JP3480972B2 - Thermosetting composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting composition, and more particularly to a cationic curable composition which is cured by heating for a short time. Since the cured product of the composition has excellent physical properties, it is suitably used as a material for molding resins, casting resins, paints, adhesives, inks and the like.

[0002]

2. Description of the Related Art Japanese Patent Laid-Open No. 58-37003 discloses a cationic polymerization initiator and its composition.
JP-A-63-223002, JP-A-56-15283
3, JP-A-2-178319, JP-A-3-1711.
No. 9 is known.

[0003]

The cationic polymerization initiator is a useful initiator that can cure a cationically polymerizable compound in a short time. In particular, the so-called thermal latent cationic polymerization initiator that initiates the polymerization reaction by heat is
It is an important initiator that can be cured at a lower temperature and for a shorter time than the conventional curing of epoxy resins with amine compounds and acid anhydrides, and can be one-component. For example, these include a sulfonium salt compound described in JP-A-58-37003 and an ammonium salt compound described in JP-A-2-178319.

However, when an epoxy compound is cured using these initiators, a sulfide or a tertiary amine having basicity is generated as a leaving component, so that the cationic polymerization is stopped on the way and a good curing is achieved. However, it is difficult to obtain a substance having a high glass transition temperature or a high crosslinking density.

The present invention has been made in view of the above-mentioned circumstances, and provides a thermosetting composition capable of obtaining a cured product having a high glass transition temperature and a high crosslink density because cationic polymerization is unlikely to stop halfway. Is intended.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and found that an onium salt compound in which a nitrogen atom of a heterocyclic ring is quaternized and capable of cationic polymerization is initiated by cationic polymerization. When used as an agent, a thermosetting composition that can prevent the cationic polymerization termination reaction of the cationically polymerizable compound from occurring and increase the glass transition temperature and crosslink density of the cured product has been completed.

That is, the present invention is a thermosetting composition characterized by containing the following components [A] and [B]. Component [A]: Cationic polymerizable heterocyclic onium salt compound having a quaternized nitrogen atom [B] cationically polymerizable compound

The present invention will be described in detail below. (Component A) The component A of the present invention is capable of cationic polymerization,
It is a heterocyclic onium salt compound having a quaternized nitrogen atom. This onium salt compound is obtained by, for example, quaternizing an in-ring nitrogen atom of a heterocyclic compound such as an oxazoline derivative, an oxazine derivative, or a thiazoline derivative with an alkyl halide, an alkenyl halide, a dialkyl sulfuric acid, an alkylsulfonic acid ester, or the like to obtain NaBF. ₄ , K
It can be easily obtained by salt exchange with a non-nucleophilic alkali metal salt such as PF ₆ , NaAsF ₆ and KSbF ₆ .

The component A of the present invention is an onium salt compound in which the nitrogen atom in the ring is alkylated by a specific substituent, and is easily ring-opened and is itself cationically polymerized together with the cationic polymerizable compound which is the component B. It is characterized by being able to do.

As typical onium salt compounds of the present invention, those shown in the following chemical formulas 1 to 3 are exemplified.

[0011]

[Chemical 1]

[0012]

[Chemical 2]

[0013]

[Chemical 3]

(Component B) Examples of the cationically polymerizable compound used in the present invention include the following compounds. (A) As a compound having an epoxy group, 1,1,3-
Tetradecadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, (3,4
-Epoxycyclohexyl) methyl-3,4-epoxycyclohexylcarboxylate, di (3,4-epoxycyclohexyl) adipate, phenylglycidyl ether, bisphenol A type epoxy resin, halogenated bisphenol A type epoxy resin, o-, m-, Epoxy compounds such as p-cresol novolac type epoxy resin, phenol novolac type epoxy resin, polyglycidyl ether of polyhydric alcohol

(B) As vinyl compounds, styrene and α
-Styrenes such as methylstyrene and p-chloromethylstyrene; alkyl vinyl ethers such as n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether and hydroxybutyl vinyl ether;
Alkenyl vinyl ethers such as allyl vinyl ether and 1-octahydronaphthyl vinyl ether; alkynyl vinyl ethers such as ethynyl vinyl ether and 1-methyl-2-propenyl vinyl ether; aryl vinyl ethers such as phenyl vinyl ether and p-methoxyphenyl vinyl ether; butanediol divinyl ether , Alkyldivinyl ethers such as triethylene glycol vinyl ether and cyclohexanediol divinyl ether; aralkyl dialkyl ethers such as 1,4-benzenedimethanol divinyl ether, N-m-chlorophenyldiethanolamine divinyl ether and m-phenylenebis (ethylene glycol) divinyl ether. Vinyl ethers; hydroquinone divinyl ether, resorcinol divinyl ether Aryl divinyl ethers such as ether; N- vinylcarbazole, N- vinylpyrrolidone and cationic polymerizable nitrogen-containing compounds such

As the (c) bicyclo orthoester compound, 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2,2,2] octane, 1-ethyl-4-
Hydroxymethyl-2,6,7-trioxabicyclo [2,2,2] octane etc.

