JP2022017462A - Conductive epoxy composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive epoxy composition which is formed into a cured product having both super flexibility and bending resistance following a flexible film.

SOLUTION: A conductive epoxy composition uses only a single component epoxy compound as a resin content, and is composed of the epoxy compound, an onium salt, and silver powder. The onium salt has a reaction initiation temperature when heated together with a bisphenol A type liquid epoxy resin of 45°C or higher, and a blending ratio of 10-70 mass% with respect to 100 mass% of the epoxy compound. A die shear tensile rupture strength of a cured product of the composition is 5 MP or more, and a coated film cured product after having been coated onto a film does not cause cracking in a bending resistant test.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2022,JPO&INPIT

Description

The present invention relates to a conductive epoxy composition.

Since General Electric Company (GE) in the United States succeeded in ring-opening polymerization of epoxy groups using onium salts in 1975, light and hot onium salts have been used in epoxy compositions (epoxy resins). It has been in the limelight again as a new latent curing catalyst, and various onium salts have been researched and developed in Japan and overseas.

The onium salt one-component epoxy composition can be (a) cured in a short time, (b) easy to formulate, (c) has less odor and vapor during heat curing, and is friendly to the human body and the environment, (d) general. No need for physical freezing and long pot life, (e) the cured product is not colored and the transparency of the epoxy resin can be maintained, and (f) the excellent physical properties of the epoxy resin itself (toughness / high strength, electrical characteristics, It has excellent characteristics such as being expressed as it is without impairing (solvent resistance, etc.). These features will be described below.

(A) Short-time curing formulation The reaction mechanism between the onium salt and the epoxy compound is that onium ions excited by energy such as light and heat open the epoxy group and form a self-condensation network at once by a chain reaction. It has become. On the other hand, ordinary epoxy compounds undergo a condensation reaction with equivalent amounts of amines and the like to proceed with the curing reaction.

(B) Ease of compounding The thermally active latent onium salt has almost no effect on the physical characteristics even by a rough measurement. Therefore, the combination of the thermally active latent onium salt and the epoxy compound is extremely simple, and even a small amount of addition is effective. Therefore, no skill is required for handling. On the other hand, for general curing agents such as amines, it is necessary to accurately measure the equivalent amount with respect to the epoxy compound.

(C) Safety When a general amine-based curing agent is used, a nitrogen compound-containing vapor is generated during curing, which has an odor and an effect on the human body and the environment of the worker. On the other hand, in the case of the onium salt, the odor and the amount of vapor at the time of curing are much smaller than those in the case of the amine-based curing agent. This has the advantage of being friendly to the human body and the environment and easy to work with.

(D) Long pot life All epoxy compositions containing a general amine-based latent curing agent must be stored frozen, which is a management problem. On the other hand, many epoxy compositions containing a thermally active onium salt whose reaction start temperature is clearly higher than room temperature are stable at room temperature and do not need to be stored frozen. This is also advantageous for improving work efficiency and saving energy. In particular, the epoxy composition stored frozen needs to be returned from the freezing temperature to room temperature before use. At this time, the moisture contained in the surrounding atmosphere was condensed and contained, and the time required for returning to room temperature was long. Further, there is a problem that the excess epoxy composition needs to be returned to a frozen state.

(E) Transparency Most of the general amine-based curing agents are colored by the amine itself due to its structure. Even when a transparent amine is used, it is easily colored during heat curing because the amine is sensitive to heat. Therefore, it was difficult to obtain a colorless and transparent cured product without some modification. On the other hand, in the case of an onium salt, since the onium salt itself is transparent, a colorless and transparent cured product can be easily obtained by using an epoxy composition which is a colorless and transparent epoxy resin.

(F) Excellent properties When using a general amine-based curing agent, the amine-based curing agent is used in an equivalent amount with respect to the epoxy compound. Therefore, the physical characteristics of the epoxy resin (cured product of the epoxy composition) are affected by the amine curing agent. On the other hand, when an onium salt is used, the effect of initiating ring-opening polymerization of an epoxy group can be exhibited even in a trace amount of 1 wt% or less. Therefore, the excellent properties of the epoxy resin itself (toughness / high strength, electrical properties, solvent resistance, etc.) can be exhibited as they are.

