarly, it can be used for producing an alkoxysilyl group-containing modified epoxy resin by an addition reaction with an epoxy group.

(3) Silicon-modified polyester resin The polyester resin having a free carboxyl group is the same as the epoxy group-containing alkoxysilane used in the addition reaction with (meth) acrylic acid to produce an alkoxysilyl group-containing acrylic monomer. To give a silicone-modified polyester resin.

The polyester resin having a free hydroxyl group is
In order to produce an alkoxysilyl group-containing acrylic monomer, it can be modified with the same isocyanate group-containing alkoxysilane that undergoes an addition reaction with a (meth) acrylic acid hydroxyalkyl ester to obtain a silicon-modified polyester resin.

[0038] As the resin containing at least two hydroxyl groups per molecule a hydroxyl group-containing resin, hydroxyl group-containing polyester resins, hydroxyl-terminated polylactone resin, an epoxy resin and hydroxyl group-containing acrylic resin is a typical example.

The polyester resin is obtained by a condensation reaction between a polycarboxylic acid or an acid anhydride thereof and a polyhydric alcohol, and a resin containing a hydroxy group at the terminal and / or intermediate of the polyester chain may be used. A hydroxyl-terminated polylactone resin may also be used.

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

The acrylic resin having a hydroxyl group is (meth)
Hydroxy group-containing monomers such as 2-hydroxyethyl acrylate and (meth) acrylic acids such as methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate Alkyl; can be obtained by copolymerizing styrene and its derivatives, other monomers such as (meth) acrylonitrile, vinyl acetate and the like by a conventional method.

Thermosetting Resin Composition The thermosetting resin composition of the present invention utilizing a self-condensation reaction of an alkoxysilyl group contains the silicone resin and the pyridinium sulfonate as essential components.

In the thermosetting resin composition of the present invention utilizing a co-condensation reaction between an alkoxysilyl group and a hydroxyl group,
Per one alkoxysilyl bond of the silicone resin,
The essential components include the hydroxyl group-containing resin in an amount such that the number of hydroxyl groups is 0.1 to 10 and the pyridinium sulfonate.

The pyridinium sulfonate is used in any case in an amount of 0.01 to 10% by weight, preferably 0.05 to 5.0% by weight, based on the solid content of the resin. If the compounding amount is too small, the curability will decrease, and if it is excessive, the appearance and physical properties will be adversely affected, such as coloring of the cured product and reduction in water resistance.

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

The composition of the present invention does not cure below the cleavage temperature of the pyridinium sulfonate and thus has good storage stability, but cures when heated above the cleavage temperature.
The curing time depends on the temperature, but is generally within one hour.

The following examples illustrate the invention. In the examples, “parts” and “%” are by weight.

I. Production Example Hexahydrophthalic acid 36 was added to a reaction vessel equipped with a heating device, a stirrer, a reflux device, a water separator, a rectification tower and a thermometer.
, 42 parts of trimethylolpropane, 50 parts of neopentyl glycol, and 56 parts of 1,6-hexanediol. When the raw materials are melted and stirring becomes possible, stirring is started and the temperature is raised to 210 ° C. The temperature is raised at a constant temperature from 210 ° C. to 230 ° C. over 2 hours, and the condensed water generated is distilled out of the system.

When the temperature reaches 230 ° C., the temperature is kept constant, and cooling is performed at a resin acid value of 1.0. After cooling, 153 parts of isophthalic acid are added, and the temperature is raised to 190 ° C again. The temperature is raised at a constant rate from 190 ° C. to 210 ° C. over 3 hours, and the condensed water generated is distilled out of the system. When the temperature reaches 210 ° C., 3 parts of xylene are added to the reaction vessel, the condensation is switched to the presence of a solvent, and the mixture is cooled to a resin acid value of 5.0.

