JPH0359001A - Polymerizable composition - Google Patents

Abstract

PURPOSE:To obtain a polymerizable composition of improved storage stability by mixing at least one cationically polymerizable substance with a specified sulfonium salt. CONSTITUTION:At least one cationically polymerizable substance is mixed with a sulfonium salt of the formula (wherein R1 is an acetyl, a methoxycarbonyl, an ethoxycarbonyl, a benzyloxycarbonyl, a benzoyl, a phenoxycarbonyl, a p-methoxybenzyloxycarbonyl or a 9- fluorenylmethoxycarbonyl, R2 and R3 which are independent of each other are each a hydrogen atom, a halogen atom or a 1-4 C alkyl; R4 and R5 which are independent of each other are each a methyl or an ethyl; and X is SbF6, AsF6 or PF6). It is desirable that 0.01-20 pts.wt. sulfonium salt of the formula is added to 100 pts.wt. cationically polymerizable substance.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a cationically polymerizable composition, a polymerization catalyst, and a polymerization method. More specifically, a cationic polymerizable substance is polymerized in a short time by radiation such as light, electron beams, and/or heat to obtain a cured product with good physical properties and a practical oligomer of a cationically polymerizable vinyl compound. The present invention relates to a polymerization composition, a catalyst for the polymerization, and a polymerization method.

[Prior Art and Problems to be Solved] Cationically polymerizable materials, especially epoxy resins, are used in a variety of applications requiring high performance materials. especially,
A method of polymerization and curing by irradiation with radiation of a predetermined wavelength, such as ultraviolet rays, can be cured in a short time and the polymerization process is simple, so it is used for various purposes.

Conventionally, epoxy resins have been mixed with active amine-containing compounds and carboxylic acid anhydrides as curing agents, and have been widely used in two-component systems. However, two-component systems using these curing agents,
The ingredients must be thoroughly mixed and the curing time can extend to several hours.

There is a boron fluoride-monoethylamine system for curing epoxy resin as a one-component system, but this takes 1 to 8 hours even at a temperature of 160 DEG C. or higher. As an example of this improvement, U.S. Patent No. 3,565,861 can be cited.
It still requires high temperatures. Therefore, these compositions cannot be used to coat heat-sensitive electronic components and the like.

Furthermore, metal halide aryldiazonium salts have been proposed for curing epoxy resins with light.

However, these are expected to polymerize rapidly and be susceptible to premature gelation, resulting in compositions that cannot be stored satisfactorily even in the dark. It has been proposed to provide epoxy materials containing metal halide aryl diazonium salts to inhibit premature gelling of the composition and also to provide storage stability in the dark, but this increases cost and is not entirely satisfactory. No results have been obtained.

These compositions also suffer from the problem that nitrogen is released during curing and the resulting cured material contains undesirable air vesicles.

By the way, various photodegradable sulfonium salts are known as onium salts. For example, JP-A-54-53181
No. p-hydroxyphenyl dimedyl sulfonium
It is known to use hexafluoroarsenates as a photocuring agent, and in JP-A-50-151997, it is known to use phenylsulfonium salts as a photocuring agent for epoxy. However, these are disclosures regarding curing by light, and there is no disclosure regarding curing by heat.

On the other hand, the onium salt is activated by applying heat,
JP-A-58-37003 and JP-A-63-22 regarding thermally latent catalysts that can cure epoxy resins.
No. 3002 reports benzylsulfonium salts such as dialkylbenzylsulfonium hexafluoroandemonate salts, and JP-A-56-152833 reports trialkyl-type sulfonium salts. However, this sulfonium salt requires 150% to cure the epoxy resin.
Both heating time and temperature are not practical, such as requiring a heating temperature of .degree. C. or higher.

Furthermore, sulfides, which are the starting materials for these aliphatic or alicyclic sulfonium salts, generally have a characteristic bad odor, which not only poses a problem in industrial production, but also leaves the odor in the cured product.

Furthermore, for special esters such as spiro-type esters, a curing agent for thermal polymerization thereof is disclosed in JP-A-60-188425.

On the other hand, examples of cationic polymerization catalysts for cationically polymerizable vinyl compounds include mineral acids, BF3. ZnC1z.

Lewis acid type catalysts such as AlCl3, AlR2C1゜A
Halogen-containing organoaluminum compounds such as IRC12 are known. However, these catalysts undergo too vigorous a cationic polymerization reaction at temperatures above 0° C., making it impossible to control the polymerization reaction as desired and preventing the degree of polymerization from increasing. Of course, it is also impossible to prepare the cationically polymerizable monomer and these catalysts into one liquid at room temperature and then store the mixture.