The onium salt-containing one-component epoxy composition is a composition having the above-mentioned characteristics. However, there were many variations (unevenness) in the activity of onium salts. For this reason, it has been difficult to select a well-balanced onium salt that can achieve both low-temperature activity and potential from a wide variety of onium salts.

In applications for films for electrical materials using an epoxy composition as an adhesive, a polyimide film having a high glass dislocation temperature and high dimensional stability even in a high temperature region is widely used. Polyimide films are very expensive compared to films of other materials. Therefore, although the heat resistance and dimensional stability are inferior, it is possible to cope with various processing, and the use of cheaper various films called PET and engineering plastics is increasing. These inexpensive films are also used in large quantities in applications such as electrical materials.

For example, the PET film has a continuous use temperature of 106 ° C. according to the UL standard (UL746). However, when the epoxy composition is cured at a high temperature, distortion occurs between the epoxy resin and the base film during curing. This strain could be a fatal defect in precision electronic materials.

Further, as a feature of the epoxy composition, there is a problem that the epoxy resin is generally hard, although the adhesive strength is excellent. The hardness of the epoxy resin, even if it imparted flexibility, was unsuitable for film applications. For this reason, it has been desired to develop an epoxy resin having flexibility so as to follow the film and deform, and a one-component epoxy composition capable of being strongly cured at a low temperature.

In addition, epoxy compositions are used in large quantities for purposes other than film applications. Many general electric and electronic parts are heat-sensitive, and it has been desired to develop a one-component epoxy composition that can be cured at a low temperature and for a short time with less thermal shock.

In industrial line production, the biggest advantage of low temperature and short time curing is improvement of productivity and cost reduction by energy saving. However, its development was accompanied by the problem of room temperature stability of the one-component epoxy composition, and low-temperature, short-time curing formulations have long been a dream.

In particular, a one-component epoxy composition that can be cured at a low temperature of 60 to 80 ° C. and has high hardness and high strength, which has been desired for electrical material applications, and ultra-flexible cured physical properties such as films having opposite properties. A one-pack epoxy composition with has not yet been found.

For example, in the case of a combination of an onium salt whose reaction start temperature is close to room temperature and a conventional epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: JER828), the shelf life is short, and when mixed with an epoxy composition, the reaction starts immediately. It is considered that many of them cannot be a one-component latent curing composition. On the other hand, in the case of a combination of an onium salt having a high reaction start temperature and an epoxy resin (trade name: JER828), the shelf life is long and stable, but at a curing temperature of less than 100 ° C., especially at a low temperature in the range of 60 to 80 ° C. Nothing was known to cure.

Further, in the one-component epoxy resin containing onium salt, the amount of onium salt used with respect to 100 parts by weight of the epoxy resin is described in, for example, Patent Documents 1 and 2. Although these patent documents describe that an onium salt can be used in the range of 0.01 to 15 parts by weight with respect to 100 parts by weight of an aromatic hydrogenated epoxy compound, the amount used and the curing characteristics of the epoxy resin are described. There was no report that clarified the characteristics of the cured product, especially the epoxy equivalent and the amount of the onium salt, and examined them in detail.

Further, in both of these patent documents, although there is a description of 0.17 parts by weight of onium salt with respect to 100 parts by weight of epoxy resin in the examples, the curing conditions of various epoxy resins are described from the relationship between the epoxy equivalent and the amount of onium salt blended. In particular, no report has been made on the characteristics of the cured product at a curing temperature of less than 100 ° C. in detail.

Japanese Unexamined Patent Publication No. 2001-19742 Japanese Unexamined Patent Publication No. 2006-348308

The present invention has been made against the background of the above-mentioned problems of the prior art, and it is an object of the present invention to provide a conductive epoxy composition which is a cured product having super-flexibility and bending resistance that can follow a flexible film. Make it an issue.