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

Synthetic Production Example 2 of Acrylic Resin A solution of Solvesso 100 was placed in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, N 2 gas inlet tube and dropping funnel.
After raising the temperature to 160 ° C. while introducing N 2 gas, 23.2 parts of 2-hydroxyethyl methacrylate, 35.65 parts of n-butyl acrylate, 40.15 parts of methyl methacrylate, and 1.15 parts of methacrylic acid. A mixture of 0 parts and 10 parts of tert-butylperoxy-2-ethylhexanoate was dropped at a constant rate using a dropping funnel.

One hour after the completion of the dropping of the mixture, a mixture of 10 parts of xylene and 1 part of tert-butylperoxy-2-ethylhexanoate was dropped at a constant speed in 30 minutes. After completion of dropping, the mixture was aged for 2 hours and then cooled to obtain an acrylic resin [A].

Synthesis and Production Example 3 of Silicon Resin 45 parts of xylene was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, an N2 gas inlet tube and a dropping funnel. After heating to γ-
A mixture of 50 parts of methacryloyloxypropyltrimethoxysilane and 4 parts of tert-butylperoxy-2-ethylhexanoate was dropped at a constant speed from the dropping funnel over 3 hours.

After maintaining the temperature for 30 minutes after the completion of dropping of the mixture, 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 dropped while maintaining the temperature. The solution was dropped at a constant speed in one hour.

After completion of the dropwise addition, 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, thermometer, reflux condenser, N2 gas inlet tube and dropping funnel, and the temperature was raised to 130 ° C. while introducing N2 gas. Later, γ-
Methacryloyloxypropylmethyldimethoxysilane 5
A mixture of 0 parts and 4 parts of tert-butylperoxy-2-ethylhexanoate was dropped at a constant speed from the dropping funnel over 3 hours.

After keeping the temperature for 30 minutes after the completion of dropping of the mixture, 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 dropped while maintaining the temperature. The solution was dropped at a constant speed in one hour.

After completion of the dropwise addition, 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, thermometer, reflux condenser, N2 gas inlet tube and dropping funnel, and the temperature was raised to 130 ° C. while introducing N2 gas. Later, γ-
Methacroyloxypropyldimethylmethoxysilane 5
A mixture of 0 parts and 4 parts of tert-butylperoxy-2-ethylhexanoate was dropped at a constant speed from the dropping funnel over 3 hours.

After keeping the temperature for 30 minutes after the completion of dropping of the mixture, 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 dropped while maintaining the temperature. The solution was dropped at a constant speed in one hour.

After completion of the 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 inlet tube and a dropping funnel, and the temperature was raised to 130 ° C. while introducing N2 gas. Later, γ-
A mixture of 50 parts of methacryloyloxypropyltriethoxysilane and 4 parts of tert-butylperoxy-2-ethylhexanoate was dropped at a constant rate from the dropping funnel over 3 hours.

After keeping the temperature for 30 minutes after the completion of dropping of the mixture, 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 dropped while maintaining the temperature. The solution was dropped at a constant speed in one hour.

After completion of the dropwise addition, 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, an N2 gas inlet tube and a dropping funnel, and the temperature was raised to 130 ° C. while introducing N2 gas. Later, γ-
Methacryloyloxypropyltriethoxysilane 25
, A mixture of 25 parts of methyl methacrylate and 4 parts of tert-butylperoxy-2-ethylhexanoate were dropped at a constant speed from the dropping funnel over 3 hours.

After maintaining the temperature for 30 minutes after the completion of dropping the mixture, 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 dropped while maintaining the temperature. The solution was dropped at a constant speed in one hour.

After completion of the dropwise addition, 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 a polyester resin solution [A] was charged into a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser. After the temperature was raised to 100 ° C., 0.2 parts of dibutyltin dilaurate was added. Plus KB
M-9007 (Shin-Etsu Chemical Co., Ltd .: Structural formula OCN (CH ₂ ) ₃ Si (OCH ₃ )
₃ ) 10 parts were dropped at a constant speed from the dropping funnel in 30 minutes. 1
After aging for a while, the mixture was cooled to obtain a silicone resin solution [F].
1720 in the IR spectrum of the obtained resin solution
The absorption due to the NCO group at cm ^-1 had disappeared.

