JPS58198532A - Curable composition - Google Patents

Abstract

PURPOSE:To provide a curable compsn. which can be cured even in the deep part by irradiation and/or low-temperature heating, by blending a polymn. initiator capable of being activated by radiation and a polymn. initiator capable of being activated by heat, with a cation-polymerizable material. CONSTITUTION:100pts.wt. cation-polymerizable material (A) such as epoxy resin, 0.01-4pts.wt. organosulfonium salt (B) of a non-nucleophilic ion capable of generating a Lewis acid by irradiation, such as bis[4-(diphenylsulfonio)phenyl] sulfide.2PF6, and 0.05-10pts.wt. organosulfonium salt (C) of a non-nucleophilic anion capable of generating a Lewis acid by heating, such as prenyl-tetramethylene-sulfonium hexafluoroantimonate, are blended together to obtain a curable resin compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a cationically polymerizable composition that can be deeply cured by irradiation with energy rays and/or heating at a relatively low temperature.

In particular, the present invention relates to a curable composition that can be completely cured by irradiation with energy rays even in a relatively thick system containing an inorganic filler.

Photopolymerization of cationic monomerizable substances, such as epoxy resins, has attracted attention due to its excellent physical properties, and aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, aromatic sulfoxonium salts, etc. of Lewis acids are cured. Photosensitive onium salts are known as photosensitive onium salts (e.g., U.S. Pat.
No. 794574, %opening f850-151994, same 5
No. 0-151997, same so-tssds.

No. 52-5089? No. 56-8428, No. 56-149402, etc.].

However, when using these known onium salts,
If the thickness is 500 cm or more, the KR part cannot be cured within the practical UV irradiation time, for example, 60 seconds, and if it contains a solid filling agent, it will be more rapid. ing. In order to improve this drawback, a method using a special aromatic sulfonium compound (%-Sho! No. 14-55420) was used, in which the surface was coated with energy rays using a thermosetting agent for epoxy resin, and then heated. Method of curing the inside of each part (Japanese Patent Application Laid-open No. 54-17979, 5
No. 7-122, No. 56-55129), and a method of accelerating hardening by using steel salt (No. 56-24927) has been proposed; It is difficult to cure within the irradiation time, and the physical properties of the cured product are not practical, either.

An object of the present invention is to provide a cationically polymerizable curable composition that can be completely cured even when relatively thick by irradiation with energy rays and/or heating at a relatively low temperature within a practical time.

The curable composition of the present invention contains, as essential constituents, a cationic polymerizable substance, and an aromatic onium salt of a non-nucleophilic anion that generates a Lewis acid upon irradiation with energy rays. (1) Contains an effective 1 organic sulfonium salt of a non-nucleophilic port ion that generates a Lewis acid from #IIK.

As the cationically polymerizable substance <11 used in the present invention, acid-polymerizable or acid-curable organic substances, particularly epoxy resins, are preferably used.

The epoxy resins used in the present invention include conventionally known aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins. Here, preferred aromatic epoxy resins are polyglycidyl ethers of multi-fl phenols having at least one aromatic nucleus or their alkylene oxide adducts, such as bisphenol A or its alkylene oxide adducts. Examples include glycidyl ether and epoxy novolak resin produced by reaction with epichlorohydrin. In addition, as an aliphatic epoxy resin, it is preferable to use a polyglycidyl ether of a polyhydric alpole having at least one alicyclic ring or a cyclohexene or cyclopentene ring-containing compound with an excessive oxidizing agent such as hydrogen peroxide or peracid. There are cyclohexene oxide- or cyclopentene oxide-containing compounds obtained by epoxidation with.

Typical examples of polyglycidyl x-, r are hydrogen &
Examples include glycidyl ethers produced by reacting Suphenol A or its alkylene oxide adduct with epichlorohydrin.