The conductive epoxy composition of the present invention that solves the above-mentioned problems is a composition comprising only an epoxy compound composed of a single component as a resin component, the epoxy compound, an onium salt, and silver powder, and the onium. The reaction start temperature of the salt when heated together with the bisphenol A type liquid epoxy resin is 45 ° C. or higher, and the compounding ratio of the onium salt is in the range of 10 to 70 mass% with respect to 100 mass% of the epoxy compound, and is cured. The die shear tensile shear strength of the cured product obtained by the above method is 5 MPa or more, and the cured coating film obtained by applying it to a film is visually displaced in a bending resistance test in which the positions are shifted between the front surface and the back surface of the film and bent by 180 °. It is characterized by not causing cracks.

FIG. 1 is a graph showing the relationship between the epoxy equivalent and the compounding ratio of the onium salt. FIG. 2 is a graph showing the relationship between epoxy equivalent and volume resistivity.

Hereinafter, the present invention will be specifically described with reference to embodiments.
(Epoxy composition)
The conductive epoxy composition of this embodiment is an epoxy composition containing only an epoxy compound composed of a single component as a resin component, the epoxy compound, an epoxy compound, an onium salt, and silver powder, and is an epoxy. The compound is composed of a single component, and the onium salt has a reaction start temperature of 45 ° C. or higher when heated together with a bisphenol A type liquid epoxy resin, and the compounding ratio of the onium salt is 10 to 70 mass with respect to 100 mass% of the epoxy compound. It is characterized by being in the range of%.

The epoxy composition of this embodiment is a one-component epoxy composition because it contains an epoxy compound, an onium salt, and silver powder.

The onium salt initiates ring-opening polymerization of the epoxy group of the epoxy compound.
The onium salt has a reaction starting temperature of 45 ° C. or higher when heated together with the bisphenol A type liquid epoxy resin. That is, the reaction start temperature when heated with the epoxy compound is 45 ° C. or higher. When the reaction start temperature is within this temperature range, the epoxy composition of the present embodiment starts curing at a relatively low temperature and does not cure at room temperature.
The upper limit of the reaction start temperature of the onium salt is not limited. For example, the temperature can be selected from temperatures such as 270 ° C, 250 ° C, 200 ° C, 170 ° C, 150 ° C, 120 ° C, 100 ° C, 75 ° C or lower, and is preferably 75 ° C or lower. The reaction start temperature of the onium salt is more preferably 50 ° C. or higher and 65 ° C. or lower.
As the reaction start temperature of the onium salt with the bisphenol A type liquid epoxy resin, the measurement result by the differential scanning calorimetry (DSC) described later can be used.

As the onium salt, the effect can be exhibited by using one kind of compound, but a plurality of kinds of two or more kinds may be used if necessary.
The specific compound of the onium salt is not limited as long as it has the above-mentioned characteristics. For example, as pyridinium salts having excellent low temperature curability, N- (αphenylbenzyl) -4-cyanopyridinium hexafluoroantimonate, N- (1-naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, N-cinnamyl Examples thereof include -2-cyanopyridinium hexafluoroantimonate, N-cinnamyl-4-cyanopyridinium hexafluoroantimonate, N-cinnamyl-2-chloronium hexafluoroantimonate and the like.

As an aliphatic sulfonium salt having excellent low-temperature curability, 1-naphthylmethyldimethylsulfonium hexafluoroantimonate, 1-naphthylmethyltetramethylenesulfonium hexafluoroantimonate, cinnamyldimethylsulfoniumhexafluoroantimonate, cinnamyltetramethylenesulfoniumhexa Fluoroantimonate, 9-fluorenyldimethylsulfonium hexafluoroantimonate, 9-fluorenetetramethylenesulfonium hexafluoroantimonate and the like can be mentioned.

