JPH05262814A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which can be cured at a still lower temperature within a short time by adding a combination of a specified pyridinium salt compound with a compound which can generate an active free radical when heated to a cationically polymerizable compound. CONSTITUTION:The title composition is produced by mixing a pyridinium salt compound (A) of formula I (wherein R<1>, R<2>, R<4> and R<5> are each H, halogen, alkyl, alkoxyl, -NO2, vinyl, -CH2CN or the like; R<3> is H, alkyl or phenyl; and X is SbF6, AsF6, PF6 or BF4) (e.g. a compound of formula II) with a compound (B) which can generate an active free radical when heated (e.g. methyl ethyl ketone peroxide) and a cationically polymerizable compound (C) (e.g. styrene). The mixing ratio is suitably such that about 0.01-20 pts.wt. component A and about 0.01-10 pts.wt. component B are added to 100 pts.wt. component A. This composition can desirably be used as the material of a molding material, a coating material or the like.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a curable composition,
More specifically, it relates to a cationically polymerizable composition that cures at low temperature in a short time by heating. The cured product of the composition is
Since it 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 A catalyst for curing a cationically polymerizable compound such as epoxy by heating and its composition are disclosed in JP-A-58-37003, JP-A-63-22003, JP-A-56-152833 and JP-A-56-152833. Sho 63-131171
No. 2, JP-A-2-178319, etc.
All of the catalysts described in these documents have a high curing temperature of the cationically polymerizable compound and are problematic in practical use.

[0003]

The present invention has been made in view of the above circumstances, and provides a high-performance curable composition capable of curing a cationically polymerizable compound at a lower temperature by heating. The purpose is to

[0004]

Means for Solving the Problems The inventors of the present invention have made extensive studies to achieve the above-mentioned object. As a result, a pyridinium salt compound alone cures by using a pyridinium salt compound and a compound capable of generating an active radical by heating. We have found a curable composition capable of curing a cationically polymerizable compound at a temperature lower than the temperature.

That is, the present invention provides the following components (A) and (B)
And (C) are contained, It is a curable composition characterized by the above-mentioned. (A) Pyridinium salt compound represented by formula (I)

[Chemical 2] (In the formula, R ¹ and R ² are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, —NO ₂ , —CN, a vinyl group, —CH ₂ CN, an alkoxycarbonyl group, a hydroxyl group, a carbamoyl group or an alkanoyl group. And R ³
Represents a hydrogen atom, an alkyl group or an optionally substituted phenyl group, and R ⁴ and R ⁵ are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, —NO ₂ , or —
CN, vinyl group, -CH ₂ CN, a hydroxyl group, a carbamoyl group, an alkanoyl group, an aldehyde group, a carboxyl group,
It represents an alkoxycarbonyl group, an optionally substituted phenyl group, an optionally substituted benzyl group or an alkylthio group, and X represents SbF ₆ , AsF ₆ , PF ₆ or BF ₄ . (B) at least one compound that generates an active radical by heating (C) at least one cationically polymerizable compound

The present invention will be described in detail below. Examples of the pyridinium salt compound that can be used in the present invention include known compounds such as the following general formulas (II) and (II
Pyridinium salt compounds represented by I) can be mentioned. These pyridinium salt compounds are, for example, T. En
It can be obtained by the synthetic method taught in do et al, Chemistry Letters., 1861 (1989).