Production Example 9 100 parts of bisphenol A diglycidyl ether was charged into a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser.
After the temperature was raised to 50 ° C., 100 parts of γ-aminopropyltrimethoxysilane was dropped at a constant speed from the dropping funnel in 1 hour.
After aging for 1 hour, the mixture was cooled to obtain a silicone resin solution [G].

II. Example 1 100 parts of acrylic resin [A], 30.9 parts of silicon resin [A], 5 parts of methanol and N-benzyl-4 '
2.62 parts of -cyanopyridinium-p-dodecylbenzenesulfonate were mixed, the mixture was uniformly applied on a steel plate, set for 2 hours, and baked at 140 ° C for 30 minutes to obtain a cured coating film. The curing reactivity of the coating film and the storage stability test of the mixed solution were performed under the conditions shown in Table 1,
The results shown in Table 1 were obtained.

Example 2 100 parts of acrylic resin [A], 28.9 parts of silicone resin [B], 5 parts of methanol and N- (2-chlorobenzyl) -4-cyanopyridinium-p-dodecylbenzenesulfonate 2.58 parts were mixed, the mixed solution was uniformly applied on a steel plate and set for 2 hours.
Baking was performed at 0 ° C. for 30 minutes to obtain a cured coating film. The study was conducted in the same manner as in Example 1.

Example 3 100 parts of acrylic resin [A], 26.9 parts of silicone resin [C], 5 parts of methanol and N- (2,4-dichlorobenzyl) -4'-cyanopyridinium-p-dodecyl After mixing 2.54 parts of benzenesulfonate, the mixed solution was uniformly applied on a steel plate, set for 2 hours, and baked at 140 ° C. for 30 minutes to obtain a cured coating film. The study was conducted in the same manner as in Example 1.

Example 4 100 parts of acrylic resin [A], 36.2 parts of silicon resin [D], 5 parts of methanol and N- (2-methylbenzyl) -2-cyanopyridinium-p-dodecylbenzenesulfonate After mixing 2.72 parts, the mixed solution was uniformly applied on a steel plate and set for 2 hours.
Baking was performed at 0 ° C. for 30 minutes to obtain a cured coating film. The study was conducted in the same manner as in Example 1.

Example 5 100 parts of acrylic resin [A], 43.4 parts of silicone resin [E], 5 parts of methanol and N- (4-nitrobenzyl) -2-methylpyridinium-p-dodecylbenzenesulfonate After mixing 2.87 parts, the mixed solution was uniformly applied on a steel plate and set for 2 hours.
Baking was performed at 0 ° C. for 30 minutes to obtain a cured coating film. The study was conducted in the same manner as in Example 1.

Example 6 100 parts of acrylic resin [A], 10.3 parts of silicone resin [A], and 20 parts of Cymel 303 (melamine resin).
2.6 parts of 6 parts, 5 parts of methanol and 2.62 parts of N- (α-methylbenzyl) -4-chloropyridinium-p-dodecylbenzenesulfonate, uniformly apply the mixture on a steel plate and set for 2 hours. 140 ℃
For 30 minutes to obtain a cured coating film. The study was conducted in the same manner as in Example 1.

Example 7 100 parts of acrylic resin [A], 28.9 parts of silicone resin [B], 5 parts of methanol and N- (α-methylbenzyl) -4-cyanopyridinium-p-dodecylbenzenesulfonate After mixing 2.58 parts of the same, the mixed solution was uniformly applied on a steel plate and set for 2 hours.
Baking was performed at 0 ° C. for 30 minutes to obtain a cured coating film. The study was conducted in the same manner as in Example 1.