As N-methylammonium salts that are thermally and photoactive, N-methyl-4-cyanopyridinium hexafluoroantimonate, N-methyl-2-chloropyridinium hexafluoroantimonate, and N-methyl-2-methoxypyridinium hexafluoroantimonate. Nate, N-Methyl-2,6-dimethylpyridinium hexafluoroantimonate, N-methyl-2-chloro-6-methoxypyridiniuhexafluoroantimonate, N-methyl-3-bromoquinolium hexafluoroantimonate, N -Benzyl-2-cyanopyridinium hexafluoroantimonate and the like can be mentioned.

As quinolium salts with thermal and photoactivity, N-benzyl-3-bromoquinolium hexafluoroantimonate, N- (α-phenylbenzyl) -3-bromoquinolium hexafluoroantimonate, N- (1-naphthyl) Methyl) -3-bromoquinolium hexafluoroantimonate, N-cinnamyl-3-bromoquinolium hexafluoroantimonate and the like can be mentioned.

As ammonium salts that are thermally and photoactive, N-benzylpyrazinium hexafluoroantimonate, N- (4-nitrobenzyl) pyrazinium hexafluoroantimonate, N- (4-methoxybenzyl) pyrazinium hexafluoro. Antimonate, N- (α-phenylbenzyl) pyrazinenium hexafluoroantimonate, N-cinnamylpyrazinium hexafluoroantimonate, N- (-1-naphthylmethyl) pyrazinenium hexafluoroantimonate, N- Benzyl-4-bromo-N, N-dimethylanilinium hexafluoroantimonate, N- (1-naphthylmethyl) -4-bromo-N, N-dimethylanilinium hexafluoroantimonate and the like can be mentioned.

As ammonium salts with high heat and light activity, N-methyl-2-methyl-, N-methyl-2- (4-methyl-) benzothiazolium hexafluoroantimonate, N-methyl-2- (1) -Methyl-) Benthiazolium hexafluoroantimonate, N-methyl-2-benzylthiopyridinium hexafluoroantimonate and the like can be mentioned.

2-Indanylphenylmethylsulfonium hexafluorophosphonate, 1-ethoxycarbonylethylphenylmethylsulfonium hexafluorophosphonate, phenylmethyl-2-methyl-2-phenylpropylsulfoniumhexa are examples of aromatic sulfonium salts with excellent thermal and photoactivity. Fluorophosphonate, 2-phenylethylphenylmethylsulfonium hexafluorophosphonate, 2-phenylpropylphenylmethylsulfonium hexafluorophosphonate, 2- (4-methoxyphenyl) ethylphenylmethylsulfonium hexafluorophosphonate, 3- (4-methoxyphenyl)- Compounds such as 2-propylphenylmethylsulfonium hexafluorophosphonate, 4-hydroxyphenylbenzylmethylsulfonium hexafluorophosphonate, and benzyldimethylsulfonium hexafluorophosphonate can also be used in the present invention as long as they exhibit the above characteristics.

Phenylboleate complexes (manufactured by Sony Chemical Co., Ltd., manufactured by Dexeria Liz Co., Ltd.) and 2-butene-1-thioniacyclopentahexafluoroantimonate (manufactured by Asahi Denka Kogyo Co., Ltd., trade names) have already been commercialized. : CP66), 3-Methyl 2-butene-1-thioniacyclopentahexafluoroantimonate (manufactured by Asahi Denka Kogyo Co., Ltd., trade name: CP77), dibutylphenyliodonium hexafluorophosphonate (manufactured by Midori Chemical Co., Ltd.), benzyl Methyl-p-methoxycarbonyloxyphenylsulfonium hexafluoroantimonate (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI-45), 1-naphthylmethylmethyl-p-hydroxyphenylsulfonium hexafluoroantimonate (Sanshin Chemical Industry Co., Ltd.) Made by Sanshin Chemical Industry Co., Ltd., trade name: SI-60), 2-methylbenzylmethyl-p-hydroxyphenylsulfonium hexafluoroantimonate (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI-80), 2-methylbenzylmethyl p -Methoxycarbonyloxyphenyl sulfonium tetrakis (pentafluorophenyl) borate (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI-B2A), benzylmethyl p-methoxycarbonyloxyphenylsulfonium tetrakis (pentafluorophenyl) borate (sanshin chemical) Industrial Co., Ltd., trade name: SI-B3A), triphenylsulfonium hexafluorophosphonate (Midori Chemical Co., Ltd.), triphenylsulfonium hexafluoroantimonate (Midori Chemical Co., Ltd.), triarylsulfonium hexafluorophosphonate (Dow) From compounds such as Chemical Japan Co., Ltd., trade name: UVI-6990), those exhibiting the above characteristics can be used.

