JPH0491182A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition suitable as a vehicle for coatings, adhesives, printing inks etc., comprising a hydroxyl group-contg. resin, melamine resin and specific benzylammonium sulfonate at a specified proportion. CONSTITUTION:The objective composition comprising (A) a hydroxyl group- contg. film-forming resin, (B) such an amount of a melamine resin as to be (50:50)-(95:5) in the weight ratio, based on the component A, in terms of solid content, and (C) as thermally potential curing catalyst, 0.01-10wt.%, based on the total amount of the components A and C, in terms of solid content, of a benzylammonium sulfonate of the formula [R1, R2 and R3 are each H, halogen, alkyl, alkoxy, nitro, alkyl(amino), cyano, etc.; R4 and R5 are each H, alkyl, halogen, etc.; R6, R7 and R8 are each alkyl, alkenyl, phenyl, etc.; R9 is H or alkyl].

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting resin composition using a novel benzyl ammonium sulfonate, which is thermally cleaved to release a sulfonic acid, as a thermally latent curing catalyst. Such compositions are useful as vehicles for paints, adhesives, printing inks, and the like.

In one-component paints that use aromatic sulfonic acids, which are proton donors, as curing catalysts, amine salts of sulfonic acids are blocked with volatile amines to prevent early curing reactions such as gelation of the paint during storage. has been used. However, in such a sulfonic acid amine salt, R5Off-・tt"N(R)i→R3O3-+H'
Since there is an equilibrium such as N(R): + ← R3Os −+ H” + N(R)s, the amount of amine must be reduced in order to exhibit the effect of sulfonic acid at relatively low temperatures. As a result, the amount of unblocked sulfonic acid increases and the storage stability of the system decreases.If the amount of amine is increased to increase storage stability, the amount of sulfonic acid that has become an amine salt will increase, making the sulfonic acid more effective. In order to achieve this, it is necessary to heat the product to a high temperature.The system using the amine salt of sulfonic acid that has been used conventionally has the disadvantage that it is difficult to control the curing temperature and achieve storage stability at the same time. was there.

For example, thermosetting resin compositions made of acrylic resins, polyester resins, epoxy resins, etc. having hydroxyl groups and melamine resins are widely used in the paint field. These melamine resin curing resin compositions contain a proton donor, such as para-toluenesulfonic acid, as a catalyst for the curing reaction. However, in systems containing free acids, the resin tends to gel, and low-temperature curability and storage stability of the composition are generally not compatible. Therefore, it has been proposed to use a compound in which sulfonic acid is blocked with an amine as a catalyst, but its curability and storage stability have not always been satisfactory.

Japanese Patent Publication No. 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, the self-condensation reaction of alkoxysilane RO5i−± −5iOR+ R20→
-5i-0-Si +2RO)1 and co-condensation reaction of alkoxysilane and hydroxyl group RO5i −+ HO−
It is believed that curing occurs by C-→-5i-0-C-+ ROH.

Conventionally, as catalysts for these self-condensation and co-condensation reactions, butylamine, dibutylamine, 1-butylamine,
Amines such as ethylenediamine, tetraisopropyl titanate, tetrabutyl titanate, tin octylate,
Metal-containing compounds such as lead octylate, zinc octylate, calcium octylate, dibutyltin diacetate, dibutyltin diacetate, dibutyltin dilaurate, p
-Acidic compounds such as toluenesulfonic acid and trichloroacetic acid were used.

However, as can be understood from the fact that systems containing such catalysts can be cured at room temperature, they cannot be stably stored for long periods of time while containing catalysts. Therefore, if long-term storage stability is desired, it is necessary to take measures such as adding a catalyst immediately before use as a two-part product, reducing the amount of catalyst, or blocking with an amine or acid that is active during curing. It is.

However, using a two-component method has problems with workability and restrictions such as having to use it within the pot life.Other countermeasures also reduce membrane performance and make it difficult to completely block the product, resulting in insufficient storage stability. There are problems such as the blocking amine or acid volatilizes and causes coloration and unpleasant odor.

Therefore, the present invention is a thermosetting resin using a compound that is stable up to a critical temperature near the curing temperature, but thermally cleaves once the critical temperature is reached, releasing sulfonic acid and exerting its catalytic effect. An object of the present invention is to provide a composition.

