JPH0243202A - Catalyst for polymerization and curable composition containing the same - Google Patents

Abstract

PURPOSE:To provide a catalyst for polymerization which gives a curable composition that is highly sensitive to heat and light and excellent in photocurability, thermocurability, storage stability and the like by using a specific pyridinium salt as an active component. CONSTITUTION:A pyridinium salt represented by formula I or II (wherein R1 and R2 are each an electron attractive group or H; X<-> is a non-nucleophilic anion; R3 is H, alkyl or alkoxy; and n is 1 or 2) is used as an active component to produce a catalyst for polymerization. Examples of the pyridinium salt of formula I or II include 1-benzyl-2-chloropyridinium hexafluoro-antimonate and 1-benzyl-2-cyanopyridinium hexafluoroantimonate. A curable composition containing the catalyst for polymerization comprising the pyridinium salt and a cationically polymerizable compound and/or a radical-polymerizable compound is effective as a latent curable composition.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a polymerization catalyst and a curable composition containing the polymerization catalyst and a cationically polymerizable compound and/or a radically polymerizable compound.

(Issue 8 to be solved by the present technology and the present invention in 1) Currently, even if a catalyst is added to a cationic polymerizable compound in advance, polymerization does not start at room temperature, and polymerization cannot be initiated immediately by light, heat, pressure, etc. A polymerization catalyst that initiates polymerization, that is, has a high so-called latent potential, is desired.

Since then, examples of photopolymerization catalysts include aromatic diazonium salts. This product is a cationic polymerizable compound, such as an epoxy resin, with light B+? 1, it can be cured quickly.

However, diazonium salts release nitrogen through photolysis, which can cause defects in the coating.

In addition, the mixture with resin has such poor storage stability that polymerization proceeds gradually even in the dark. Also, JP-A-48-
There is an example of photo-curing using a compound that generates carboxyl groups and amino groups by light irradiation, as shown in No. 88197, but the activity of this compound is not sufficient.
Releases carbon dioxide during curing, causing defects in the coating.

Studies were conducted to improve the above rI problem, and
131996 and JP-A-50-151997 disclose photocurable pellets containing aromatic iodonium salts and aromatic sulfonium salts. Although these problems have been improved, the curability is still not sufficient, and furthermore, aromatic sulfonium salts are bad-smelling low-molecular-weight compounds that decompose and produce when irradiated with light, so the coating film is tinged with odor and electricity. That's it!
! There was a problem.

In addition, thermal polymerization catalysts (so-called thermosetting latent curing agents)
Conventionally, Lewis acid-amine complexes such as BFz.H2N CtHs are known, but these do not have sufficient curability.

Furthermore, it decomposes during curing and generates BFz gas, which may attack metals. In addition, dicyandiamide is a widely used thermal polymerization catalyst.
This product provides a cured product with good adhesion and has a long pot life. However, it requires a lot of heat during curing and its compatibility with resins is ¥! For this reason, fine powder is used by dispersing it, but there was a problem in that the specific gravity of the two particles was high and caused them to settle.

(!!Means for solving the problem) First, 1-benzyl-4-cyanopyridinium hexafluorophosphate was filtered out. It was discovered that it is effective as a thermal polymerization catalyst that has interstitial properties and is active against heat, and filed an application (Special Edition No. 62-218967). The present inventors are even more keen! As a result of extensive investigation, it was discovered that when a curable composition containing the second catalyst and a cationically polymerizable compound is immediately exposed to light, it is rapidly cured. We have also discovered that a curable composition containing this catalyst and a radically polymerizable compound can be rapidly cured when exposed to light. These are two things that could not have been predicted in the past. In addition, the present inventors have investigated various pyridinium salts.
As a result of investigation, the inventors discovered that a specific pyridinium salt has excellent latent properties and is effective as a polymerization catalyst that exhibits high activity against heat and light, leading to the completion of the present invention.

That is, the present invention provides the following formula: (]) (R
+, RS imaginary and hydrogen atom at the same time; Also, n represents 1 or 2 (However.

One of R1 and R2 is a hydrogen atom, and the other is a 4-
(2) A thermosetting composition containing the polymerization catalyst of (1) and a cationic polymerizable compound, (3) General formula (■), (In the formula, R1 and R2 represent an electron-withdrawing group or a hydrogen atom; R+, R2! are not hydrogen atoms at the same time), represents an alkoxy group, and n represents 1 or 2. )), and (4) a composition curable by light or a combination of light and heat, containing the photopolymerization catalyst of (3) and a cationically polymerizable compound and/or a radically polymerizable compound. It is something that is placed between things.