The onium salt may be mixed with an auxiliary agent. Examples of the auxiliary agent include an activity modifier that regulates the activity of polymerization and an auxiliary agent that has a reaction suppressing effect and improves storage stability. The amount of the auxiliary agent added is not limited, but is preferably 10 mass% or less when the total mass of the onium salt and the auxiliary agent is 100 mass%. The onium salt does not have to be mixed with an auxiliary agent. That is, it may be 0 mass%.
Examples of the auxiliary agent added to the onium salt include Sanshin Chemical Industry Co., Ltd., trade name: Sun Aid SI auxiliary agent.
The epoxy compound consists of a compound having an epoxy group. The epoxy group of the epoxy compound is ring-opened by the onium salt and cured by the polymerization reaction.

As long as the epoxy compound has the above-mentioned properties, the specific compound is not limited. For example, bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade names: JER828 and JER834), bisphenol F type epoxy resin (manufactured by ADEKA Co., Ltd., trade name: EP-4901), bisphenol E type epoxy resin (purin Co., Ltd.). Tech, product name: R710), hydride bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd., product name: YX8000 and YX8034), bisphenol A type polymer epoxy resin (Mitsubishi Chemical Co., Ltd., product name: JER1256) , Phenol novolak type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., product name: JER152), Cresol novolak type epoxy resin (manufactured by DIC Co., Ltd., product name: N660), Biphenyl type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., product name: YX4000), naphthalene type epoxy resin (manufactured by DIC Co., Ltd., trade name: HP-4032D), cyclopentadiene type epoxy resin (manufactured by DIC Co., Ltd., trade name: HP-7200), and the like.

The epoxy compound may also be mixed with an auxiliary agent. Examples of the auxiliary agent include additives such as a viscosity modifier (or viscosity stabilizer) for adjusting the viscosity of the epoxy composition and an activity modifier for adjusting the activity of polymerization. The amount of the auxiliary agent added is not limited. It can be a preferable addition amount for each auxiliary agent.

Examples of the auxiliary agent (viscosity adjuster, viscosity stabilizer) added to the epoxy compound include an alkyl glycidyl ether type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: YED216D), and a compound having a monovalent epoxy group (Mitsubishi). Chemical Co., Ltd., trade names: YED188 and YED122) can be mentioned.

The epoxy composition of the present embodiment may be formed of an epoxy compound, an onium salt, or a silver powder as a single component as a resin component, or may contain other components. The other component refers to a component that does not affect the reaction between the onium salt and the epoxy compound (a component that does not promote or inhibit the ring-opening polymerization reaction of the epoxy group).

Examples of the other component include a solvent (or a solvent) for adjusting the miscibility and viscosity of both the epoxy compound and the onium salt component. The type of solvent is not limited. For example, low boiling point solvents such as n-hexane, methyl ethyl ketone, and toluene, and esters having a boiling point of 150 to 250 ° C. can be mentioned. Since the curing reaction of the epoxy composition of this embodiment proceeds at a relatively low temperature, it is preferable to use a solvent having a relatively high volatility so that the residual solvent does not adversely affect the curing after curing. ..