Honshuhadasotou! The present invention provides a thermally latent curing catalyst using the formula [wherein R1, R
2 and R3 are hydrogen, halogen, alkyl, alkoxy, nitro, amino, alkylamino, cyano, alkoxycarbonyl or carbamoyl, R=Rs is hydrogen, alkyl or halogen, Rb Rt and R8 are alkyl, alkenylmathaphenyl (optionally substituted with alkyl, halogen, nitro, cyano, alkoxy, amino or dialkylamino) and R1 is hydrogen or alkyl.

] using benzyl ammonium sulfonate.

In terms of use, the present invention comprises: (a) a film-forming resin containing hydroxyl groups;
9515, and (c) the benzyl ammonium sulfophyte in an amount of 0.01 to 10% by weight of the total amount of the hydroxyl group-containing resin and the melamine resin in terms of solid content weight ratio. A thermosetting resin composition is provided.

In another application aspect, the present invention comprises: (a) a silicone resin containing an alkoxysilyl bond; and (b) the benzylammonium sulfonate in an amount of 0.01 to 10% by weight of the silicone resin in terms of solid content. Provided is a thermosetting resin composition characterized by the following.

In yet another aspect of use, the present invention provides (a) a silicone resin containing an alkoxysilyl group bond; and (b) the silicone resin having 0.1 to 10 hydroxyl groups per alkoxysilyl bond. and (c) the benzyl ammonium sulfonate in a solid content of 0.01 to 10% by weight of the total amount of the silicone resin and the hydroxyl group-containing resin. A thermosetting resin composition is provided.

The benzylammonium sulfonate compound is stable until a critical temperature is reached and therefore does not exhibit the catalytic effect of sulfonic acid. However, when a critical temperature is reached, the bond between the benzyl group and the nitrogen atom is broken and a benzyl cation is generated, which reacts with the OH group or water in the system and donates a proton, which is the first time that sulfonic acid is supplied. Ru.

Therefore, the system containing the benzylammonium sulfonate compound as a catalyst has a critical storage condition in which a substantial curing reaction does not occur below the cleavage temperature of the compound, but the curing reaction proceeds only when heated above the cleavage temperature. Has stability.

1. The quaternary ammonium salt of the synthesis formula of benzylammonium sulfonate is the ammonium salt produced by quaternizing the tertiary amine of the formula (the blank below) with the benzyl halide of the formula (wherein, X is a halogen). It can be produced by reacting the halide anion of a halide with the corresponding benzenesulfonic acid or an alkali metal salt of an alkylhenzenesulfonic acid whose alkyl moiety has up to 20 carbon atoms.

In the formula, R5 to R, are as described above.

The ammonium sulfonate of formula (1) cleaves when the temperature rises to generate the corresponding hensyl cation, which reacts with OH groups or moisture in the system to donate protons to the sulfonate anion, producing acid For the first time, a sulfonic acid is provided which acts as a catalyst.

(2) Systems containing melamine resin Film-forming resins using melamine resin as a curing agent are widely used in the paint field.

Examples of these are polyester resins, polylactone resins,
Epoxy resin, acrylic resin, etc.

The polyester resin can be obtained by a condensation reaction of a polyhydric carboxylic acid or its acid anhydride with a polyhydric alcohol, and may contain a hydroxy group at the end and/or the middle of the polyester chain.

Hydroxyl terminated polylactone resins may also be used.

Examples of the epoxy resin include resins having an epoxide group at the end and a hydroxyl group in the middle of the molecular chain, such as bisphenol type epoxy resin and/or novolac type epoxy resin.

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;
It can be obtained by copolymerizing styrene and its derivatives with other monomers such as (meth)acrylonitrile and vinyl acetate by a conventional method.

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

Thermosetting resin compositions comprising a combination of a film-forming resin having hydroxyl groups and a melamine resin are well known in the paint field, and the composition of the present invention uses the above-mentioned thermally cleavable ammonium sulfonate as a catalyst for the curing reaction. Except for this, it may be the same as a known melamine resin curing type thermosetting composition.

The ratio of the film-forming resin having hydroxyl groups to the melamine resin may be 50,150 to 9,515 by weight.

The ammonium sulfonate is blended 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 amount is too small, the curability will decrease, and if it is too much, it will cause adverse effects on the appearance and physical properties, such as coloration of the cured product and a decrease in water resistance.

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

(2) Typical examples of silicone resins containing silicon alkoxysilyl bonds that utilize a self-condensation or co-condensation reaction of alkoxysilyl groups include the following.

(1) Alkoxysilyl 4 A monomer having an alkoxysilyl group and an ethylenic double bond in the acrylic molecule can be made into an alkoxy group-containing acrylic polymer or copolymer by homopolymerization or by copolymerization with other polymerizable monomers. Create.