(D) As the spiro-orthocarbonate compound, 1,5,7,11-tetraoxaspiro [5,5]
5] Undecane, 3,9-dibenzyl-1,5,7,1
1-tetraoxaspiro [5,5] undecane, etc.
4,6-trioxaspiro [4,4] nonane, 2-methyl-1,4,6-trioxaspiro [4,4] nonane,
Examples thereof include spiro orthoester compounds such as 1,4,6-trioxaspiro [4,5] decane.

These may be used alone or in combination of two or more. Of the compounds (a) to (d), the compound having an epoxy group (a) is preferably used.

In the present invention, the onium salt compound and the cationically polymerizable compound are the cationically polymerizable compound 10
The onium salt compound is added in an amount of 0.01 to 20 parts, preferably 0.1 to 10 parts, relative to 0 parts. When the amount of this onium salt compound is small, the curability of the cationically polymerizable compound is lowered, and when it is excessive, the cured product properties are lowered.

The thermosetting composition of the present invention can be easily cured by heating. When heat curing, 20 to 200 ° C,
Preferably, it is used in the range of 50 to 180 ° C.

The thermosetting composition of the present invention contains α rays, β rays,
It can be easily cured in a short time by ionizing radiation such as γ rays, neutron rays, X rays, and accelerated electron rays. In the case of curing by ionizing radiation, it is usually 0.5 to 60 Mr.
A dose range of ad can be used, with a range of 1-50 Mrad being preferred. It is also possible to use ionizing radiation and heat in combination for curing.

To the thermosetting composition of the present invention, a curing agent such as a phenolic curing agent or an acid anhydride curing agent, which is usually used as a curing agent for epoxy resins, is used in combination within a range that does not impair the performance. You may use it.

When the initiator of the present invention is blended with the above-mentioned cationically polymerizable compound and used, a reactive diluent, a curing accelerator, a solvent, a pigment, a dye, a coupling agent, if necessary,
It is used by adding an inorganic filler, carbon fiber glass fiber, surfactant and the like.

[0024]

[Operation] The present invention is characterized in that an onium salt compound in which a nitrogen atom in a ring is alkylated by a specific substituent is used as a polymerization catalyst, and the onium salt compound is a polymerization catalyst and at the same time, a cation. To open the ring more easily,
It is capable of undergoing cationic polymerization by itself with the cationically polymerizable compound which is the B component.

That is, by quaternizing the nitrogen of a nitrogen-containing heterocycle capable of ring-opening by a cation and using an onium salt compound salt-exchanged with a non-nucleophilic anion as an initiator for cationic polymerization, (1) The nitrogen-containing heterocyclic compound produced by desorption of the cation can react with the cation at the polymerization end, and thus is not incorporated into the polymerization chain and does not itself inhibit the cationic polymerization. (2) The nitrogen-containing heterocycle of the onium salt compound itself opens at the start of polymerization,
Since it is incorporated into the polymer chain terminal, it does not itself inhibit the cationic polymerization. It is considered that the reaction occurs in any of these. Therefore, it is considered that the eliminated nitrogen-containing heterocycle does not hinder the cationic polymerization, so that the cationic polymerization is less likely to stop in the middle, and a cured product having a high glass transition temperature and a high crosslink density can be obtained. .

