JPH0641215A - Solution of cation generator - Google Patents

Abstract

PURPOSE:To obtain the soln. which is excellent in storage stability at room temp. in a dark place and gives a cationically polymerizable org. compsn. by dissolving a sulfonium salt in a high-boiling ether compd. CONSTITUTION:The soln. is obtd. by dissolving 80-5 pts.wt. high-activity sulfonium salt of formula I (wherein R<1> is H, CH3, acetyl, methoxycarbonyl, benzoyl, etc.; R<2> and R<3> are each H, a halogen, or 1-4C alkyl; Q<1> is benzyl, p-methylbenzyl, p-nitrobenzyl, m-chlorobenzyl, alpha-naphthylmethyl, methyl, etc.; R<4> is methyl or ethyl; and X is SbF6, PF6, AsF6, or BF6) in an ether compd. having a b.p. of 120 deg.C or higher. If necessary, a sulfonium salt of formula II (wherein R<5> is H, CH3, acetyl, etc.; R<6> and R7 are each H, a halogen, or 1-4C alkyl; Q<2> is benzyl, etc.; R<8> is CH3 or C2H5; and Y is a halogen, a perchloric acid group, etc.) is added to the soln. as a stabilizer of one-component system.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a solubilized cation generator. More particularly, it relates to a catalyst solution of a heat and / or light latent curing catalyst for a cationically polymerizable organic material or a catalyst type curing agent solution for room temperature curing. The cation generator solution of the present invention is prepared by mixing with a cationically polymerizable organic material, for example, an epoxy resin, a cyclic ether or a vinyl ether resin to provide a thermal and / or photolatent curing catalyst composition having excellent storage stability, Alternatively, a curing catalyst solution to be used in two parts is provided.

[0002]

Use of a sulfonium salt as a cationically polymerizable curing catalyst is disclosed, for example, in Japanese Patent No. 952.
No. 498, No. 887187, No. 131119, No. 1305282, No. 1289446, No. 14662.
No. 84, No. 1511862, No. 1618088 and the like. The inventors of the present invention have also disclosed, for example, in Japanese Patent Laid-Open No.
-196812, JP-A-3-59001, JP-A-3
-72569, JP-A-3-205405, JP-A-3
No. 237107, the formula I

[0003]

[Chemical 3] It is disclosed that the sulfonium salt represented by can generate a cationic species by an external stimulus such as heat and / or light, and can polymerize and cure the cationically polymerizable organic material. Further, according to Japanese Patent Application No. 3-301041, For improving the storage stability of catalyzed compositions, for example, compounds of formula II

[0004]

[Chemical 4] It was also taught to additionally use a sulfonium salt represented by

By the way, a mixture of a photoinitiator and propylene carbonate or ethylene carbonate, which is considered to be useful in preparing a composition comprising a cationically polymerizable organic material and a sulfonium salt, is disclosed in Patent No. 124.
No. 5439. However, there is a limit to the solubility of the sulfonium salt in propylene carbonate or ethylene carbonate, and it is not only necessary to use a large amount of a solvent, but also in the curing of the cationically polymerizable composition using this, it is caused by the solvent. A relatively long curing time is required, and particularly when curing is performed at room temperature, propylene carbonate or ethylene carbonate in the solution remains as an unreacted product, which causes deterioration of physical properties of the cured product.

[0006]

The present inventors have conducted extensive studies to solve the above problems, and as a result, use a high boiling point ether compound having a boiling point of 120 ° C. or higher as a solvent for preparing a cation generator. This makes it possible to dissolve a cation generator or a stabilizer if necessary at a high concentration, is effective for preparing a one-part composition of a cationically polymerizable organic material, and is a cured product immediately under appropriate heating conditions. Found to give. It was also found that the ether compound used was incorporated into the network structure of the cured product to give an excellent cured product even for the purpose of curing at room temperature, and the present inventors have found a stable cation generator solution of the present invention.

That is, the present invention is a cation characterized in that a sulfonium salt represented by the following formula I and, if necessary, a sulfonium salt represented by the following formula II are dissolved in a high boiling ether compound having a boiling point of 120 ° C. or higher. It relates to a generator solution. However, the ether compound is a part by weight (a =
100-b, and a ≧ 20. ), The sulfonium salt represented by the formula I is b parts by weight (5 ≦ b ≦ 80), the formula II
The sulfonium salt represented by is 0.1 to 20% by weight based on the sulfonium salt of the formula I.