The first class of such monomers is - up to % formula %)
: It is an alkoxysilylalkyl ester of acrylic acid or methacrylic acid represented by: 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-methacroyloxypropyltrimethoxysilane, γ-methacroyloxypropylmethyldimethoxysilane, γ-methacroyloxypropyldimethylmethoxysilane, T-methacroyloxypropyltriethoxysilane, T-Methacroyloxypropylmethyljethoxysilane, γ-
Methacroyloxypropyltriproboxysilane, T
-Metacroyloxypropylmethyldipropoxysilane, γ-Metacroyldimethylpropoxysilane, γ
-Methacroyloxypropyltributoxysilane, T
-methacroyloxypropylmethyldibutoxysilane, γ-methacroyloxypropyldimethylptoxysilane, and the like.

The second class are adducts of (meth)acrylic acid with alkoxysilanes containing epoxy groups, such as T-glycidoxypropyltrimethoxysilane or δ-(3°4-epoxycyclohexyl)ethyltrimethoxysilane.

The third class consists of hydroxyalkyl esters of (meth)acrylic acid, such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and - up to % formula %), such as adducts with γ-isocyanatopropyltrimethoxysilane, T-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropyltriethoxysilane, T-isocyanatopropylmethyljethoxysilane, etc.

The last class is (meth)acrylic acid glycidyl ester and alkoxysilanes containing amino groups, such as T-aminopropyltrimethoxysilane, T-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyl Dimethoxysilane, N-(2-aminoethyl)-3-aminoprobyltrimethoxysilane, T
It is an adduct with -aminopropyldimethylethoxysilane, T-aminopropylmethyljethoxysilane, etc.

Monomers that can be copolymerized with alkoxysilyl group-containing acrylic monomers include various (meth)acrylic acid esters, styrene, (meth)acrylic acid, (meth)acrylonitrile, (meth)acrylamide, vinyl chloride, vinyl acetate, etc. .

(2) Silicon/Epoxy The amino group-containing alkoxysilane compounds listed just before are:
It can likewise be used to produce modified epoxy resins containing alkoxysilyl groups by addition reaction with epoxy groups.

(3) Silicon Polyester Polyester resins with free carboxyl groups are modified with the same epoxy group-containing alkoxysilanes used in the addition reaction with (meth)acrylic acid to produce acrylic monomers containing alkoxysilyl groups, and silicon It can be a modified polyester resin.

Polyester resins with free hydroxyl groups can be modified with the same isocyanate group-containing alkoxysilanes that are subjected to an addition reaction with (meth)acrylic acid hydroxyalkyl esters to produce alkoxysilyl group-containing acrylic monomers, resulting in silicone-modified polyester resins. .

Typical examples of resins containing hydroxyl groups include hydroxyl group-containing polyester resins, hydroxyl group-terminated polylactone resins, epoxy resins, and hydroxyl group-containing acrylic resins.

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

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

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

The thermosetting resin composition of the present invention that utilizes the self-condensation reaction of hyalkoxysilyl groups contains the silicone resin and the ammonium sulfonate as essential components.

In the thermosetting resin composition of the present invention that utilizes a co-condensation reaction between an alkoxysilyl group and a hydroxyl group, the number of hydroxyl groups is 0.1 to 10 per alkoxysilyl bond of the silicone resin. Such amounts of the hydroxyl group-containing resin and the ammonium sulfonate are essential components.

The ammonium sulfonate is used in an amount of 0.01 to 10% by weight, preferably 0.01% by weight, based on the resin solid content in each case.
05 to 5.0% by weight. If the amount is too small, the curability will decrease, and if it is too much, it will cause adverse effects on the physical properties such as a decrease in the water resistance of the cured product.

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 harden below the cleavage temperature of the ammonium sulfonate and therefore has good storage stability, but hardens when heated to a temperature above the cleavage temperature. The curing time depends on the temperature, but is generally within 1 hour.

The invention will be illustrated by the following examples. In the examples, "part" and "1%" are by weight.

(2) Production Example Polyester 11 Production Example 1 36 parts of hexahydrophthalic acid and 42 parts of trimethylolpropane were placed in a reaction tank equipped with a heating device, a stirrer, a reflux device, a water separator, a rectification column and a thermometer. , 50 parts of neopentyl glycol, and 56 parts of 1,6-hexanediol were charged and heated. When the raw materials are melted and can be harvested, the harvesting is started and the temperature is raised to 210°C. The temperature is raised from 210°C to 230°C over 2 hours at a constant temperature, and the condensed water produced is distilled out of the system.