(Examples) The present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is
It is not limited to these examples. (Synthesis Example 1) Synthesis of N-benzyl-2-methyloxazolinium hexafluoroantimonate 8.55 g of benzyl bromide and 4.26 g of 2-methyloxazoline were mixed and reacted at 50 ° C for 24 hours.
The obtained liquid material was washed with ether and dried under reduced pressure at 40 ° C to obtain a precursor N-benzyl-2-methyloxazolinium bromide. 2.56 g of N-benzyl-2-methyloxazolinium bromide was dissolved in 15 g of distilled water, 3.10 g of sodium hexafluoroantimonate was added, stirred well, and cooled. The solution obtained by separating the two layers was separated, and then dried under reduced pressure at 40 ° C. Yield: 71%

(Synthesis Example 2) N-benzyl-2,4,4-
Synthesis of trimethyloxazolinium hexafluoroantimonate 8.55 g of benzyl bromide and 5.66 g of 2,4,4-trimethyloxazoline were mixed and reacted at 50 ° C for 6 days. The obtained liquid material was washed with ether and dried under reduced pressure at 40 ° C to obtain a precursor N-benzyl-2,4,4-trimethyloxazolinium bromide. 2.84 g of N-benzyl-2,4,4-trimethyloxazolinium bromide was dissolved in 15 g of distilled water, 3.10 g of sodium hexafluoroantimonate was added, and the mixture was stirred well and cooled. The solution obtained by separating the two layers was separated, and then dried under reduced pressure at 40 ° C. Yield: 84%

(Synthesis Example 3) N- (2-methylbenzyl)
Synthesis of -2'-methyloxazolinium hexafluoroantimonate 7.40 g of 2-methylbenzyl bromide and 3.40 g of 2-methyloxazoline were mixed and reacted at room temperature for 3 days. The obtained liquid material was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor N- (2-methylbenzyl) -2 ′.
-Methyloxazolinium bromide was obtained. N- (2
-Methylbenzyl) -2'-methyloxazolinium bromide 2.70 g was dissolved in a mixed solution of 10 g of distilled water and 3 g of methyl ethyl ketone (hereinafter referred to as MEK),
3.10 g of sodium hexafluoroantimonate was added, well stirred, and cooled. Distilled water (30 g) was added to this liquid, and the mixture was stirred well to separate the precipitated compound and dried under reduced pressure at 40 ° C. Yield: 84%

(Synthesis Example 4) N- (vinylbenzyl)-
Synthesis of 2,4,4-trimethyloxazolinium hexafluoroantimonate Chloromethylstyrene (mixture of meta and para isomers) 7.
64 g and 2,4,4-trimethyloxazoline 5.66
g were mixed and reacted at 50 ° C. for 28 days. The obtained liquid material was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor N- (vinylbenzyl) -2,4,4-trimethyloxazolinium chloride. 2.66 g of N- (vinylbenzyl) -2,4,4-trimethyloxazolinium chloride was dissolved in a mixed solution of 5 g of distilled water and 3 g of MEK to give 3.10 g of sodium hexafluoroantimonate.
Was added, stirred well, and cooled. 40g of distilled water in this liquid
In addition, the mixture was well stirred, the precipitated compound was separated, and dried under reduced pressure at 40 ° C. Yield: 92%

(Synthesis Example 5) Synthesis of N- (4-methoxybenzyl) -2'-methyloxazolinium hexafluoroantimonate 4.70 g of 4-methoxybenzyl chloride and 2.55 g of 2-methyloxazoline are mixed to give 50. The reaction was performed at 18 ° C for 18 days. The liquid obtained is washed with ether and kept at 40 ° C.
Dried under reduced pressure with N- (4-methoxybenzyl) -precursor
2'-Methyloxazolinium chloride was obtained. N-
2.42-g of (4-methoxybenzyl) -2'-methyloxazolinium chloride was dissolved in 20 g of distilled water,
3.30 g of potassium hexafluoroantimonate was added, well stirred and cooled. After separating the solution separated into two layers, 40 ℃
It was dried under reduced pressure. Yield: 30%

(Synthesis Example 6) N- (4-bromobenzyl)
Synthesis of -2'-methyloxazolinium hexafluoroantimonate 7.50 g of 4-bromobenzyl bromide and 2.55 g of 2-methyloxazoline were dissolved in 3 g of acetonitrile and reacted at 50 ° C for 6 months. The obtained liquid material was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor N-
(4-Bromobenzyl) -2'-methyloxazolinium bromide was obtained. N- (4-bromobenzyl)-
3.55 g of 2'-methyloxazolinium bromide was dissolved in a mixed solvent of 5 g of distilled water and 2 g of MEK, 3.30 g of potassium hexafluoroantimonate was added, and the mixture was well stirred and stirred and cooled. Distilled water (45 g) was added to this liquid, and the mixture was stirred well, and the solution separated into two layers was separated and dried under reduced pressure at 40 ° C.
Yield: 84%