[0007]

[Chemical 3] (In the formula, R ⁶ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, —NO ₂ , —CN, a vinyl group, —C.
H ₂ represents CN, alkoxycarbonyl group, a hydroxyl group, a carbamoyl group or an alkanoyl group, R ⁷ is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, -NO
_2, -CN, a vinyl group, -CH ₂ CN, a hydroxyl group, a carbamoyl group, an alkanoyl group, an aldehyde group, a carboxyl group, an alkoxycarbonyl group, an optionally substituted phenyl group, an optionally substituted benzyl group or alkylthio Represents a group, and X is SbF ₆ , AsF ₆ , PF
Represents ₆ or BF ₄ . )

[0008]

[Chemical 4] (In the formula, R ⁸ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, —NO ₂ , —CN, a vinyl group, a hydroxyl group, a carbamoyl group or an alkanoyl group, and R ⁹
Is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, —NO ₂ , —CN, a vinyl group, a hydroxyl group, a carbamoyl group, an alkanoyl group, an aldehyde group, a carboxyl group, an alkoxycarbonyl group, or a phenyl group which may be substituted. Represents an optionally substituted benzyl group or an alkylthio group, and X represents SbF ₆ , AsF ₆ , PF ₆
Or represents BF ₄ . )

Further, a compound which is not known may be used, and in this case, it can be obtained, for example, by the following method. A benzhydryl halide such as benzhydryl bromide and pyridine or a pyridine derivative are equimolarly reacted in the presence of a solvent such as methyl alcohol, acetone or acetonitrile at room temperature to 80 ° C. for several hours to 30 days, if necessary. Then, the obtained solid matter was dissolved in water or water-methanol system, sodium hexafluoroantimonate was added and stirred vigorously, and the precipitated liquid or solid product was separated and purified, and then dried. can get. Examples of the compound are shown in the following general formula (IV).

[0010]

[Chemical 5] (Wherein, n represents 1 or 2, R, is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, -NO _2, -C
N, vinyl _{group, -CH 2 CN, -CONH 2,} -COR
^{1, -CONR 1 R 2, -COOR} 1 (R 1, R 2 are,
Each represents an alkyl group or an optionally substituted phenyl group), and substituted or unsubstituted -CH ₂ C ₆ H
₅ , a phenyl group or a thioalkoxy group, and X represents SbF ₆ , AsF ₆ , PF ₆ or BF ₄ . )

Examples of the compound which generates an active radical upon heating used in the present invention include generally known azo compounds such as azoisobutyronitrile, azide compounds, disulfide compounds and peroxide compounds. .. Among these compounds, a peroxide compound is particularly preferably used, and examples thereof include ketone peroxides such as methyl ethyl ketone peroxide, silohexanone peroxide, and acetylacetone peroxide, 1,1-bis (t-butylperoxy). Cyclohexane, peroxyketals such as 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, hydroperoxides such as cumene hydroperoxide, dicumyl peroxide, di-t-butyl. Dialkyl peroxide such as peroxide, dibutyl peroxide such as isobutyl peroxide, acetyl peroxide, benzoyl-oxide, peroxy carbo such as diisopropyl peroxycarbonate, etc. Sulfonates, t- butyl peroxy acetate, peroxy esters such as cumyl peroxy neodecanate, acetyl cyclohexyl sulfonyl peroxide, such as tetra (t-butyl peroxy carbonyl) benzophenone can be used. In particular, aromatic diacyl peroxide and peroxy ester are preferably used.

Examples of the cationically polymerizable compound used in the present invention include the following compounds. (A) As the 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-, p-cresol novolac type epoxy resin, phenol novolac type epoxy resin, epoxy compound such as polyglycidyl ether of polyhydric alcohol,

(B) Styrene and α as vinyl compounds
-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 divinyl ether and cyclohexanediol divinyl ether; aralkyl such as 1,4-benzenedimethanol divinyl ether, N-m-chlorophenyldiethanolamine divinyl ether and m-phenylenebis (ethylene glycol) divinyl ether Divinyl ethers; hydroquinone divinyl ether, resorcinol divinyl Aryl divinyl ethers such as ether; N- vinylcarbazole, a cationic polymerizable N-containing compounds such as N- vinylpyrrolidone.

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) Undecane-3,9-dibenzyl-1,5,7,1
1-tetraoxaspiro (5,5) undecane, etc. 1,
4,6-trioxaspiro (4,4) nonane, 2-methyl-1,4,6-trioxaspiro (4,4) nonane,
Examples 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 kinds. (A) ~
Among (d), the compound having an epoxy group of (a) is preferably used.