When the temperature reaches 230°C, the temperature is kept constant and the resin is cooled to a resin acid value of 1.0. After cooling, 153 parts of isophthalic acid was added and the temperature was raised to 190°C again. 190°C to 21
The temperature is raised at a constant rate over 3 hours to 0"C, and the condensation water produced is distilled out of the system. When the temperature reaches 210°C, 3 parts of xylene is added to the reaction tank, and the condensation is switched to the presence of a solvent. , and cooled at a resin acid value of 5.0.

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

Acrylic 8-A Production Example 2 Into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a N2 gas introduction tube, and a dropping funnel, 1. After charging 90 parts of OO and raising the temperature to 160°C while introducing N2 gas, 23.2 parts of 2-hydroxyethyl methacrylate, 35°65 parts of n-butyl acrylate, 40.15 parts of methyl methacrylate, 1.0 part of methacrylic acid and ter
t-Butylperoxy-2-functional tylhexanoate 10
The mixture was added dropwise at a constant rate using a dropping funnel.

One hour after the completion of dropping the mixture, a mixture of 10 parts of xylene and 1 part of tert-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate over 30 minutes.

After aging for 2 hours after the completion of dropping, cool the acrylic resin (A).
I got it.

Silicone Production Example 3 of 2 45 parts of xylene was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a N2 gas introduction tube, and a dropping funnel, and the temperature was raised to 130'C while introducing N2 gas. After warming, γ
-Methacroyloxypropyltrimethoxysilane 50
A mixture of 1 part and 4 parts of tert-butylperoxy-2-ethylhexanoate was added dropwise from the dropping funnel at a constant rate over 3 hours.

After incubating for 30 minutes after dropping the mixture, the inside of the reaction system was heated to 90"
tert-butylperoxy-
A mixture of 1 part of 2-ethylhexanoate and 5 parts of xylene was added dropwise from the dropping funnel at a constant rate over 1 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, a thermometer, a reflux condenser, a N2 gas introduction pipe, and a dropping funnel, and the temperature was raised to 130'C while introducing N2 gas. T
A mixture of 50 parts of -methacroyloxypropylmethyldimethoxysilane and 4 parts of tert-butylperoxy-2-ethylhexanoate was added dropwise from the dropping funnel at a constant rate over 3 hours.

After incubating for 30 minutes after dropping the mixture, the inside of the reaction system was heated to 90°.
tert-butylperoxy-
A mixture of 1 part of 2-ethylhexanoate and 5 parts of xylene was added dropwise from the dropping funnel at a constant rate over 1 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 CB).

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 introduction pipe, and a dropping funnel, and the temperature was raised to 130°C while introducing N2 gas. T-
Methacroyloxypropyldimethylmethoxysilane 5
A mixture of 0 parts and 4 parts of tert-butylperoxy-2-ethylhexanoate was added dropwise from the dropping funnel at a constant rate over 3 hours.

After incubating for 30 minutes after dropping the mixture, the inside of the reaction system was heated to 90"
tert-butylperoxy-
A mixture of 1 part of 2-ethylhexanoate and 5 parts of xylene was added dropwise from the dropping funnel at a constant rate over 1 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 [C].

Production Example 6 45 parts of xylene was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a N2 gas introduction tube, and a dropping funnel, and the temperature was raised to 130°C while introducing N2 gas. T-
A mixture of 50 parts of methacroyloxypropyltriethoxysilane and 4 parts of tert-butylperoxy-2-ethylhexanoate was added dropwise from the dropping funnel at a constant rate over 3 hours.

After incubating for 30 minutes after dropping the mixture, the inside of the reaction system was heated to 90°.
tert-butylperoxy-
A mixture of 1 part of 2-ethylhexanoate and 5 parts of xylene was added dropwise from the dropping funnel at a constant rate over 1 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 CD).

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 introduction pipe, and a dropping funnel, and the temperature was raised to 130°C while introducing N2 gas, and then γ - 25 parts of methacroyloxyprobyltriethoxysilane,
A mixture of 25 parts of methyl methacrylate and 4 parts of tert-butylperoxy-2-ethylhexanoate was dropped isocratically from the dropping funnel over 3 hours.

After incubating the mixture for 30 minutes, the inside of the reaction system was heated to 90°C.
tert-butylperoxy-2 while keeping warm.
- A mixture of 1 part of ethylhexanoate and 5 parts of xylene was added through the dropping funnel in a constant manner over a period of time.