(Synthesis Example 7) N- (α-methylbenzyl)
Synthesis of 2-methyloxazolinium hexafluoroantimonate 7.40 g of α-phenethyl bromide and 3.40 g of 2-methyloxazoline were mixed and reacted at 50 ° C. for 23 hours. The obtained liquid material was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor N- (α-methylbenzyl) -2-
Methyloxazolinium bromide was obtained. N- (α-
2.70 g of (methylbenzyl) -2-methyloxazolinium bromide was dissolved in a mixed solvent of 10 g of distilled water and 3 g of MEK to obtain 3.30 g of potassium hexafluoroantimonate.
Was added, and the mixture was well stirred and stirred, and cooled. Distilled water 4 in this liquid
Add 0 g, stir well, separate the two-layer separated solution, and
It was dried under reduced pressure at 0 ° C. Yield: 52%

(Synthesis Example 8) Synthesis of N- (α-phenylbenzyl) -2-methyloxazolinium hexafluoroantimonate 12.36 g of benzhydryl bromide and 4.26 g of 2-methyloxazoline were mixed and the mixture was heated to 50 ° C. And reacted for 4 days. The obtained liquid material was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor N- (α-phenylbenzyl) -2.
-Methyloxazolinium bromide was obtained. N- (α
3.32 g of -phenylbenzyl) -2-methyloxazolinium bromide was dissolved in 20 g of distilled water, 3.30 g of potassium hexafluoroantimonate was added, and the mixture was well stirred and cooled. The solution obtained by separating the two layers was separated, and then dried under reduced pressure at 40 ° C. Yield: 42%

(Synthesis Example 9) Synthesis of N-fluorenyl-2-methyloxazolinium hexafluoroantimonate 6.13 g of 9-bromofluorene and 4.26 g of 2-methyloxazoline were mixed and reacted at 50 ° C. for 17 hours. It was The obtained liquid material was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor N-fluorenyl-2-methyloxazolinium bromide. N-fluorenyl-2-
3.30 g of methyloxazolinium bromide was dissolved in a mixed solvent of 10 g of distilled water and 3 g of MEK, 3.10 g of sodium hexafluoroantimonate was added, and well stirred,
Cooled. Distilled water (40 g) was added to this liquid, and the mixture was stirred well to separate the precipitated compound and dried under reduced pressure at 40 ° C. Yield: 48%

(Synthesis Example 10) Synthesis of N-cinnamyl-2-methyloxazolinium hexafluoroantimonate 9.85 g of cinnamyl bromide and 4.26 g of 2-methyloxazoline were mixed and reacted at 50 ° C. for 4 days. .
The obtained liquid substance was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor N-cinnamyl-2-methyloxazolinium bromide. 2.82 g of N-cinnamyl-2-methyloxazolinium bromide was dissolved in 20 g of distilled water to give 3.10 g of sodium hexafluoroantimonate.
Was added, stirred well, and cooled. The solution obtained by separating the two layers was separated, and then dried under reduced pressure at 40 ° C. Yield: 75%

Synthesis Example 11 Synthesis of N-crotyl-2-methyloxazolinium hexafluoroantimonate 6.75 g of crotyl bromide and 4.26 g of 2-methyloxazoline were mixed and reacted at 50 ° C. for 3 days. . The obtained liquid material was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor N-crotyl-2-methyloxazolinium bromide. 2.20 g of N-crotyl-2-methyloxazolinium bromide was dissolved in 20 g of distilled water, 3.10 g of sodium hexafluoroantimonate was added, and the mixture was well stirred and cooled. The solution obtained by separating the two layers was separated, and then dried under reduced pressure at 40 ° C. Yield: 15%

(Synthesis Example 12) Synthesis of N- (1-naphthylmethyl) -2'-methyloxazolinium hexafluoroantimonate 8.83 g of 1-chloromethylnaphthalene and 4.26 g of 2-methyloxazoline were mixed, The reaction was carried out at 50 ° C for 6 days. The obtained liquid material was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor N- (1-naphthylmethyl) -2 ′.
-Methyloxazolinium chloride was obtained. N- (1
1.31 g of -naphthylmethyl) -2'-methyloxazolinium chloride was dissolved in a mixed solution of 7 g of distilled water and 3 g of MEK and allowed to add 1.55 g of sodium hexafluoroantimonate, followed by stirring well and cooling. Distilled water (40 g) was added to this liquid, and the mixture was stirred well, and the solution obtained by separating the two layers was separated and dried under reduced pressure at 40 ° C. Yield: 70%