[0008]

[Chemical 5]

[0009]

[Chemical 6] (Here, R ¹ and R ⁵ are hydrogen, a methyl group, an acetyl group,
A methoxycarbonyl group, an ethoxycarbonyl group, a benzoyl group, or a benzyloxycarbonyl group, wherein R ² , R ³ , R ⁶ , and R ⁷ are each independently hydrogen,
Either halogen or a C ₁ -C ₄ alkyl group,
Q ¹ and Q ² are benzyl group, p-methylbenzyl group, o-
Methylbenzyl group, m-methylbenzyl group, p-nitrobenzyl group, o-nitrobenzyl group, m-nitrobenzyl group, 2,5-dinitrobenzyl group, p-chlorobenzyl group, m-chlorobenzyl group, o- Chlorobenzyl group,
It is either an α-naphthylmethyl group, a methyl group or an ethyl group, and R ⁴ and R ⁸ are either a methyl group or an ethyl group. X is any of SbF ₆ , PF ₆ , AsF ₆ , and BF ₄ , and Y is halogen, methylsulfate, ethylsulfate,
It is either p-toluenesulfonic acid or perchloric acid. ) Examples of the high boiling point ether compound used in the present invention include methyl carbitol, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, butyl carbitol acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dicyclohexane, 18-crown. Examples thereof include crown ethers such as -6, methyl cellosolve, ethyl cellosolve, and butyl cellosolve, and they can be used alone or in combination of two or more.

The sulfonium salt represented by the formula I is benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4.
-Hydroxyphenylmethylsulfonium hexafluorophosphate, benzyl-4-hydroxyphenylmethylsulfonium tetrafluoroborate, benzylethyl-4-hydroxyphenylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylethylsulfonium hexafluorophosphate, benzyl-4- Methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-
Methoxyphenylmethylsulfonium hexafluorophosphate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate (or hexafluorophosphate), benzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate (or , Hexafluorophosphate), 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate (or hexafluorophosphate), benzyl-4- (methoxycarbonyloxy) phenylmethylsulfonium hexafluoroantimonate (or hexafluorophosphate), benzyl -4-Ethoxycarbonyloxy) phenylmethylsulfonium hexafluoroantimo (Or hexafluorophosphate), benzylmethyl-4- (ethyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate (or hexafluorophosphate), benzyl-4- (benzyloxycarbonyloxy) phenylmethylsulfonium hexafluoro Antimonate (or hexafluorophosphate), p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate (or hexafluorophosphate), o-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate (or , Hexafluorophosphate), m-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonet (Or hexafluorophosphate), dinitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate (or hexafluorophosphate), 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate (or hexafluorophosphate), α- Naphthylmethyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate (or hexafluorophosphate), α-naphthylmethyl-4- (methoxycarbonyloxy) phenylmethylsulfonium hexafluoroantimonate (or hexafluorophosphate), p- Chlorobenzyl-4-acetoxyphenylethylsulfonium hexafluoroarsenate, 4-methylbenzyl-4- Methoxycarbonyloxy-3-chlorophenylmethylsulfonium tetrafluoroborate, 4-phenoxycarbonyloxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium
Hexafluoroantimonate (or hexafluorophosphate), 4-methoxycarbonyloxyphenyldimethylsulfonium hexafluoroantimonate (or hexafluorophosphate) and the like can be mentioned, and one or more kinds can be used in combination. it can.

Further, examples of the sulfonium salt for stabilizing the one-liquefied composition represented by the formula II include benzyl-4-hydroxyphenylmethylsulfonium chloride, benzyl-4-hydroxyphenylethylsulfonium chloride and benzyl-4-. Hydroxyphenylmethyl methylsulfate, p-chlorobenzyl-
4-hydroxyphenylmethylsulfonium chloride, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium chloride, o-methylbenzyl-4
-Hydroxyphenylmethylsulfonium chloride, m-methylbenzyl-4-hydroxyphenylmethylsulfonium chloride, benzyl-4-methoxyphenylmethylsulfonium chloride, benzyl-
3-methyl-4-hydroxyphenylmethylsulfonium chloride, benzyl-3-methyl-4-hydroxy-5-tert-butylphenylmethylsulfonium chloride, α-naphthylmethyl-4-hydroxyphenylmethylsulfonium chloride, 4-hydroxyphenyldimethyl Methylsulfate and 4- (benzyloxycarbonyloxy) phenyldimethyl methylsulfate can be mentioned, and one kind or a combination of two or more kinds can be used.