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 A reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser was charged with a polyester resin solution (100 parts of AE, and heated at 100"C.
After raising the temperature to
z) ssi(OCH+>3) 10 parts were added to the solution through a dropping funnel in 30 minutes. After aging for 1 hour, it was cooled to obtain a silicone resin solution [F]. The absorption caused by the NCO group at 1720 cm-' in the IR spectrum of the obtained resin solution 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 an M flow cooling device, and 1
After the temperature was raised to 50° C., 100 parts of γ-aminopropyltrimethoxysilane was added isocratically through the dropping funnel over a period of 1 hour.

After aging for 1 hour, it was cooled to obtain a silicone resin solution [G].

■ Melamine resin curing system Example 1 70 parts of Plaxel 308 (trifunctional polycaprolactone polyol, molecular weight 860, manufactured by Daicel), 30 parts of Cymel 303 (melamine resin, manufactured by Mitsui Toatsu) and N-
Two parts of (p-methylbenzyl)-N,N-dimethylanilium-p-dodecylbenzenesulfonate were added and mixed, and the mixture was coated on a tin plate and baked at 140°C to obtain a cured coating. The curing reactivity and storage stability of the mixture were tested under the conditions shown in Table 1, and the results shown in Table 1 were obtained.

Example 2 Cymel 303 (melamine resin manufactured by Mitsui Toatsu Co., Ltd.) N-(p-chlorobenzyl)-N,N-dimethylayulinium to 70 parts of Plaxel 308 (trifunctional polycaprolactone polyol manufactured by Daicel, molecular weight 860) -5 parts of p-dodecylbenzenesulfonate were added and mixed, and the mixture was coated on a tin plate and baked at 140°C to obtain a cured coating. The following study was conducted in the same manner as in Example 1.

Example 3 50 parts of Cymel 303 (melamine resin manufactured by Mitsui Toatsu Co., Ltd.) and N-
Two parts of (2,4-dichlorobenzyl)-N,N-dimethylayulinium-p-dodecylbenzenesulfonate were added and mixed, and the mixture was coated on a tin plate and baked at 140°C to obtain a cured coating. The following study was conducted in the same manner as in Example 1.

Example 4 Polyester resin A Cymel 3 for 90 parts solids
03 (melamine resin manufactured by Mitsui Toatsu Co., Ltd.) 10 parts and N-(2
-methylbenzyl)-NN-diethyl aurinium-p
- Add 2 parts of dodecylbenzene sulfonate and mix;
It was applied to a tin plate and baked at 140°C to obtain a cured coating. The following study was conducted in the same manner as in Example 1.

Example 5 Polyester resin A: 60 parts of solids to kneepants 2
03E (melamine resin manufactured by Mitsui Toatsu Co., Ltd.) as a resin solid content of 40 parts and N-(2,4-dimethylpencil)-N,
1 part of N-dimethylanilinium p-)luenesulfonate was added and mixed, coated on a tin plate and baked at 140°C to obtain a cured coating. The following study was conducted in the same manner as in Example 1.

Example 6 Polyester resin A Kneepan 2 for 70 parts solids
03E (melamine resin manufactured by Mitsui Toatsu Co., Ltd.) as a resin solid content of 30 parts and N-(4-methoxybenzyl)-N,N-
Dimethylanilinium-P-toluenesulfonate 0
．． 05 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 following study was conducted in the same manner as in Example 1.

Example 7 Polyester resin A: 20 parts of knee pants for 60 parts of solid content
40 parts of SE (melamine resin manufactured by Mitsui Toatsu Co., Ltd.) as a resin solid content and N-(α,α-dimethylbenzyl)-N,N
-Two parts of dimethylanilinium P-dodecylbenzenesulfonate were added and mixed, and the mixture was coated on a tin plate and baked at 140°C to obtain a cured coating. The following study was conducted in the same manner as in Example 1.

Example 8 Polyester resin A Knee pan 2 for 70 parts solids
30 parts of 03E (melamine resin manufactured by Mitsui Toatsu Co., Ltd.) as a resin solid content and 2 parts of N-(α-methylhensyl-N-hydroxyethyl-NN-dimethylammonium-p-dodecylbenzenesulfonate) were added and mixed. It was applied to a plate and baked at 140°C to obtain a cured coating film.The following study was conducted in the same manner as in Example 1.