Furthermore, preferred aliphatic epoxy resins include polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts; typical examples include diglycidyl ether of 1,6-hexanediol and triglycidyl ether of glycerin. One or more alkylene oxides (ethylene oxide , propylene oxide) can be mentioned. Furthermore, monoglycidyl ethers of aliphatic higher alcohols, phenol, cresol, or monoglycidyl ethers of polyether alcohols which can be prepared by adding fullkylene oxide to these may also be incorporated as diluents.

Other acid-curing or acid-curing organic substances that can be used as the cation-curing substances of the present invention include episulfide resins, cyclic ethers, lactones, organosilicone rings, vinyl ethers, phenol/formaldehyde flanks, etc. Examples include organic substances. Such cationically polymerizable substances can be used alone or in a mixture of two or more.

The seaweed ion used in the present invention is a non-nucleophilic seaweed ion, and is an energy-sensitive aromatic onium salt (II is the general formula [1'J It is expressed as

[Mu]9B)-[1] (In the formula, A represents an &substituted onium structure containing an energy-sensitive 41! group, and B represents a non-nucleophilic anion.) The above non-nucleophilic Preferable seagull ions B have the general formula (where M is B, P, 8b, A@, F@, A
/ #Cu.

An atom selected from TL, 01, Zn, and Bn, qft halogen atom, ■ is an anion represented by a number of 1 to 60;
PF6), hexafluoroantimonate (sby
, ), hexuro-o antimonate (sbct6)
, hexafluoro p-arsenate (mF6), etc. are being discussed.

Sarabusy general formula MQI1. An anion represented by OH (in the formula, Q, and ■ are the same as above) can also be used. Furthermore, other non-nucleophilic ions include perchlorate ion (01
04),) Lifluoromethyl sulfite ion (at, so
',), fluorosulfonic acid ion (R80;),)
Examples include luenesulfonate anion, trinitropensene sulfonate anion, and the like.

These 5% K 8bF6 and 5br5(oH) have excellent deep hardening properties. Mu in general formula (1) is a cationic component of an onium salt having an energy ray-sensitive structure, and is efficiently decomposed by irradiation with energy rays. Many compounds with desirable structures have been discovered, among them Japanese Patent Application Laid-open Nos. 50-158680 and 1983-158680;
Aromatic halonium salts described in -15199+6 etc., No. 50-151997, No. 52-50899, No. 56-55420, No. 56-8428, No. 56-1
■ Mu group aromatic onium salts (aromatic sulfonium salts, oxosulfonium salts, etc.) described in No. 49402, etc., No. 5
r)-158698 and the like are preferred.O Also, Go's objective is to apply the composition of the present invention to the curing of thin films such as paints and obtain a blood film V with more excellent physical properties. For example, the aromatic diazonium salts described in Properties 1@49-170401'FK can be used, and dithiolium salts, thiopyrylium salts, and the like can also be effectively used.

Further, the onium salt that can constitute the cation moiety A may be in the form of a bis-oelam salt or a tris-onium salt described in JP-A No. 855-125105.

Particularly preferred for the purposes of the present invention are aromatic (oxo)
These are sulfonium salts and aromatic iodonium salts, and aromatic sulfonium salts are particularly effective.

Another 1* component of the present invention is a heat-sensitive organic sulfonium salt in which the ion is non-nucleophilic (ail is (1
It is selected from sulfonium salts that can be activated in the presence of an epoxy resin or the like to cause cationic polymerization at temperatures below 1150°C.

In addition, as another condition, although not necessarily essential, 1 of the present invention
In order to effectively reach the target, k must be (2) 240f Rimicrons or more and 400 millimicrons or less Ff) substantially have no large ultraviolet absorption in the wavelength range, and (3) the activation energy of thermosensitive decomposition is 17 to 20 kcal/ It is preferable that the amount is mol· or more.

Preferred heat-sensitive sulfonium salts satisfying the above conditions are those having a special organic group selected from aliphatic sulfonium salts, and can be represented by the general formula F.