When trying to polymerize vinyl compounds, it is necessary to control chain transfer reactions and termination reactions. Usually, a cationically polymerizable monomer dissolved in an appropriate solvent is cooled to a predetermined cryogenic temperature, and then a catalyst solution is added to initiate polymerization. A reaction takes place. However, the polymerization reaction is industrially carried out at extremely low temperatures (e.g. -130 to
-40°C), it is necessary to use a low-temperature refrigerant, which makes the operation complicated and increases the cooling cost, which is not a satisfactory method.

[Object of the Invention] An object of the present invention is to be able to polymerize cationic polymerizable substances such as epoxy resins with radiation and/or heat, to have excellent storage stability at room temperature, and to be able to polymerize cationically polymerizable substances such as epoxy resins with radiation and/or heat, and to have excellent storage stability at room temperature, and to The purpose of this invention is to provide a cationic polymerizable composition that can be used as a matrix resin for materials, and to propose a polymerization method and a catalyst for the polymerization.

Alternatively, it is possible to polymerize a cationically polymerizable vinyl compound such as styrene under certain conditions, provide a seven-mer composition with poor storage stability when mixed with a polymerization catalyst, and provide a practical composition. The purpose of this project is to provide industrially available vinyl monomer oligomers, and to propose methods for their polymerization and catalysts for the polymerization.

[Means for Solving the Problems] The present inventors have conducted intensive research to solve the above-mentioned problems, and as a result, they have arrived at the present invention.

That is, the present invention provides a polymerizable composition containing a cationic polymerizable substance, a cationically polymerizable substance of the following general formula [I1] which can be polymerized by radiation and/or heat, and The present invention relates to a polymerization catalyst as a component and a polymerization method.

Ru.

R1 niacetyl group, methoxycarbonyl group.

Ethoxycarbonyl group, benzylhokidicarbonyl group,
It is any one of a benzoyl group, a phenoxycarbonyl group, a p-methoxybenzyloxycarbonyl group, and a 9-fluorenylmethoxycarbonyl group.

R2, R,: each independently hydrogen and halogen.

Any of C1 to C4 alkyl groups be.

R, 1, Rt: Each independently represents either a methyl group or an ethyl group.

X: SbF6. AsF+;, PFr, .

[Structure of the Invention] The polymerization catalyst of the present invention is a compound of a dialkyl-4-substituted oxyphenyl sulfonium compound and a predetermined anion, and has these as constituent elements.

The cationic polymerizable substance used in the present invention is preferably an acid polymerizable or acid curable substance, especially an epoxy resin. Examples of suitable materials are epoxide monomers, evisulfide monomers, polyepoxides (
or epoxy resin), polyevisulfides (or ebylyl sulfide resin), phenol/formaldehyde resin, melamine/formaldehyde resin,
Urea/formaldehyde resin, spiro orthoester,
Bicycloorthoesters, cyclic ethers and cyclic thionidels (other than epoxides and evisulfides) such as spiroorthocarbonates and their polymers, lactones, styrenes, vinyl ethers and vinyl thioethers, and cross-linking resins when treated with acids. Alternatively, it is a resin containing a cross-linking agent to be cured, and it may be used alone or in combination of two or more types.

[Function] The sulfonium salt used as the polymerization catalyst of the present invention is as described above, and this sulfonium salt has the following properties:
A high yield can be obtained by reacting the corresponding 4-(substituted oxyphenylalkyl sulfide with an alkyl sulfate to synthesize a sulfonium salt having a methyl sulfate ion, and then performing anion exchange with a predetermined complex salt.

Preferred sulfonium salts in the present invention are 4
-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4-(benzyloxycarbonyloxy)phenylsulfonium hexafluoroantimonate, diethyl-4-(benzyl Oxycarbonyloxy)phenylsulfonium hexafluorophosphate.

Dimethyl-4-(benzoyloxy)phenylsulfonium hexafluoroantimonate, -dimethyl-4
-(benzoyloxy)phenylsulfonium hexafluoroacenate, dimethyl-4-(p-methoxybenzyloxycarbonyloxy)phenylsulfonium hexafluoroantimonate, dimethyl-4-(phenoxycarbonyloxy)phenylsulfonium hexafluoroarsenate , dimethyl-4-(9-fluorenylmethoxycarbonyloxy)phenylsulfonium hexafluorophosphate.

Dimethyl-2-chloro-4-(benzyloxycarbonyloxy)phenylsulfonium hexafluoroantimonate, dimethyl-3-methyl-4-(benzyloxycarbonyloxy)phenylsulfonium hexafluoroantimonate, dimethyl-3-chloro- 4-
Examples include acetoxyphenylsulfonium hexafluoroantimonate.