Example 9 Contains acrylic resin Cymel 303 for 90 parts solids
Add 10 parts of melamine resin (manufactured by Mitsui Toatsu Co., Ltd.) and 0.5 part of N-benzyl-NN-dimethylayulinium-p-dodecylbenzenesulfonate, mix, apply on a tin plate, and harden by baking at 140°C. A coating film was obtained. Example 1 below
We conducted a similar study.

Example 10 Acrylic resin A Kneepan 203 for 60 parts solids
E (melamine resin manufactured by Mitsui Toatsu Co., Ltd.) as a resin solid content of 4
0 part and 0.1 part of N-(2-chlorobenzyl)-N,N-dimethylayulinium-p-toluenesulfonate were added and mixed, and the mixture was coated on a tin plate and baked at 140°C to form a cured coating. Obtained.

The following study was conducted in the same manner as in Example 1.

Example 11 Acrylic resin A Kneepan 203 for 70 parts solids
E (melamine resin manufactured by Mitsui Toatsu Co., Ltd.) as a resin solid content of 3
0 parts and 2 parts of N-(4-methoxybenzyl)-N,N-dimethylayulinium-p-toluenesulfonate were added and mixed, and the mixture was coated on a tin plate and baked at 140'C to obtain a cured coating. .

The following study was conducted in the same manner as in Example 1.

Example 12 Acrylic resin A Cymel 303 for 90 parts solids
(Melamine resin manufactured by Mitsui Toatsu Co., Ltd.) 10 parts and N-(α-methylbenzyl)-N,N-dimethylayulinium-p-
Two parts of dodecylbenzenesulfonate were added and mixed, applied to a tin plate and baked at 140°C to obtain a cured coating.

The following study was conducted in the same manner as in Example 1.

Example 13 Acrylic resin A Kneepan 203 for 70 parts solids
E (melamine resin manufactured by Mitsui Toatsu Co., Ltd.) as a resin solid content of 3
0 parts and N-(α,α-dimethylpencyl)-N,N-
Add 2 parts of dimethylanilinium-P-dodecylbenzenesulfonate, mix, apply on a tin plate, and heat at 140°C.
A cured coating film was obtained by baking. The following study was conducted in the same manner as in Example 1.

Comparative Example 1 30 parts of Cymel 303 (melamine resin manufactured by Mitsui Toatsu) and p-
) Two parts of luenesulfonic acid triethylamine salt were added and mixed, and the mixture was coated on a tin plate and baked at 140°C to obtain a cured coating. The curing reactivity and storage stability of the mixture were tested under the conditions shown in Table 1, and the results shown in Table 1 were obtained.

Comparative Example 2 Cymel 3 for 90 parts of solid content of polyester resin A
10 parts of 03 (melamine resin manufactured by Mitsui Toatsu Co., Ltd.) and 2 parts of p-dodecylbenzenesulfonic acid pyridine salt 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 following study was conducted in the same manner as in Example 1.

Comparative Example 3 Acrylic resin A Kneepan 203 for solid content 60 parts
Add and mix 40 parts of E (melamine resin manufactured by Mitsui Toatsu Co., Ltd.) as resin solids and 2 parts of p-)luenesulfonic acid pyridine salt, apply on a tin plate, and bake at 140°C to obtain a cured coating. Ta. The following study was conducted in the same manner as in Example 1.

(Left below) Table 1. Characteristics of mixed liquid and cured coating reactivity 1) ◎ ○ ○ ○ ◎ ○ ◎ ○ ◎
Storage stability 2ゝ O◎ ◎ ◎ ○ ◎ ○ ◎ Q curing reactivity 1) Storage stability 2) ○ ○ ○ ◎ ◎ ◎ ◎ OO○ ××× 1) MEK ◎2△: 2〕 40 ◎: △ Appearance of paint film after Nirubbing test (100 times back and forth) No abnormalities in the paint film, ○: Slightly dissolved paint film, cloudy paint film, ×: Change in viscosity in closed system at °C after melting paint film (2 weeks) No viscosity increase, ○ : Slightly thickened.

Thickening, x: gelation after 2 weeks ■, co-condensation system of alkoxysilyl group and hydroxyl group, and self-condensation system of alkoxysilyl group Example 14 100 parts of acrylic resin (A), 30 parts of silicone resin (A). 9 parts, methanol 5 parts and N-benzyl-N,
Mix 2.62 parts of N-dimethylanilinium-P-dodecylbenzenesulfonate, apply the mixture uniformly on a steel plate, let it set for 2 hours, and then bake at 140°C for 30 minutes to form a cured coating. I got it. The curing reactivity of the coating film and the storage stability test of the mixed solution were conducted under the conditions shown in Table 2, and the results shown in Table 2 were obtained.