Example 8 100 parts of acrylic resin [A], 26.9 parts of silicon resin [C], 5 parts of methanol and 2.54 of N- (α-dimethylbenzyl) -pyridinium-p-toluenesulfonate The mixed solution was uniformly applied on a steel plate and set for 2 hours, and baked at 140 ° C. for 30 minutes to obtain a cured coating film. The study was conducted in the same manner as in Example 1.

Example 9 100 parts of a polyester resin [A], 30 parts of a silicon resin [F], 5 parts of methanol and 2.87 of N- (2-methylbenzyl) -4-fluoropyridinium-p-toluenesulfonate Partly mixed, uniformly apply the mixture on a steel plate and set for 2 hours.
It was baked at 30 ° C. for 30 minutes to obtain a cured coating film. Example 1 below
The study was conducted in the same manner as described above.

Example 10 100 parts of a polyester resin [A], 18 parts of a silicone resin [G], 5 parts of methanol and 2.87 parts of N- (4-methoxybenzyl) -pyridinium-p-toluenesulfonate were mixed. The mixture was uniformly applied on a steel plate, set for 2 hours, and baked at 140 ° C. for 30 minutes to obtain a cured coating film. The study was conducted in the same manner as in Example 1.

Example 11 100 parts of acrylic resin [A], 10.3 parts of silicone resin [A], Cymeru 303 (melamine resin)
2.6 parts of 6 parts, 5 parts of methanol and 2.62 parts of N-benzylpyridinium-p-dodecylbenzenesulfonate, uniformly apply the mixture on a steel plate, set for 2 hours, and baked at 140 ° C. for 30 minutes. Thus, a cured coating film was obtained. The study was conducted in the same manner as in Example 1.

Comparative Example 1 100 parts of acrylic resin [A], 30.9 parts of silicone resin [A], 2 parts of pyridine dodecylbenzenesulfonate and 5 parts of methanol were mixed, and the mixture was uniformly spread on a steel plate. After applying for 2 hours and setting at 140 ° C
For 30 minutes to obtain a cured coating film. Hereinafter, the same examination as in Example 1 was performed.

Comparative Example 2 100 parts of acrylic resin [A], 30.9 parts of silicone resin [A], 2.62 parts of triethylamine dodecylbenzenesulfonate and 5 parts of methanol were mixed.
The mixed solution was uniformly applied on a steel plate, set for 2 hours, and baked at 140 ° C. for 30 minutes to obtain a cured coating film. Hereinafter, the same examination as in Example 1 was performed.

[0083]

[Table 1]

1) MEK rubbing test (100 round trips)
Times) Appearance of coating film after ◎: No abnormality in coating film, ○: Slightly dissolved film, Δ: Cloudy film,
×: Dissolution of coating film 2) Change in viscosity in a closed system at room temperature (2 weeks) ：: No thickening, ○: Slightly thickening, Δ: Gelling after 2 weeks, ×: Gelling after 1 week

III. Example 12 Self-Condensation System of Alkoxysilyl Group Example 12 100 parts of a silicon resin solution [A], 5 parts of methanol and 0.5 part of N- (2-chlorobenzyl-4-cyanopyridinium-p-dodecylbenzenesulfonate) were mixed. The mixed solution was uniformly applied on a steel plate, set for 2 hours, and baked at 140 ° C. for 30 minutes to obtain a cured film, which was examined in the same manner as in Example 1.

Example 13 A cured film was obtained in the same manner as in Example 12 except that the silicone resin solution [A] was used instead of the silicone resin solution [A]. Hereinafter, the same examination as in Example 1 was performed.

Example 14 A cured film was obtained in the same manner as in Example 12, except that the silicone resin solution [A] was used instead of the silicone resin solution [A]. Hereinafter, the same examination as in Example 1 was performed.

Example 15 A cured film was obtained in the same manner as in Example 12 except that the silicone resin solution [F] was used instead of the silicone resin solution [A]. The study was conducted in the same manner as in Example 1.