General formula (1) and (■) above! Specifically, Kookero R and R2 are a hydrogen atom, or an electron-withdrawing group such as a chlorine atom, a bromine atom, an iodine atom, a cyano group, a flukoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group, a vinyl group, styryl group, carbamoyl group, N-
Examples include N-substituted rubamoyl groups such as methylcarbamoyl group and N,N-dimethylcarbamoyl group. R5
and R2 are not water-branched atoms at the same time, especially in general formula (1), when one of R1 and R2 is a hydrogen atom, the other is not a cyano group at the 4-position. , it is preferable that at least one of them is in the α- or β-position.In addition, R1 specifically represents an alkyl group such as methyl, ethyl, propyl, butyl, t, er t-butyl group, methoxy, Examples include alkoxy groups such as ethoxy, propoxy, isopropoxy, butoxy, and ter↑-butoxy groups, and hydrogen atoms, and substituent groups such as ortho or) (ortho or) are preferred.

The cations of the pyridinium salt according to the present invention include lolobiridine, bromopyridine, cyanopyridine, vinylpyridine, styryl pyridine, carboxymethylpyridine, carboxyethylpyridine, carbamoylpyridine, dichloropyridine, dicyanopyridine, chlorocyanobi+7dine, etc. Substituted pyridine, benzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group,
Examples of cations derived from substituents such as ethoxybenzyl group, isopropoxybenzyl group, and phenylenebis(methylene) group are given below.
) is a non-tussophilic 7-ion, specifically S b
F 6-, As F *-, P Fa-, B
Examples include F a-, C104- and CF+SOt-.

More specific examples of the pyridinium salts according to the present invention include, for example,
-'t-zν "8-2-ri OO Little One" Chive L -1
4 1 no 1st Ronesfeet (1-C) I-Benseea 1t-2-Uro 0 Hi'lin Niu L11 No. 71 0? (1-D) 1-Henshi R-2-
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Month 101 (Nate (3) l-(4・Mefil)
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l-henshi It-2no? Call 710047.71-to (4-(2) l-to "Jino" 11-2-no? no 7'reshi: Umtetraf atn Negotiation (54) to l-) ；NT3-ノ7ノHI0
linonium l1t07 int nate (5-B)
I. Heshinium It-3-n R nohi'nium Hex-Drop II Oromoto Sufu 2-) (5-C) To l-"
Synth 3-7 No. 0 polymer tetrafluoro (6-A) 1- No. 4- No. 7 No. 11 No. 17" To leek L 17 look t07 Digit (6-A) -B)
l-to-L sea 1f-4-no? /H"Q sonium to 417MtO book 27ite (6・C)l-・λ"2 note 4-norno70 lithium tetrafluor to book 1
-To (7・G l-) In-2-hi 2 nhi 59
Color: Umhexaph 8 o 07 inch tnate (7-8)
,-,,+S,゛to4-hi''2hehi0lissiniumtoNo.1ftoyintimode2-to(8-Ul-he゛)No.2-2chiryrrhythiniumheheheheNo.1 full 407
ft2-t (8-8) 1-'s -L J'''n
-4-15Shhi"l>-2') 41 full tOr> to L
ft2-) (9) 1-Heshin "toko.5-no"ri 0
0 Hi 0 Renew Niu L・11 call F1140? Shi4tnate(to)l-\”shishito3,5-Nono?Nohi1
1ν゛2 Rim-14! Function (ll-4) l-=1-shi'1-n-2-hn ~ Noe 4 Ruhi 0 Lissinium lIA Call Form 4 Or Notimont (ll-8) 1-Hesi -11, -4-1) Le book ``Hesier 5 Rubilishi'': Rim 11 Ki-Ko Fluororone 4t Neat(+2) I- t2-t(130,I'-[1,4-phenyl(megton)]hexaphent(14),I' 4, 4-7
Single or two! One or more types may be used in combination.