The sulfur-1;nium salt used in the present invention not only increases its activity against heat, but also has activity against radiation such as light and electron beams. That is, it is thought that these sulfonium salts excited by heat or radiation release acyl cations and promote polymerization of the above-mentioned cationic polymerizable substance.

Further, in the present invention, when the cationically polymerizable substance is a vinyl compound, solution polymerization using an inert solvent for the catalyst, monomer, etc. is usually performed during the polymerization reaction, but bulk polymerization is also performed in some cases. Examples of the solvent include aromatic hydrocarbons such as toluene, benzene, and xylene; aliphatic hydrocarbons such as n-hexane and n-hebutane; alicyclic hydrocarbons such as dichlorohexane; Hydrocarbon mixtures such as petroleum ether and ligroin, halogenated hydrocarbons such as chlorobenzene and dichloroethane, etc. can be used, and the polymerization reaction of these vinyl compounds is carried out under normal pressure or increased pressure, and the reaction temperature is 8
The temperature is 0°C or higher, preferably 100-150°C.

Furthermore, since the sulfonium salt used as a polymerization catalyst in the present invention does not initiate a cationic polymerization reaction at room temperature, if necessary, it is also possible to prepare the monomer and catalyst in one liquid using an appropriate solvent and store it. be.

The sulfonium salt used in the present invention is 0.01 to 20 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the resin.
5 parts by weight. If it is less than 0.01 part by weight, a sufficient polymer cannot be obtained. If the amount added exceeds 20 parts by weight, favorable physical properties cannot be obtained after polymerization, and it is also unfavorable in terms of cost. Further, polymerization curing is performed by radiation treatment or heat treatment, and heating and radiation irradiation can be used together if necessary.

Further, during polymerization, a solvent can be used if necessary.

The radiation according to the invention has a wavelength of 250 to 400 nm.
Ultraviolet rays in the m range are the most efficient, so light sources include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, carbon arc lamps, etc. Polymerization and curing can also be achieved by irradiating electron beams. be able to.

The composition of the present invention may further contain additives such as fillers, flame retardants, antistatic agents, surfactants, and acid anhydrides.

The composition of the present invention can be used for polishing surfaces, inks, paints, adhesives, laminates, prepregs, molding materials, sealing materials, and the like.

The curable composition of the present invention can be stored for a long period of time at room temperature, has the ability to quickly start polymerization when heated to 150°C or less, has excellent high temperature curability, is non-hygroscopic, has water resistance, and chemical resistance. Provides a cured product with excellent properties and electrical properties.

In addition, in the cationically polymerizable vinyl compound composition,
It is now possible to store the 7-mer and catalyst in one liquid, which was previously difficult, and to perform cationic polymerization reactions at temperatures above 80°C.
The point is that it has become possible to obtain a practical polymer with a high degree of polymerization by simple heating.

[Example] The present invention will be described in detail in the following examples, but the present invention is not limited to the following examples.

Examples 1 to 7 0.030 g of various sulfonium salts were mixed with 1 g of phenyl glycidyl ether, this mixture was sealed in a degassed tube, and polymerized at 60°C and 140°C for 1 hour, respectively. Conversion was determined using 'H-NMR.

The results are shown in Table 1. In addition, the composition prepared here was
When it was left at ℃ for 1 month, no significant thickening was observed.

(Left below) Example 8 Dimethyl-4-(benzyloxycarbonyloxy)phenyl to 0.5 g of 3.9-dibenzyl-1,5,7,11-tetraoxaspiro[5,5]undecane Sulfonium hexafluoroantimonate 3n
o1% (0,0231 g) was mixed, degassed, and sealed. This mixture was subjected to bulk polymerization at 140°C for 2 hours. After polymerization,
A conversion rate of 99% was confirmed by 'H-NMR spectrum.

Next, the polymer was dissolved in 2 ml of methylene chloride and poured into 100 ml of hexane. Then, dry the hexane-insoluble portion to obtain 0.45 g of polymer.

Example 9 1 mOL'6 of dimethyl-4-(benzyloxycarbonyloxy)phenylsulfonium hexafluoroantimonate was mixed with 0.5 g of purified styrene, and the mixture was degassed and sealed. Then, polymerization was carried out at 140°C while stirring. After 30 minutes, the solidified reaction solution was diluted with 2 carbon tetrachloride.
ml, and a conversion rate of 96% was confirmed from this 'H-NMR spectrum.

Next, this was poured into methanol to stop polymerization and precipitate a polymer. The purified and dried polymer was white crystals with a yield of 83%.

Also, Mn=310 by GPC (polystyrene equivalent)
0. Mw/Mn=2.12, and no thermal polymer (radical polymer) was included.