Example 16 100 parts of silicone resin [B], 5 parts of methanol and 2.58 of N- (α, α-dimethylbenzyl) -4-chloropyridinium-p-dodecylbenzenesulfonate
The mixed solution was uniformly applied on a steel plate and set for 2 hours, and baked at 140 ° C. for 30 minutes to obtain a cured coating film. The study was conducted in the same manner as in Example 1.

Comparative Example 3 100 parts of a silicone resin [A] and 5 parts of methanol were mixed, the mixture was uniformly applied on a steel plate, set for 2 hours, baked at 140 ° C. for 30 minutes, and cured. I got

Comparative Example 4 100 parts of the silicone resin [A], 2 parts of triethylamine dodecylbenzenesulfonate and 5 parts of methanol were mixed, and a cured film was obtained in the same manner as in Comparative Example 3. Hereinafter, the same examination as in Example 1 was performed.

[0092]

[Table 2]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C08L 63/00 NJP C08L 63/00 NJP 67/00 LPB 67/00 LPB (72) Inventor Masamichi Furukawa 19-17 Ikedanakacho, Neyagawa-shi, Osaka Japan Paint Co., Ltd. No. 19-17 Japan Paint Co., Ltd. (56) References JP-A-51-58952 (JP, A) JP-A-50-56438 (JP, A) US Pat. No. 4,789,614 (US, A)

Claims (5)

(57) [Claims] 1. A silicone resin containing 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 ₆ are hydrogen, halogen, alkyl, alkoxy, nitro, amino, alkylamino, cyano, alkoxycarbonyl or carbamoyl, and R ₄ and R ₅ are hydrogen, alkyl or halogen Wherein R ₇ is hydrogen or alkyl.) With benzylpyridinium sulfonate. 2. The silicone resin is an acrylic polymer or copolymer containing at least one monomer having the alkoxysilane bond and the ethylenic double bond in the molecule, and a polyester resin having a carboxyl group. A silicon-modified polyester resin obtained by reacting an epoxy group-containing alkoxysilane with an epoxy group, a silicon-modified polyester resin obtained by reacting a hydroxyl group-containing polyester resin with an isocyanate group-containing alkoxysilane, or an amino group-containing alkoxysilane with an epoxy resin 4. The thermosetting resin composition according to item 3, which is a silicon-modified epoxy resin obtained by reacting 3. A silicone resin containing at least two alkoxysilyl group bonds per molecule, and (b) 0.1 to 10 hydroxyl groups per alkoxysilyl bond in the silicon resin. An amount of a film-forming resin containing at least two hydroxyl groups per molecule, and (c) a formula of 0.01 to 10% by weight of the total amount of the silicone resin and the hydroxyl group-containing resin in a solid content ratio. Embedded image Wherein R ₁ , R ₂ , R ₃ and R ₆ are hydrogen, halogen, alkyl, alkoxy, nitro, amino, alkylamino, cyano, alkoxycarbonyl or carbamoyl, and R ₄ and R ₅ are hydrogen, alkyl or halogen Wherein R ₇ is hydrogen or alkyl.) With benzylpyridinium sulfonate. 4. The silicone resin is an acrylic polymer or copolymer containing at least one monomer having the alkoxysilane bond and the ethylenic double bond in a molecule, and a polyester resin having a carboxyl group. A silicon-modified polyester resin obtained by reacting an epoxy group-containing alkoxysilane with an epoxy group, a silicon-modified polyester resin obtained by reacting a hydroxyl group-containing polyester resin with an isocyanate group-containing alkoxysilane, or an amino group-containing alkoxysilane with an epoxy resin 4. The thermosetting resin composition according to item 3, which is a silicon-modified epoxy resin obtained by reacting 5. The thermosetting resin composition according to claim 3, wherein the hydroxyl-containing resin is a hydroxyl-containing polyester resin, a hydroxyl-terminated polylactone resin, an epoxy resin, or a hydroxyl-containing acrylic resin.