The pyridinium salts represented by formulas (1) and (■) of the present invention can be produced by known methods. For example, in a solvent such as methanol, acetonitrile, N, N-dimethylformamide, or in the absence of a solvent. After substituting and reacting lysine with substituted or unsubstituted benzyl halide in one chamber to one stream, anion exchange is performed with NaMFs (M = Sb, P, As, etc.) in water or methanol. It can be easily obtained by

A polymerization catalyst consisting of a pyridinium salt represented by the general formula (■) of the present invention, or a photopolymerization catalyst consisting of a pyridinium salt represented by the general formula (■) (hereinafter, these catalysts are collectively referred to as the polymerization catalyst of the present invention). ) is particularly limited; however, cationic polymerizable compounds and radical polymerizable compounds are suitable. As cationic polymerizable compounds, for example, , 13-tetradecadiene dioxide, Limonene dioxite, 4-vinylcyclono＼
Xene dioxide, 3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexylcarboxylate, bis(3,4-epoxycyclohexyl)adipate, phenyl glycidyl ether, bisphenol, helical epoxy resin, halogen bisphenol A
type epoxy resin, o-, m-, p-cresol novolac type epoxy resin, phenol novolac type epoxy resin, epoxy compounds such as polyglycidyl ether of polyhydric alcohol, styrene, α-methylstyrene, p-chloromethylstyrene, etc. Styrenes, alkyl vinyl ethers such as n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, allyl vinyl ether,
Alkenyl vinyl ethers such as 1-octahydronaphthyl vinyl ether, alkynyl vinyl ethers such as ethynyl vinyl ether and propargyl vinyl ether,
7-aryl vinyl ethers such as phenyl vinyl ether and p-methoxyphenyl vinyl ether, allyl vinyl ether dimethanol divinyl ether such as butanediol divinyl ether, triethylene glycol divinyl ether, and cyclohexanediol divinyl ether, N-m-chlorophenyl diethanolamine divinyl ether, 7-ralkyl divinyl ethers such as m-phenylene bis(ethylene glycol) divinyl ether, aryl divinyl ethers such as hydroquinone divinyl ether and resorcinol divinyl ether, N-vinylcarbazole, N
- Cationically polymerizable N-containing compounds such as vinylpyrrolidone,
Cyclic ether compounds such as tetrahydrofuran, s-trioxane, 3,3-bischloromethyloxetane,
l-Phenyl-4-ethyl-2.6.7-dryoxabicyclo[2,2,21 octane, 1-ethyl-4-hydroxymethyl-2,6,7-)lioxabicyclo[2
, 2,21 octane and other bicycloorthoester compounds, 5.7°11-tetraoxaspiroC5,5]undecane, 3.9-dibenzyl-1,5,7°11-tetraoxaspiro[:5.5 ]'7-ndecane and other spiroorthocarbonate compounds; These include spiroorthoester compounds such as 4,51 decane, and these may be used alone or in combination of two or more.

In addition, radical polymerizable compounds (for example, styrenes such as styrene, p-chloromethylstyrene,
Vinyl pyridines, monofunctional acrylates such as ethyl acrylate, isopropyl acrylate, hydroxypropyl acrylate, propylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, neobentyl glycol hydroxybiparate diacrylate, trimethylolpropane Triacrylate, polyfunctional acrylate monomers such as pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and oligomers thereof, methacrylate Q such as methyl methacrylate, hydroxyethyl methacrylate, isopropyl methacrylate, vinyl chloride, vinylidene chloride, vinyl acetate, butadiene, maleic anhydride, acrolein, acrylonitrile, methacrylateril, etc.;
They may be used alone or in combination of two or more.

In addition, lV! of cationically polymerizable compounds! Alternatively, a mixture of two or more kinds and 1 fl or two or more kinds of radically polymerizable compounds in an appropriate ratio may be used.

The curable composition of the present invention can be used, for example, in adhesives, paints, laminates, and the like. Furthermore, since it can be photocured, heat-sensitive electrons can be used as a coating or sealant for materials. Furthermore, by using both light and heat, it is possible to cover and bond objects with complex shapes.

The curable composition of the present invention also includes an inert solvent, a pigment,
Dyes, talc, calcium carbonate, glass fibers, surfactants, etc. may be added.

Cationically polymerizable compound and/or by the polymerization catalyst of the present invention
Alternatively, the polymerization of the radically polymerizable compound is carried out in the presence or absence of a solvent, with respect to the polymerizable compound at a rate of 0.1-1
Adding 5% by weight, preferably 0.5-101i% of the catalyst of the present invention and irradiating with light such as electron beams or ultraviolet rays, or heating to 100° C. or higher, preferably 120”C or higher. It can be implemented by

It can also be carried out by using both light and heat.