The preferred mixing ratio of the ether compound / sulfonium salt (I) / sulfonium salt (II) in the cation generator solution of the present invention is 30 to 70 parts by weight of the ether compound,
70 to 30 parts by weight of the sulfonium salt (I) which is a cation generator. If necessary, a sulfonium salt (II) is added as a stabilizer, and the proportion thereof is preferably 0.5 to 10% by weight based on the amount of the sulfonium salt (I) used.

[0013]

According to the present invention, in the curing of the cationically polymerizable organic material composition with the cation generator solution using the high boiling point ether compound of 120 ° C. or higher, at the end of the cationic polymerization, for example, the ether compound in the growth terminal carbenium ion is converted into the ether compound. It is considered that the formation of an oxonium salt due to the attack of oxygen atoms occurs and the ether compound is incorporated into the cured product, so that the physical properties of the cured product are not adversely affected. Further, it is considered that a transfer reaction occurs between the growth terminal and the ether compound during curing, and new cation species (H ⁺ ) are generated, so that a rapid curing reaction occurs. A cationically polymerizable composition using a cation generator solution prepared by using the sulfonium salt represented by the formula I and the sulfonium salt represented by the formula II in combination with the high-boiling point ether compound of the present invention as a stabilizer is prepared in the dark. It has excellent storage stability and can form a cured product in a short time by heating or irradiation with energy rays such as ultraviolet rays. Furthermore, cation generation consisting of a highly active sulfonium salt represented by the formula I and a high boiling ether compound. A composition consisting of an agent solution and a cationically polymerizable substance can form a cured product promptly at room temperature.
It is widely applicable to cast products, adhesives, paints, etc.

[0014]

The present invention is described in detail below with reference to examples, but the present invention is not limited to the following.

Example 1, Comparative Example 1 p-Nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate 15.0 g
1.0 g of 4-hydroxyphenyldimethylsulfonium methylsulfate was added to 10 g of methyl carbitol, and the mixture was stirred at room temperature. As a result, it quickly dissolved and became a uniform transparent solution. When propylene carbonate was used instead of methyl carbitol, it did not dissolve safely even after stirring for a long time, and 30 g of propylene carbonate was required to completely dissolve it.

Examples 2 to 4 and Comparative Example 2 A composition of alicyclic epoxy resin Celoxide 2021 (manufactured by Daicel Chemical Industries, Ltd.) was prepared by using the cation generator solution prepared according to Example 1. This composition was allowed to stand at 25 ° C for 1 month under light-shielding, and the viscosity and curability (high pressure mercury lamp, 2KW, 80W / cm, 1 lamp, 8cm below each composition were spin coated on a hardened PVC plate. The coated material was passed through so as to have a thickness of about 5 μm, and ultraviolet rays were irradiated until the tack on the coated surface disappeared, which was expressed by the irradiation amount (mJ / cm ² ) until the tack disappeared. The results are shown in Table 1.

[0017]

[Table 1] Examples 5 to 16 and Comparative Examples 3 to 7 Using the cation generator solution prepared according to Example 1, a composition of Epicoat 815 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy) was prepared, and this composition was prepared. The product was left at 40 ° C. in the dark. The viscosity of the composition was measured immediately after preparation and one month later (25 ° C.). In addition, the gelation time of the composition immediately after preparation and after storage at 40 ° C. for 1 month is determined by JI.
According to SC2104, Nisshin Scientific Co., Ltd. gelation tester
It was measured at a predetermined temperature using a GT-JIS type. The results are shown in Tables 2 and 3.

[0018]

[Table 2]

[0019]

[Chemical 7]

[0020]

[Table 3]

[0021]

[Chemical 8] Examples 17 to 22 and Comparative Examples 8 to 11 Tables 4 and 5 show the results of measuring the solubility of various highly active sulfonium salts in ether compounds at 25 ° C.