Here, R4, R, are the same or different substituted or unsubstituted aliphatic or aliphatic S group groups, R, and R2 may form a ring, and the groups include unsaturated bonds, alkoxy groups, Nitro group, tetragen group, hydroxyl group, carboxyl group, ester group,
It can contain functional groups such as an ether group, a cyano group, a carbonyl group, a sulfone group, and a thionidel group.

Y is an aliphatic group having an electron-withdrawing functional group at the a-position or I-position with respect to the sulfur atom, and has the general formula [Paulownia or [4]
Preferably, it is marked with a button.

3 - a -x (s) 4 Here, R3-R6 are hydrogen atoms, r11p! or unsubstituted aliphatic group j! ! Depending on the selected group, R1 and R4 or R5 and 16 may be the same or different. X is an electron-withdrawing i-functional group.

Here, the term "electron-withdrawing functional group" refers to a group that has an ignition effect due to the electron KvIc attraction of the carbon atom in contact with @.
Such groups include nitro groups, cyano groups, alkenyl groups, alkynyl groups, carboxyl groups, carbonyl groups, ester groups, sulfone groups, halogen groups, and the like.

Among these, preferable % is an allyl group or a tertiary aliphatic group in which Y is wIL-substituted with at least one aliphatic group, and has a group represented by the following general formula (5) or [6]. It is something.

1 '11 -0-R1, (S'12 (where R7~B, . is a hydrogen atom or a substituted or non-I
ll-substituted aliphatic group, preferably an alkyl group, R7
At least one of -R9 must be a substituted or unsubstituted aliphatic group, preferably an alkyl group.

In addition, ``11~R1, are selected from substituted or unsubstituted aliphatic groups, preferably alkyl groups. There may be a benzyl group represented by !. B has the same meaning as the general formula (1).

Such sulfonium salts are relatively easily synthesized, for example, by reacting the corresponding sulfide with an active A--alkylno-1-lide).
MQI, 18. It can also be obtained by anion exchange using a reagent such as MQm (M, Q, m are the same as above), or directly by reacting sulfide with Meerwine such as triethyloxonium tetrafluoroborate. It is also possible to synthesize it with a better yield than K.

When a tertiary aliphatic group is reacted with a sulfide, the reaction can be carried out under acidic conditions using the corresponding alcohol as a starting material to obtain a sulfonium salt.

The composition of the present invention is an energy-sensitive aromatic onium which is a cationic polymeric substance (xlloo is an anionic non-ice-nucleating, non-ice-nucleating, non-ice-nuclear ion based on the weight part and is capable of generating a Lewis acid by energy @ irradiation with 5J). Contains 0.01 to 4 parts by weight of salt (1+). For deep hardening of 1+, add up to 1
For 2), it is preferable to determine the amount of rock so that the light transmittance is improved by using 1 part, preferably as little as possible without impairing the curability. The amount of heat-sensitive organic sulfonium salt (2) whose ion is non-nucleophilic is the same as above (1).
) 0.05 to 10 JiJi for 100 weight J11fK
It can be contained within a range of 100%. The heat-sensitive sulfonium salt (2) of the present invention is an energy-sensitive aromatic onium salt (
Since it does not easily impair the light transmittance which is essential for decomposing 1), the amount to be used can be determined within a relatively wide range.

The compositions of the present invention can contain inorganic negative fillers if desired. Examples of typical fillers are silica,
! Examples include transparent quartz powder, white clay, glass, glass fiber, water-containing alumina, asbestos, palite, and fumo powder.

Further, conductive fine particles such as gold or - may be used. In the case of conventional optical cationic fibers, the amount of the additive is at most 15 to 15 g per 100 parts by weight of Kana 121 synthetic organic matter (1).
Although up to 1 part of OA could be used, a much wider range can be used in the compositions of the present invention. A preferred inorganic filler cap is 0 to 50,031 parts, preferably 0 to 2,001 parts.

The compositions of the present invention can be used in various II! The coated, impregnated, or injected @: can be cured by irradiating it with energy rays and/or heating it on a coated object or a molded object.