The present invention will be specifically described below with reference to Examples. In the text, unless otherwise specified, parts represent parts by weight.

Synthesis Example 1 Synthesis of 1-benzyl-2-chloropyridinium I\xafluoroantimonate (example (synthesis of arsenic compound (1-1)).

200 equipped with a stirrer, reflux condenser, and thermometer
85.ml of benzyl aromide in a 4 flask.
15g (0.5 mol), 2-chloropyridine 56.8g
(0.5 mol) and reacted at 60° C. for 6 hours with stirring. After the reaction, acetonitrile was added to the product and the crystals were filtered.

The obtained crystals were recrystallized from ethanol to give 56.9 g of 1-
Benzyl-2-chloropyridinium bromide was obtained.

Dissolve the i4 rare crystals in water and add Na5bFs.
5.7 g (0.2 mol) was added, and the precipitated rope-colored crystals were separated. By recrystallizing these crystals with methanol, 1-benzyl-
2-chloropyridinium hexafluoroantimonate was obtained (yield 22%).

IR (cm-'): KBr method 1610. 1560. 1490. 1450
゜7B0. 750° 660° Synthesis Example 2
-5 Several types of pyridinium salts were synthesized by the same method as Synthesis W41. The results are shown in Table 1.

Make 15 fruits 100 parts of Epicoat 828 (Hisphenol A epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.); 1-J\
5 parts of 2-chloropyridinium hexafluoroantimonate (exemplified compound (A)) was added to obtain a homogeneous curable composition. After applying this material on a glass plate using a #8 bar coater, we irradiated it with ultraviolet rays from a distance of 10 cm using a 120 W/cm metal halide lamp made of Eye Graphics 7, and it became tack-free in 15 seconds. Ta. Also, 180℃ of this formulation
The gelation time was 208. Furthermore, the pot life of this product at 40°C under light shielding is 6 months or more, and the potency is very good.

Real 1i! ! lt.2-8 In the same manner as in step 1, the vinyldinium salt and 1-benzyl-4-cyanopyridinium salt obtained in Synthesis Example 2-6 were subjected to ultraviolet curing and pot life tests. The results are shown in Table 2.

Table 2 For comparison, a curable composition containing a diazonium salt (Asahi Denka Co., Ltd. 7 Deca Ultraset PP-33) was similarly cured with ultraviolet light.
C brought tears to my eyes. Further, the cured film obtained from the curable composition of the present invention did not have any bubbles or odor.

Note that all of these curable compositions were homogeneous.

Example 9 Seven Oxide 2021 (NOKU 3.4 manufactured by Daicel Chemical Co., Ltd.)
-epoxycyclohexyl)methyl-3,4-epoxycyclohexyl carboxylate) to 100 parts
5 g of benzyl-2-chloropyridinium hexafluoroantimonate (exemplified compound (1-A)) was added to obtain a uniform curable composition. Place this on the glass plate #8
The coating was applied using a bar coater of
When ultraviolet rays were irradiated from a distance of cm, it became tack-free in 9 seconds.

Examples 10-13 The pyridinium salts shown in Table 3 were cured with ultraviolet light in the same manner as in Example 9. The hardness of these materials was uniform. The results are shown in Table 3.

Example 14 5 parts of 1-benzyl-2-chloropyridinium hexafluoroantimonate (exemplified compound (1-A)) was added to 100 parts of Epicote 828 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.). A uniform curable composition was obtained. This one has a temperature of 25 at 160°C.
It was separated and hardened.

Table 3 Examples 15-16 In the same manner as in Example 6, the pyridinium salts shown in Table 4 were thermally cured at 150°C. These curable compositions also had uniform rolling properties. The results are shown in Table 4.

Table 4 Example 17 Sumi-epoxy ESCN-220L-15 (0-cresol novolac type epoxy resin manufactured by Sumitomo Chemical Co., Ltd.) 100
and 5 parts of 1-benzyl-2-chloropyridinium hexafluoroantisupernate were kneaded using a three-roll mill to obtain a curable product. This one has a temperature of 4 at 150℃
It was cured in 5 minutes.