Examples 10 to 14 Styrene was polymerized according to Example 9 using various sulfonium salts. The results are shown in Table 2.

(Left below) Example 15 Styrene was polymerized at 40° C. for 60 minutes in accordance with Example 9, but the conversion rate was 0%.

Example 16 10 g of purified styrene and 0.50 g of dimethyl-4-(benzyloxycarbonyloxy)phenylsulfonium hexafluoroantimonate were mixed with 1 gram of chlorobenzene.
The solution was dissolved in 00 ml of water, degassed, sealed, and kept in an apparatus at room temperature for one month, but no styrene polymerization occurred.

Examples 17-22 A blend consisting of 100 parts by weight of Epicoat 828 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy) and 2 parts by weight of a sulfonium salt of Seed No.
Take mg and heat it to 150℃ on a hot plate (Japan, Shin Kagaku Co., Ltd. gelation test [';!?:n GT D
The gelation time was measured using JIS model). The results are shown in Table 3.

(The following is a blank space) Example 23 The compositions prepared in Examples 10 to 14 were stored at 40° C. for one month, but no significant thickening was observed.

Examples 24 to 28 0.030 g of various sulfonium salts were mixed with 1.0 g of phenyl glycidyl ether.

This mixture was degassed, sealed, and subjected to bulk polymerization for 60 minutes.
The conversion rate was determined by 'H-NMR. A 400W high-pressure mercury lamp was used as a light source, and a rotary photochemical reaction device manufactured by Rikou Kagaku Sangyo was used. The polymerization temperature was 20'C (under water cooling). The results are shown in Table 4.

(The following is a blank space) [Effects of the Invention] As described above, the predetermined sulfonium salts according to the present invention are effective as polymerization catalysts for cationic polymerizable substances, and polymerization compositions containing them can be polymerized by a polymerization method using heat treatment. Can be hardened.

Furthermore, this liquefied composition is stable even after mixing and has excellent shelf life at room temperature. Therefore, the intended purpose can be achieved.

Claims (14)

[Claims] (1) A polymerizable composition containing one or more cationically polymerizable substances and a sulfonium salt represented by the general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] R_1: Acetyl group, methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, benzoyl group, phenoxycarbonyl group, p-methoxybenzyloxycarbonyl group, 9-fluorene Any of the nylmethoxycarbonyl groups. R_2, R_3: each independently hydrogen, halogen, C
Any one of _1 to C_4 alkyl groups. R_4, R_5: Each independently represents either a methyl group or an ethyl group. X: One of SbF_6, AsF_6, and PF_6. (2) The polymerizable composition according to claim 1, wherein the cationically polymerizable substance is a compound having an epoxy group. (3) The polymerizable composition according to claim 1, wherein the cationically polymerizable substance is a cationically polymerizable vinyl compound. (4) The polymerizable composition according to claim 1, wherein the cationically polymerizable substance is a compound having one or more types of spiroorthoester groups, bicycloorthoester groups, and spiroorthocarbonate groups. (5) The amount of the sulfonium salt represented by the general formula [I] is 0.01 to 20 parts by weight per 100 parts by weight of the cationically polymerizable substance.
The polymerizable composition according to claim 1, wherein parts by weight are added. (6) A polymerization catalyst for a cationically polymerizable substance containing as a main component a sulfonium salt represented by the general formula [I] according to claim 1. (7) The polymerization catalyst according to claim 6, wherein the sulfonium salt is 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate. (8) The polymerization catalyst according to claim 6, wherein the sulfonium salt is dimethyl-4-(benzyloxycarbonyloxy)phenylsulfonium hexafluoroantimonate. (9) The polymerization catalyst according to claim 6, wherein the sulfonium salt is dimethyl-4-(benzoyloxy)phenylsulfonium hexafluoroantimonate. (10) The polymerization catalyst according to claim 6, wherein the sulfonium salt is diethyl-4-(benzyloxycarbonyloxy)phenylsulfonium hexafluoroantimonate. (11) adding one or more sulfonium salts represented by the general formula [I] according to claim 1 to one or more cationically polymerizable substances as a catalyst;
A method for polymerizing a cationically polymerizable substance, which comprises initiating polymerization using radiation and/or heat. (12) The polymerization method according to claim 11, wherein the radiation is ultraviolet rays. (13) The polymerization method according to claim 11, wherein the polymerization is carried out at a temperature of 80° C. or higher. (14) A claim in which 0.01 to 20 parts by weight of a sulfonium salt represented by the general formula [I] described in claim 1 is added to 100 parts by weight of a cationically polymerizable substance. The polymerization method according to item 11.