Suitable energy beams may be any energy source that has the energy to decompose or ferment photosensitive onium salts, but preferably high/low pressure mercury lamps, xenon lamps, killing lights, laser beams, solar lights, etc. 2 obtained from
, 000 X to 7,000 μm of wavelength, energy rays such as electromagnetic waves, electron beams, X-rays, and radiation are used.

Exposure to energy rays varies depending on the type and intensity of energy rays, the type, thickness, etc. of the composition of the present invention, but usually 10 seconds to 2 minutes is sufficient.

When curing the composition of the present invention, heating is not always necessary in many cases, but in some cases it is possible to cure the composition by heating alone at °C, and it is possible to cure even areas that are not exposed to light. Its application range is wide. Alternatively, more complete curing can be effectively achieved by combining heating before, simultaneously with, or after energy ray irradiation. When heating is performed alone, the temperature is 50 to 150°C.
: Can be hardened after several seconds to several minutes in a yoke. Further, when energy rays are used in combination and heating is performed prior to irradiation, it is preferable to heat the material at a temperature of 80° C. or lower. When a cured product is obtained using energy rays and then completely cured by heating, it is also effective to maintain the temperature within the range of 100 to 200°C for several seconds to several hours.

If you want to heat at the same time as energy rays, you can use heat rays, convection heating, induction heating, or other heating methods, but in most cases it is best to use a lamp such as a solar lamp that emits heat rays as energy rays. The purpose can be achieved even if the temperature is 1°C.

The composition of the present invention may further contain a solvent for dilution and a non-reactive resin or greborimer for modification within a range that does not impair cation binding. In addition, for example, organic carboxylic acids and acid anhydrides are used for the purpose of improving physical properties, or polyols and other 5'J! l! It is also good to mix I type grepolymer.

The composition of the present invention may further include powders, dyes, thickeners, flame retardants,
C is also used in combination with antistatic agents, antigelation agents, density improvers, flow control agents, surfactants, antioxidants, sensitizers, and the like. One of these additives is determined by the balance between function and curability, and these compositions can be used for metals, wood, rubber, plastics, glass, and Nanami Mikuku products 4GK.

Specific uses of the present invention include paints, inks,
Adhesives, molding materials, casting materials, glass fiber-impregnated tapes,
Examples include putty and filler. In addition, epoxy resin has excellent electrical properties, so each! It can also be used for materials for Ii, condensers, resistors, light emitting diodes, semiconductors, printed circuit boards, transformers, morphs, -wires,
It can also be applied to solar cells, relays, switches, and other electrical and electronic components. Also, due to its excellent transparency, it can be used for various optical applications.

The composition of the present invention has a long pot life at room temperature, and can be cured in a short time by short-term heating or energy ray irradiation, or by using a combination of both, and has a ## area that could not be achieved with conventional technology. It enables hardening and deep hardening in the presence of inorganic fillers, and can also provide cured products with better physical properties.

The effect of the present invention is that it provides a cationic curable composition that can be completely cured even when relatively thick by irradiation with energy rays and/or heating at a relatively low temperature within a practical time.

The effects of the present invention are specifically listed below.

(1) Practical curing is possible even at a thickness of 5 mm or more.

(2: A material with a thickness of 5 ms or more mixed with a large amount of inorganic light can be practically cured.

(31 Heat-sensitive -Fi functional sulfonium salts do not inhibit the curing of photosensitive aromatic onium salts (for example, BF and amine complexes do not inhibit curing).

(4) Pot life is short.

(51 Transparency is good.

(6) Good physical properties.

EXAMPLES The effectiveness of the present invention will be explained in detail below using examples, but the present invention is not limited to the following examples unless the gist of the invention is exceeded.