Example 15 100 parts of acrylic resin (A), 28.9 parts of silicone resin CB), 5 parts of methanol, and N-(2-chlorobenzyl)-N,N-dimethylanilinium-p-F decylbenzenesulfonate. After 2.58 parts of the mixture was uniformly applied onto a steel plate and allowed to set for 2 hours, it was baked at 140°C for 30 minutes to obtain a cured coating. The following study was conducted in the same manner as in Example 14.

Example 16 100 parts of acrylic resin (A), 26.9 parts of silicone resin (c), 5 parts of methanol, and N-(2,4-dichlorobenzyl)-N,N-dimethylanilinium-p-
2.54 parts of dodecyl hanzene sulfonate was mixed, and the mixed solution was uniformly applied onto a steel plate, allowed to set for 2 hours, and then baked at 140°C for 30 minutes to obtain a cured coating film. The following study was conducted in the same manner as in Example 14.

Example 17 100 parts of acrylic resin (A), 36.2 parts of silicone resin CD), 5 parts of methanol, and N-(2-methylbenzyl)-N,N-dimethyl-N=(m-)lyl)ammonium -P-dodecylbenzenesulfonate 2.7
Two parts were mixed, and the mixed solution was uniformly applied onto a steel plate, set for 2 hours, and then baked at 140°C for 30 minutes to obtain a cured coating film. The following study was conducted in the same manner as in Example 14.

Example 18 100 parts of acrylic resin (A), 43.4 parts of silicone resin (E), 5 parts of methanol, and N-(4-nitrobenzyl)-N,N-dimethylayulinium-p-dodecylbenzenesulfonate. 28,787 parts mixed, after applying the mixed solution uniformly on the steel plate and setting it for 2 hours,
A cured coating film was obtained by baking at 140°C for 30 minutes. The following study was conducted in the same manner as in Example 14.

Example I9 100 parts of polyester resin (A), silicone resin CF
), 5 parts of methanol, and 2.87 parts of N(2-methylhensyl)-N,N-diethylanilinium-P-dodecylbenzenesulfonate, and the mixture was evenly applied onto a steel plate. After setting the time,
A cured coating film was obtained by baking at 140°C for 30 minutes. The following study was conducted in the same manner as in Example 14.

Example 20 100 parts of polyester resin (A), silicone resin [G
), 5 parts of methanol, and 2.87 parts of N(4-methoxybenzyl)-N,N-dimethylanilinium-P-dodecylbenzenesulfonate were mixed, and the mixed solution was uniformly applied onto a steel plate. After setting for 2 hours, it was baked at 140°C for 30 minutes to obtain a cured coating. The following study was conducted in the same manner as in Example 14.

Example 21 100 parts of acrylic resin (A), 10.3 parts of silicone resin (8), 20.6 parts of Cymel 303 (melamine resin)
5 parts of methanol and 2.62 parts of N-(α-methyl=4-chlorobenzyl)-N-hydroxyethyl-N,N-dimethylammonium-p-dodecylbenzenesulfonate, and the mixture was After applying it uniformly onto a steel plate and setting it for 2 hours, it was baked at 140°C for 30 minutes to obtain a cured coating. The following study was conducted in the same manner as in Example 14.

Example 22 100 parts of acrylic resin [A], 28.9 parts of silicone resin [B], 5 parts of methanol, and N-(α-methylhensyl)-N,N,N-)dimethylammonium-p-
A mixture of 28,585 parts of dodecylbenzene sulfonate was mixed and the mixed solution was uniformly applied onto a steel plate, set for 2 hours, and then baked at 140"C for 30 minutes to obtain a cured coating film. The following was the same as in Example 14. We conducted a study on the following.

Example 23 100 parts of acrylic resin CA, ), silicone resin [C
], 5 parts of methanol, and 2.54 parts of N-(αmethylbenzyl)-N,N-dimethylayulinium-p-toluenesulfonate, and the mixture was uniformly spread on a steel plate. After applying and setting for 2 hours,
A cured coating film was obtained by baking at 0°C for 30 minutes. The following study was conducted in the same manner as in Example 14.

Example 24 100 parts of silicone resin CB), 5 parts of methanol and N-(α,α-dimethyl-4-chlorobenzyl)-N,
Mix 2.58 parts of N-dimethylayulinium-p-dodecylbenzenesulfonate, apply the mixture uniformly on a steel plate, let it set for 2 hours, and then bake it at 140"C for 30 minutes to harden the coating. A membrane was obtained.