Example 18 100 parts of Sumi-epoxy ESCN-22OL-15 (
0-cresol novolak type epoxy resin manufactured by Sumitomo Chemical Co., Ltd. and 5 parts of l-benzyl-2-cyanopyridinium hexafluoroandemonate were kneaded with a three-roll mill,
A curable composition was obtained. This cured in 15 minutes at 150°C.

Example 19 A glass plate coated with the curable composition obtained in Example 1 was
After heating to ℃, ultraviolet rays were emitted from a distance of 20 cm using an 80 W/cm metal halide lamp.
It hardened in 9 seconds.

The glass plate coated with the curable composition obtained in Example 3 was subjected to 60%
After heating to °C, ultraviolet light was applied from a distance of 20 cm using an 80 W/cm metal halide lamp, and the film was cured in 6 seconds.

Example 21 50 parts of Bisphenol A type epoxy resin manufactured by Heavy Shell Epoxy Co., Ltd. and UNION CA
RBIDE ERL-4299 (bis[3,4-epoxycyclohexylmethyl] manufactured by Union Carbide)
Adipate) 508B mixed resin with 1-benzyl-
Five parts of 2-chloropyridinium hexafluoroantimonate (exemplified compound (1-A)) was added to obtain a uniform curable silk composition. Coat this on a glass plate using a #8 bar coater, and
When irradiated with ultraviolet rays from a distance of 20 cm using a 0 W/cm metal halide lamp, it became tack-free in 16 seconds.

Example 22 Epicor) 828 (Bisphenol A epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.) 70 Qi and RAP ICtJR
E DYE-3 (GAF?) Add 5 parts of 1-benzyl-2-chloropyridinium hexafluoroantimonate (exemplified compound (1-A)) to a resin mixed with the nitriethylene glycol divinyl ether part of the above product to make a homogeneous mixture. A curable 8II product was obtained. This product was coated onto a glass plate using a #24 bar coater, and immediately exposed to ultraviolet light from a distance of 20 Cnl using a 1201 V/cm metal halide lamp manufactured by Eye Graphics. However, it became tack free in 4 seconds.

Fruit 11! Example 23 80 parts of Epicote 154 (phenol novolak type epoxy tree N manufactured by Yuka Shell Epoxy Co., Ltd.) and 2Ofll<
3 parts of 1-benzyl-2-chloropyridinium hexafluoroantimonate (exemplified compound (1-A)
) was added to obtain a uniform curable composition. #2 things
41 on a glass plate using a bar coater of 8! When the ultraviolet rays were analyzed from a distance of 20 cm using a 120 V/cm metal halide lamp manufactured by I-Graphics, it became tack-free in 1 second.

Example 24 1-benzyl-
5 parts of 2-chloropyridinium hexafluoroantimonate (exemplified compound (1-A)) was added to make a homogeneous v1
1 humiliation of 1 person.

This was applied onto a glass plate using a #8 bar coater, and coated with 120 W/C11 manufactured by Eye Graphics.
1. Ultraviolet rays are emitted from a distance of 20 cm using a metal halide lamp [! ? When I shot it, it became tack-free in 6 seconds.

Example 25 The initiator was converted from 1-benzyl-2-chloropyridinium hexafluoroantimonate (exemplified compound (1-A)) to 1-benzyl-4-cyanopyridinium hexafluoroantimonate (exemplified compound (6-A)). The same operation as in Example 24 was performed except for changing to 8)).As a result, 4
It became tack free in 0 seconds.

Example 26 50 parts of Ebicor) 82B (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.) and Viscoat 300
3 parts of 1-benzyl-2-chloropyridinium hexafluoroantimonate (exemplified compound (1-A)) was added to a resin mixed with 50 parts of pentaerythritol triacrylate (manufactured by Osaka Organic Co., Ltd.) to form a homogeneous system. A curable silk composition was obtained. This was applied onto a glass plate using a #8 bar coater, and 120XS manufactured by Eye Graphics was applied.
Ultraviolet rays from a distance of 20cm with a T/cm metal halide lamp! 1r4It L/, it became tack free in 5 seconds.

Example 27 The initiator was 1-\resilyl 2-chloropyridinium hexafluoroantimonate (exemplary compound (to l-0))
The same operation as in Example 26 was performed except that 1-non\nji-4-cyanobiricinium hexafluoroantimonate (exemplified (arsenic compound (6-A)) was used. As a result, in 35 seconds. It became tack free.