The composition of the present invention contains the pyridinium salt compound 0.01 to 20 relative to the cationically polymerizable compound.
Parts, preferably 0.05 to 10 parts, compounds that generate radicals by heating 0.01 to 10 parts, preferably 0.0
It is mixed in a ratio of 5 to 5 parts. If both are less than 0.01 parts, the curability is deteriorated, and if they exceed 20 and 10 parts respectively, the physical properties of the cured product are deteriorated. The composition of the present invention is cured by heating, but in some cases, heating and light irradiation may be used in combination to be cured.

The pyridinium salt compound used in the present invention is generally used alone, but it may be used in combination with another cationic polymerization initiator. When the compound having an epoxy group of (a) above is used, a phenolic curing agent usually used as a curing agent for epoxy resins,
A curing agent such as an acid anhydride curing agent can be used in combination as long as the performance is not impaired.

If necessary, a reactive diluent, a curing accelerator, a solvent, a pigment, a dye, a coupling agent, an inorganic filler, a carbon fiber, a glass fiber or a surfactant is added to the curable composition of the present invention. You may add and use it.

[0019]

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to these examples. (Example) Various pyridinium salt compounds are dissolved in propylene carbonate to obtain 2.5 parts as a pure component in ERL-4221 (UCC alicyclic epoxy) or UVR-6410 (UCC glycidyl epoxy). As described above, 2.5 parts of the compound generating various active radicals was added to each epoxy to prepare a resin composition.

Further, a resin formulation was prepared in the same manner as a comparative example corresponding to the example without adding a compound generating an active radical.

DSC measurements were carried out on these formulations to determine the exothermic onset temperature and peak top temperature. The results are shown in Table 1 (Examples) and Table 2 (Comparative Examples). The measurement conditions of DSC are as follows. 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

[0022]

[Table 101]

[0023]

[Table 102]

[0024]

[Table 103]

[0025]

[Table 104]

[0026]

[Table 105]

[0027]

[Table 106]

(In the table, TCP is bis (4-t-butylcyclohexyl) peroxydicarbonate, TMHP
Is 3,5,5-trimethylhexanoyl peroxide, AIBN is azoisobutyronitrile, and LP is lauroyl peroxide. )

[Table 201]

[0029]

[Table 202]

[0030]

[Table 203]

[0031]

[Table 204]

[0032]

[Table 205]

[0033]

[Effect of the Invention] In curing a cationically polymerizable compound, by using a pyridinium salt compound and a compound capable of generating an active radical by heating in combination, more than in the case of curing the cationically polymerizable compound only with the pyridinium salt compound, It has been found that it cures at low temperatures in a short time.
This curable composition can be cured at a lower temperature and in a shorter time than conventional ones, and thus is very useful in practice.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C08G 59/68 NKL 8416-4J

Claims (1)

[Claims] 1. A curable composition comprising the following components (A), (B) and (C). (A) Pyridinium salt compound represented by the general formula (I): (In the formula, R ¹ and R ² are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, —NO ₂ , —CN, a vinyl group, —CH ₂ CN, an alkoxycarbonyl group, a hydroxyl group, a carbamoyl group or an alkanoyl group. And R ³
Represents a hydrogen atom, an alkyl group or an optionally substituted phenyl group, R ⁴ and R ⁵ are each a hydrogen atom,
Halogen atom, an alkyl group, an alkoxy group, -NO _2,
-CN, a vinyl group, -CH ₂ CN, a hydroxyl group, a carbamoyl group, an alkanoyl group, an aldehyde group, a carboxyl group, an alkoxycarbonyl group, an optionally substituted phenyl group, an optionally substituted benzyl group or an alkylthio group Where X is SbF ₆ , AsF ₆ , PF ₆
Or represents BF ₄ . (B) at least one compound that generates an active radical by heating (C) at least one cationically polymerizable compound