(Synthesis Example 13) Synthesis of N-phenoxycarbonylmethyl-2-methyloxazolinium hexafluoroantimonate 8.60 g of phenyl bromoacetate and 3.40 g of 2-methyloxazoline were mixed and allowed to react at room temperature for 13 days. It was The obtained liquid material was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor N-phenoxycarbonylmethyl-2-methyloxazolinium bromide. 3.00 g of N-phenoxycarbonylmethyl-2-methyloxazolinium bromide was dissolved in a mixed solution of 5 g of distilled water and 2 g of MEK, and allowed to add 3.10 g of sodium hexafluoroantimonate, and well stirred and cooled. Distilled water (445 g) was added to this liquid, and the mixture was stirred well, and the solution obtained by separating the two layers was separated and dried under reduced pressure at 40 ° C. Yield: 59%

(Synthesis Example 14) Synthesis of N-ethoxycarbonylmethyl-2-methyloxazolinium hexafluoroantimonate 6.68 g of ethyl bromoacetate and 3.40 g of 2-methyloxazoline were mixed and reacted at 50 ° C. for 3 days. Let The obtained liquid material is washed with ether and dried under reduced pressure at 40 ° C.,
A precursor N-ethoxycarbonylmethyl-2-methyloxazolinium bromide was obtained. 2.52 g of N-ethoxycarbonylmethyl-2-methyloxazolinium bromide was dissolved in 10 g of distilled water and allowed to be added, 3.10 g of sodium hexafluoroantimonate was added, well stirred and cooled. This solution was extracted with ethyl acetate, and after removing ethyl acetate, it was dried under reduced pressure at 40 ° C. Yield: 46%

(Synthesis Example 15) Synthesis of N- (1-ethoxycarbonylmethyl) -2'-methyloxazolinium hexafluoroantimonate 5.43 g of ethyl 2-bromopropionate and 2.55 g of 2-methyloxazoline are mixed. Then, the mixture was reacted at 50 ° C. for 2 days. The obtained liquid material was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor N- (1-ethoxycarbonylmethyl) -2′-methyloxazolinium bromide. 2.66 g of N- (1-ethoxycarbonylmethyl) -2'-methyloxazolinium bromide was added to distilled water 2
It was dissolved in 0 g and allowed to be added, and 3.10 g of sodium trifluoroantimonate antimonate was added, well stirred, and cooled. This solution was extracted with ethyl acetate, and after removing ethyl acetate, it was dried under reduced pressure at 40 ° C. Yield: 34%

(Synthesis Example 16) N-methyl-2- (2'-)
Synthesis of nitrobenzylthio) thiazolinium hexafluoroantimonate 2- (2'-nitrobenzylthio) thiazoline 7.63
g and 3.78 g of dimethylsulfate were dissolved in 2 g of dioxane and reacted at 50 ° C. for 25 hours. The obtained liquid material was washed with ether and dried under reduced pressure at 40 ° C., and the precursor N-
Methyl-2- (2'-nitrobenzylthio) thiazolinium sulfate was obtained. N-methyl-2- (2'-nitrobenzylthio) thiazolinium sulphate 3.8
0 g was dissolved in 50 g of distilled water, 3.10 g of sodium hexafluoroantimonate was added, well stirred, and cooled.
The precipitated compound was separated and dried under reduced pressure at 40 ° C. Yield: 82%

(Synthesis Example 17) Synthesis of N-benzyl-2-methylthiazolinium hexafluoroantimonate 6.84 g of benzyl bromide and 4.05 g of 2-methylthiazoline were mixed and reacted at room temperature for 7 days. The obtained liquid material was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor N-benzyl-2-methylthiazolinium bromide. 2.72 g of N-benzyl-2-methylthiazolinium bromide was dissolved in 20 g of distilled water, 3.30 g of potassium hexafluoroantimonate was added, and the mixture was well stirred and cooled. The precipitated compound was separated and dried under reduced pressure at 40 ° C. Yield: 84%

<Curing test> An onium salt compound was dissolved in propylene carbonate, and ERL-4221 (U
CC alicyclic epoxy) and UVR-6410 (UC
A glycidyl type epoxy manufactured by Company C) was added to each of them so as to have a pure content of 2.5 parts to prepare a mixture. A DSC measurement was performed on this blend to determine the top temperature of the exothermic peak. The measurement conditions of DSC are as follows, and the measurement results are shown in Tables 1 and 2. DSC measuring instrument: DSC220C (manufactured by Seiko Denshi Kogyo Co., Ltd.) Atmosphere: Nitrogen gas stream 30 ml / min Temperature rising rate: 10 ° C / min Sample amount: 0.3-0.8 mg

[0044]

[Table 1]

[0045]

[Table 2]

(Comparative Onium Salt 1) For comparison with the present invention, benzyl-4-cyanopyridinium hexafluoroantimonate was used as an initiator, and DSC measurement was carried out in the same manner as in Examples.