Example 28 50 parts of Epicoat 828 (oil (Hisphenol, He-type epoxy resin manufactured by Hinel Epokin) and 1 (HeYpeR)
50 parts of DDPHA (noventaerythritol hexaacrylate manufactured by Nippon Joyaku Co., Ltd.) was polymerized with r#: 1-benzyl-2-chloropyridinium hexafluoroantimonate (exemplified compound (1-)). A homogeneous curable composition was obtained. This material was coated on a glass plate using a #8 bar coater, and ultraviolet rays were irradiated on 20 copies from a distance of 1 from the mouth using a 120 W/cm metal halide lamp manufactured by Eye Graphics.
It became tack-free below 1 ft.

Really! 29 50 parts of Epicote 154 (phenol novolac type epoxy tree N manufactured by Yuka Shell Epoxy Co., Ltd.) and 30 parts of L
IN I ON CA RB [DEERL-4
221 (a cycloaliphatic epoxy resin manufactured by Union Carbide) and 20 parts of R9 to P ICURE DYE-3 (
A homogeneous hard ( Hypoallergenic MJ compound No. 11 was applied onto a glass plate using a #8 bar coater and coated with l2 manufactured by I-Graphics.
0 W/cm metal halide lamp with 20C111
UV rays from the mouth, from a distance? In Q1, he was tack free in 2 seconds.

Real control 151130 Ebiko) 82B (Hisphenol Yatsu epoxy resin manufactured by Oil 1 Hishiel Eboxy Co., Ltd.) 50 parts and 1-ethyl-4
-Hydroxymethyl-2,6,7°-trioxabincroC2,2,2] To a resin mixed with 50 parts of octane
-Benzyl-2-chloropyridinium I\xafluoroantimonate ()
A homogeneous @i1 arsenic grain was obtained. Coat the second thing on the glass plate using a #8 bar coater,
When I fired the purple 91 line [13] from a distance of 20 cm using a 120 V/cm metal halide lamp made by Icrafix, it became tack-free in 10 seconds.

(Effects of the Invention) As explained above, the curable silk fabric containing the polymerization catalyst and the cationically polymerizable compound and/or the radically polymerizable compound of the present invention has high photocurability and thermocurability, and The polymerization catalyst of the present invention has good solubility with cationically polymerizable compounds and radically polymerizable compounds. 1, ii It is an excellent injection catalyst.

Claims (1)

[Claims] 1. General formula (I), ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, R_1 and R_2 represent an electron-withdrawing group or a hydrogen atom (R_1 and R_2 are (not at the same time a hydrogen atom), X^- represents a non-nucleophilic anion and R_1 represents a hydrogen atom, an alkyl group or an alkoxy group.
n represents 1 or 2. (However, one of R_1 and R_2 is a hydrogen atom and the other is not a cyano group at the 4-position.)) A polymerization catalyst consisting of a pyridinium salt. 2. General formula (II), ▲Mathematical formula, chemical formula, table, etc.▼(II) (In the formula, R_1 and R_2 represent an electron-withdrawing group or a hydrogen atom (R_1 and R_2 are not hydrogen atoms at the same time) , X^- represents a non-nucleophilic anion and R_3 represents a hydrogen atom, an alkyl group or an alkoxy group.
n represents 1 or 2. ) A photopolymerization catalyst consisting of a pyridinium salt. 3. A composition curable by light or a combination of heat and light, which contains the photopolymerization catalyst according to claim 2 and a cationically polymerizable compound and/or a radically polymerizable compound. 4. A thermosetting composition comprising the polymerization catalyst according to claim 1 and a cationically polymerizable compound. 5. The pyridinium salt according to claim 1 or 2 is 1-benzyl-2-chloropyridinium hexafluoroantimonate, 1-benzyl-2-chloropyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoro At least one member selected from the group consisting of antimonate, 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-3-cyanopyridinium hexafluoroantimonate, and 1-benzyl-3-cyanopyridinium hexafluorophosphate. A polymerization catalyst that is a compound of 6. The polymerization catalyst according to claim 3 or 4 is 1-benzyl-2-chloropyridinium hexafluoroantimonate, 1-benzyl-2-chloropyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoro antimonate, 1-benzyl-2-
Cyanopyridinium hexafluorophosphate, 1-
A curable composition comprising at least one compound selected from the group consisting of benzyl-3-cyanopyridinium hexafluoroantimonate and 1-benzyl-3-cyanopyridinium hexafluorophosphate.