[0022]

[Table 4]

[0023]

[Table 5] Example 23 Using the cation generator solution obtained in Example 19 and the cation generator solution after storing it at room temperature for 1 month, 1.9 parts by weight to Epicoat 815 (100 parts by weight), respectively, was used. Stir to about 0.1 on a glass plate.
It was applied to the plate and left at room temperature. As a result, in both cases, it became tack-free after 5 hours.

Comparative Example 12 The cation generator solution obtained in Comparative Example 8 was epicoat 8
When the curability was evaluated by the same method as in Example 23 using 2.82 parts by weight per 15 parts by weight of 100, the surface was sticky for 48 hours.

[0025]

As described above, the cation generator solution prepared by dissolving the high boiling point ether compound according to the present invention is
It has a high solubility in sulfonium salts, and the cation-polymerizable organic material composition using this cation generator solution has excellent storage stability in the dark at room temperature, and can be heated or irradiated with energy rays such as UV light. It is possible to polymerize and cure in a short time. Further, a cationically polymerizable composition using a cation generator solution containing a highly active sulfonium salt can be rapidly cured at room temperature. Therefore, the intended purpose can be achieved.

Claims (9)

[Claims] 1. An ether compound having a boiling point of 120 ° C. or higher 20
~ 95 parts by weight of Formula I A cation generator solution characterized by dissolving 80 to 5 parts by weight of a sulfonium salt represented by the formula (in the above formula, R ¹
Is hydrogen, a methyl group, an acetyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a benzoyl group, or a benzyloxycarbonyl group, and R ² and R ³ are independently hydrogen, halogen, and C _{1 to} C ₄ Q ¹ is any of alkyl groups, and benzyl group, p-methylbenzyl group, o-methylbenzyl group, m-methylbenzyl group, p-nitrobenzyl group, o-nitrobenzyl group, m
-Nitrobenzyl group, dinitrobenzyl group, p-chlorobenzyl group, m-chlorobenzyl group, o-chlorobenzyl group, α-naphthylmethyl group, methyl group, ethyl group, R ⁴ is a methyl group, It is one of the ethyl groups. X is any of SbF ₆ , PF ₆ , AsF ₆ , and BF ₄ . 2. The cation generator solution according to claim 1,
Furthermore, the formula II 0.1 to 20% by weight of a sulfonium salt represented by the formula I is dissolved in a cation generator solution (wherein R ⁵ is hydrogen, a methyl group, an acetyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a benzoyl group, or a benzyloxycarbonyl group, R ^6, R ⁷ is a independently hydrogen, halogen, or an alkyl group having C ₁ ~C _4, Q ²
Are benzyl group, p-methylbenzyl group, o-methylbenzyl group, m-methylbenzyl group, p-nitrobenzyl group, o-nitrobenzyl group, m-nitrobenzyl group, dinitrobenzyl group, p-chlorobenzyl group, It is any one of m-chlorobenzyl group, o-chlorobenzyl group, α-naphthylmethyl group, methyl group and ethyl group, and R ⁸ is either methyl group or ethyl group. Y is any one of halogen, methylsulfate, ethylsulfate, p-toluenesulfonic acid, and perchloric acid). 3. The cation generator solution according to claim 1, wherein the sulfonium salt represented by the formula I is benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate. 4. The sulfonium salt represented by the formula I is benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and the sulfonium salt represented by the formula II is 4-hydroxyphenyldimethylsulfonium methylsulfate. The cation generator solution described. 5. The sulfonium salt of formula I is 4-
Hydroxyphenyl-p-nitrobenzylmethylsulfonium hexafluoroantimonate.
The cation generator solution described. 6. The sulfonium salt of formula I is 4-
The cation generator solution according to claim 2, which is hydroxyphenyl-p-nitrobenzylmethylsulfonium hexafluoroantimonate and the sulfonium salt represented by the formula II is 4-hydroxyphenyldimethylsulfonium methylsulfate. 7. The cation generator solution according to claim 1, wherein the ether compound is ethyl carbitol. 8. The cation generator solution according to claim 1 or 2, wherein the ether compound is methyl carbitol. 9. The cation generator solution according to claim 1, wherein the ether compound is diethylene glycol dimethyl ether.