(Comparative Onium Salt 2) N-benzyl-N-
Using ethyl-N-methylanilinium hexafluoroantimonate as an initiator, ERL was prepared in the same manner as in the example.
-4221 (UCC alicyclic epoxy) and UVR
-6410 (glycidyl type epoxy manufactured by UCC Co.) was added to each to be 2.5 parts as a pure content, the mixture was adjusted, and (Comparative Examples 1-2 and Comparative Examples 3-4) DSC measurement was performed. The top temperature of the exothermic peak was determined. The results are summarized in Tables 1 and 2 above.

<Measurement of glass transition temperature of cured product> An onium salt compound is dissolved in propylene carbonate, and UV is applied.
The mixture was added to R-6410 in a pure content of 2 parts, and the mixture was adjusted and heated at 150 ° C. for 30 minutes. Dynamic viscoelasticity measurement was performed on the obtained cured product, and the glass transition temperature was determined from the top peak of the loss elastic modulus. The dynamic viscoelasticity measurement conditions are as follows, and the measurement results are shown in Table 3. Dynamic viscoelasticity measuring instrument: Rheovibron RHEO-
2000: manufactured by Toyo Baldwin Co., Ltd. Frequency: 35Hz Temperature rising rate: 3 ° C / min

[0049]

[Table 3]

(Comparative Onium Salt 1) In contrast to the present invention, benzyl-4-cyanopyridinium hexafluoroantimonate was used as an initiator and heat treatment was carried out in the same manner as in Example, but it was not cured.

(Comparative Onium Salt 2) N-benzyl-N-
When ethyl-N-methylanilinium hexafluoroantimonate was used as an initiator and heat treatment was carried out in the same manner as in the example, it was not cured.

(Comparative Onium Salt 3) N- (4-methoxybenzyl) -4'-cyanopyridinium hexafluoroantimonate was used as an initiator, and dynamic viscoelasticity was measured in the same manner as in the examples.

(Comparative Onium Salt 4) N-benzyl-N-
Using ethyl-N-methylanilinium hexafluoroantimonate as an initiator, UVR was performed in the same manner as in the example.
-6410 was added so as to be 2 parts as a pure content, the formulation was adjusted (Comparative Examples 4 to 8), and dynamic viscoelasticity measurement was performed.
The glass transition temperature was determined from the top peak of loss modulus. The results are summarized in Table 3 above.

[0054]

INDUSTRIAL APPLICABILITY The present invention is characterized in that an onium salt compound obtained by quaternizing the nitrogen of a cationically polymerizable nitrogen-containing heterocycle and salt-exchanged with a non-nucleophilic anion is used as a cationic polymerization initiator. It is a curable composition.

In the curable composition of the present invention, when a conventional so-called thermal latent cationic polymerization initiator is used to cure an epoxy compound, a basic sulfide or tertiary amine is produced as a leaving component. , The cationic polymerization is stopped on the way, and a good cured product, for example, a material having a high glass transition temperature or a high crosslink density is to improve the drawback that it is difficult to obtain. It is possible to obtain a cured product having a high crosslinking density.

Continuation of front page (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 4/00-4/82 C08G 59/00-59/72

Claims (2)

(57) [Claims] 1. A thermosetting composition comprising the following components [A] and [B]. Component [A]: N ⁺ ═C—X—C—C bond in the ring (X is
Represents an oxygen atom or a sulfur atom. And a heterocyclic onium salt compound having a quaternized nitrogen atom capable of undergoing cationic polymerization. [B] A cationically polymerizable compound. 2. The component [A] is an oxozaolii derivative,
The thermosetting composition according to claim 1, which is a heterocyclic onium salt compound having a quaternized nitrogen atom capable of undergoing cationic polymerization, selected from a dihydrooxazine derivative and a thiazoline derivative. .