Example 1 Bis-[4-(diphenylsulfonio)phenyl sulfide bischloride was obtained using the method of 1982-125104, and HPF in water sa.
By performing salt exchange with sF, or Na15bF, photosensitive sulfonium salts A, 2PF4t^, 2^IF6゜^, each having a corresponding non-nucleophilic anion are obtained.
28bF6 was obtained (hereinafter referred to as the cation component, Ml, bis-(<-(diphenylsulfonio)phenyl)sulfide). Using this photosensitive sulfonium salt, the following basic formulation-1 was obtained. Ta.

Celloxide 2021 (Daicel #Alicycloaliphatic Eboxy)') 100 1
Ji@A-2AIF,
0.41.1 m This composition was placed in an aluminum cup with a diameter of 5011 so that the thickness of the composition was 4 cm.
It was irradiated with a high-pressure mercury lamp at 50 W/(III* degree) from a distance of (II). After 50 seconds of irradiation, the composition had a low viscosity DTF. Although a thin film was observed to form, the inside remained uncured.In order to further improve the curing properties, Mu-20F,
f: Although the production was increased by q, the thickness and hardness of the surface film only increased slightly, but the inside remained uncured. Mu・2mu sF
When the n of , was reduced, no thin film formation was observed. However, a formulation in which 11 parts of o, sl, prenyl tetramethylene sulfonium hexfluoroantimonate was added as a heat-sensitive sulfonium salt to this basic formulation-1 was cured to part # in 30 seconds under the same irradiation conditions. , Shore D hardness 8
A hard cure of 5 or higher was obtained. Reduce ftam・2mgF4 to 0.2 to 1 part and add 0.5J of heat-sensitive sulfonium salt.
The formulation in which 1 part of K was added also cured uniformly to the deep part.

Example 2 The following basic formulation-1 was obtained using silica and Merck.

Celloxide 2021 100 Part by weight A-28
bF, 0.21kllii silica filler 50 & Okibe talc filler
1 part of 50Jk This mixture was placed in an aluminum cup to a thickness of 4cm, and from a distance of 15 (Im) 80w/
When irradiated for 45 seconds using a high-pressure mercury lamp, the surface was cured, but the deeper parts remained uncured. However, the formulation to which 174 parts of the heat-sensitive sulfonium salt 'tO,4h of Example H1 was added was sufficiently swollen to the deep part and gave a strong solid product.

Example 5 A formulation in which silica photodeposition agent 70 Higashikurabe and the heat-sensitive sulfonium salt described in Example 1 were added to Example 10 basic formulation-1 was cured to the deep part under the same irradiation conditions to form a strong solid product. Gave.

Example 4 The following basic formulation - JIliIJIl! did.

IP-4100 (Asahi Denka Chest Bisphenolum Type Epoxide) 100j [i1 Part A-281) F2O,
Parts of IJi This mixture was placed in an aluminum cup in the same manner as in Example 1, and irradiated with ultraviolet rays for 50 seconds to obtain four rhinoceros disks. On the other hand, 0.2 part of the same heat-sensitive sulfonium salt as in Example 1 was added to this mixture and irradiated to obtain a disc V having a size of 4 cm.

When I immersed the disc in methyl ethyl ketone for a day and night, I found that either the former disc had completely collapsed, or the latter disc had remained intact. In addition, the basic formulation in which the amount of photosensitive sulfonium salt 5by6 was increased to 0.4 parts by weight was similarly adapted. Furthermore, formulations in which the amount was increased to 1 part or more of 1.0jlj had the problem of deep hardening. Formulations with heat-sensitive sulfonium salts have a temperature below [
It remained stable for at least 3 months.

Example 5 The two disks obtained in Example 4 were heat-treated with taott##fli4 and then crushed, and the glass transition temperature was measured using a D13G-2i differential scanning calorimeter (manufactured by PerkinElmer). The vow not to mix sulfonium is 70.
℃, and the mixed formulation was heated to 140℃.

Example 6 A metal fitting consisting of triphenylsulfonium quinafluoroantimonate 0.11JllS and 100 m of celoxide and the IT part was cured under Condition F of Example 10 to a thickness of 1 m.
Obtained a disk. This cured product is methyl ethyl ketone,
After soaking for 15 hours, I added 14 to 7%.
Sumimasu was born to the above. To this formulation, 1 part of 0.21 Jl of the heat-sensitive sulfonium salt of Example 1 was added.
The amount increase was 0.4% or less.