The following study was conducted in the same manner as in Example 14.

Example 25 100 parts of silicone resin (A), 5 parts of methanol, and 0.5 parts of N-benzyl-N,N-dimethylanilinium-P-dodecylhenzensulfonate were mixed, and the mixed solution was spread uniformly on a steel plate. After setting for 2 hours, it was baked at 140°C for 30 minutes to obtain a cured film. The following study was conducted in the same manner as in Example 14.

Comparative Example 4 100 parts of silicone resin (A), 5 parts of methanol, and 2 parts of p-toluenesulfonic acid triethylammonium salt
．． After 58 parts of the mixture was uniformly applied onto a steel plate and allowed to set for 2 hours, it was baked at 140''C for 30 minutes to obtain a cured coating.

The same study as in Example 14 was conducted below.

Comparative Example 5 100 parts of acrylic resin (A), 30.9 parts of silicone resin [A], 2.62 parts of p-dodecylbenzenesulfonate pyridine salt, and 5 parts of methanol were mixed, and the mixed solution was poured onto a steel plate. After applying it uniformly to the surface and setting it for 2 hours, it was baked at 140°C for 30 minutes to obtain a cured coating film.

The same study as in Example 14 was conducted below.

(Leaving space below) Table 2. Characteristics of mixed solution and cured coating film Curing reactivity I) ◎ ◎ ◎ ◎ ◎ ◎ ◎ O storage stability 2) ○ ○ ○ ○ ○ ○ 0 Example curing reactivity 1) Storage Stability 2ゝ0 ◎ ◎ ◎ ○ ◎ OO○ ○ △ × 1) Paint film appearance after MEK rubbing test (100 round trips) ◎: No paint film abnormality, ○: Slight film dissolution, △: Paint film cloudy, ×: Paint film dissolution 2) Viscosity change in a closed system at room temperature (2 weeks)

Claims (3)

[Claims] (1) (a) A film-forming resin containing a hydroxyl group,
(b) 50 in terms of solid content weight ratio to the hydroxyl group-containing resin
melamine resin in an amount of /50 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 melamine resin in solid content weight ratio ▲ Numerical formula, chemical formula, table, etc. Yes▼ [In the formula, R_1, R_2 and R_3 are hydrogen, halogen,
alkyl, alkoxy, nitro, amino, alkylamino, cyano, alkoxycarbonyl or carbamoyl, R_4 and R_5 are hydrogen, alkyl or halogen, R_6, R_7 and R_8 are alkyl, alkenyl or phenyl (alkyl, halogen, nitro, optionally substituted with cyano, alkoxy, amino or dialkylamino), and R_9 is hydrogen or alkyl. A thermosetting resin composition comprising benzyl ammonium sulfonate. (2) (a) A silicone resin containing an alkoxysilyl bond and (b) A formula of 0.01 to 10% by weight of the silicone resin in terms of solid content ratio ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [R_1 in the formula , R_2 and R_3 are hydrogen, halogen,
alkyl, alkoxy, nitro, amino, alkylamino, cyano, alkoxycarbonyl or carbamoyl, R_4 and R_5 are hydrogen, alkyl or halogen, R_6, R_7 and R_8 are alkyl, alkenyl or phenyl (alkyl, halogen, nitro, Cyano,
optionally substituted with alkoxy, amino or dialkylamino), and R_9 is hydrogen or alkyl. A thermosetting resin composition comprising benzyl ammonium sulfonate. (3) (a) a silicone resin containing an alkoxysilyl group bond; and (b) containing an amount of hydroxyl groups such that the number of hydroxyl groups is 0.1 to 10 per alkoxysilyl bond in the silicone resin. A film-forming resin and (c) a solid content ratio of 0.01 to 10% by weight of the total amount of the silicone resin and the hydroxyl group-containing resin▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2 and R_3 is hydrogen, halogen,
alkyl, alkoxy, nitro, amino, alkylamino, cyano, alkoxycarbonyl or carbamoyl, R_4 and R_5 are hydrogen, alkyl or halogen, R_6, R_7 and R_8 are alkyl, alkenyl or phenyl (alkyl, halogen, nitro, Cyano,
optionally substituted with alkoxy, amino or dialkylamino), and R_9 is hydrogen or alkyl. A thermosetting resin composition comprising benzyl ammonium sulfonate.