Example 7 The following basic formulation-■ was prepared.

Celloxide 2021 100 1 part^・2PF
, 1.5-layer lid silicone surfactant 0.5-layer lid stiffness mixture was applied to Alden test panels (o, 3■#) [10μ■] under two 80W/plow mercury lamps. I was able to pass through the tank at a speed of 501mm per minute, making it tank-free. A mixture obtained by mixing 5 parts by weight of crotyl tetramethylene sulfonium hexafluoroarsenate as a heat-sensitive sulfonium salt with this mixture could be cured by both heating at 150° C. or less and UV curing. Further, the obtained formulation was stable for more than 3 months at room temperature in the Ili place, and by mixing 2s of catalyst, the curing properties and physical properties were improved and did not affect each other. However, in the above basic formulation (■), BF, which is known as a typical example of a latent cation 1-cocatalyst for epoxy resin, is added.
A blend containing 311 parts of monoethylamne complex significantly inhibited the curability and physical properties of the blend. The pot life of the formulation was within one week at room temperature in a dark place.

Example 8 A formulation consisting of triphenylsulfonium hexafluoroarsenate 1.53 mis, crotyl tetramethylenesulfonium hexfluoroantimonate O,S) seams, and 100 parts of ceroxide 2021 was kept in the dark under straw temperature for at least 6 months. More stable molten-free steel with low viscosity [
given the composition. The gel time of the formulation at 150'C is 5
The photocuring property could be cured within 10 seconds by irradiating it with a water lamp of sol,/m for less than 10 seconds. If used as is, for example, as a varnish for impregnating stator coils, etc., the surface side can be cured by ultraviolet irradiation to prevent sagging, and parts that cannot be irradiated with light can be hardened by thermosetting. In addition, if you want to give 5J flexibility thermal shock resistance, etc., use polyol, a] Flexible epoxy, Flexible Im! It is possible to remove dust by adding anhydride or the like.

Example 9 Celloxide 2021 100 parts by weight, A.28b-0
, 1 part by weight, crotyl tetramethylene sulfonium
Hechinafluoroantimone) 0. ! 1 compound containing 1 part of phenolic antioxidant is UV 4
A cured product with excellent transparency (transmission aI of 9% or more) was obtained by post-heating for 1 hour at 160° C. for I irradiation. This cured product has a transmittance of 85% even after aging at 120°C for more than 500 hours.
I admired all of the above. This formulation can be applied to light emitting diode stabbing and optical 92 applications.

Applicant's agent Kaoru Furuya Procedural amendment (spontaneous) June 25, 1980 Japan Patent Office Director Kazuo Wakasugi 1 Indication of case Patent application No. 1982-828211 2 Name of invention Curable composition 5 Person making the amendment Relationship to the case Patent applicant (0! 581 Asahi Denka Kogyo Co., Ltd. 4 Detailed description of the invention in the agent's specification - does not accurately convey the mechanism of the reaction)'' (1
) Insert K "or tertiary aliphatic group" next to "...Aliphatic group" on page 11, line 4 (1) On page 11, line "[ 3] or [4]” by r [! 5
].

[4] or [6]” (1) Same line 2az11 1tlJ corrected to [yo*j

Claims (1)

[Claims] t (1) a cationic polymerizable substance, (1) an effective amount of an aromatic onium salt of a non-nucleophilic anion that is generated as a Lewis acid upon irradiation with energy rays, and (1) by heat. A curable composition containing as an essential component an effective amount of an organic sulfonium salt of a non-repellent anion that generates a Lewis acid. & The curable composition according to claim 1, wherein the aromatic onium salt is an aromatic sulfonium salt. The curable composition according to claim M1g4, wherein the organic sulfonium salt is an aliphatic sulfonium salt.