The epoxy composition of this embodiment can be used as an adhesive. Since the epoxy composition of this embodiment is an epoxy composition that can be cured at a low temperature, which was difficult with the conventional one-component epoxy composition, it is a high-strength epoxy resin that the conventional epoxy composition is good at. In addition, it is possible to obtain both an ultra-flexible epoxy resin that is as supple as a film, which conventional epoxy compositions are not good at. Therefore, the epoxy composition of this embodiment exhibits the effects of improving productivity by low-temperature and short-time curing, cost reduction by energy saving, and improvement of workability in industrial line production.

The epoxy composition of this embodiment may contain a filler. Examples of the filler include fillers used in conventional epoxy compositions. By containing the filler, the desired properties can be imparted to (the cured product of) the epoxy composition.
Examples of the filler include metal particle powder, inorganic particle powder, carbon powder, organic particle powder and the like. The filler is more preferably amorphous silica powder.
When the epoxy composition of this embodiment contains a filler, the blending ratio thereof is not limited. For example, when the epoxy composition of the present embodiment contains silica powder as a filler, it is preferably 20 mass% or less when the total mass of the epoxy composition is 100 mass%. The blending ratio of the filler is more preferably 10 mass% or less, further preferably 5 mass% or less.

That is, when the total mass of the epoxy composition is 100 mass%, it is preferable to contain a filler made of amorphous silica at 20 mass% or less.

The epoxy composition of this embodiment can be suitably used as a conductive adhesive. The conductive adhesive can be formed by adding a conductivity-imparting material to the epoxy composition of the present embodiment. The conductive material is not limited as long as it is made of a conductive material. For example, silver, copper, gold, nickel, aluminum, palladium, platinum, metal coated polymers and fillers, carbon black, carbon fiber, graphite, nanosilver, nanocopper, nanoaluminum, nanogold, nanonickel, carbon nanotubes. Such as conductive powder can be mentioned. The particle shape of the conductive powder is not limited, and examples thereof include a spherical shape, a needle shape, a flake shape, and the like, and a flake shape is more preferable. The conductive powder may consist of one type, but may be a combination of a plurality of conductive powders having different particle shapes, particle diameters, surface cleanliness, and the like.
Of these, it is more preferable to use flake-shaped silver powder as a conductivity-imparting material. The silver powder may consist of one type, but may be a combination of a plurality of silver powders having different particle shapes, particle diameters, surface cleanliness, and the like.
Further, the silver powder can exhibit the same effect regardless of whether it is washed or unwashed.

When silver powder is used, the amount used is preferably 75 to 95 mass% when the total mass of the epoxy composition (or the conductive adhesive) is 100 mass%. If it is less than 75 mass%, sufficient conductivity cannot be obtained. When it exceeds 95 mass%, the proportion of the epoxy composition decreases, the brittleness after curing increases, and the function as an adhesive is not sufficiently exhibited. When silver powder is used, it is more preferably 80 to 92 mass%, and even more preferably 85 to 90 mass%, when the entire epoxy composition is 100 mass%.

When silver powder is used, it is preferably a powder of flake-shaped particles. The flake shape is also called a flaky shape, and examples thereof include a substantially plate shape, a substantially rod shape having an axis extending in one direction, and a dendritic shape having an axis extending in a plurality of directions. Flake-shaped particles are more likely to come into contact with other adjacent particles than spherical particles. That is, it is easy to form a conductive path.

When silver powder is used, the viscosity of the conductive adhesive is preferably 1 to 90 Pa · s at 25 ° C. The viscosity of the conductive adhesive can be measured by the measuring method described later. When the viscosity at 25 ° C. is in this range, it can be handled as a conductive adhesive. If the viscosity is less than 1 Pa · s, it becomes difficult to prevent the silver powder from settling. When the viscosity exceeds 90 Pa · s, the viscosity of the conductive adhesive becomes high, which makes it difficult to handle when using. The viscosity at 25 ° C. is more preferably 5 to 70 Pa · s, further preferably 10 to 50 Pa · s.

That is, it is preferable that the epoxy composition of the present embodiment contains silver powder at 75 to 95 mass% and has a viscosity at 25 ° C. of 1 to 90 Pa · s when the whole is 100 mass%. The silver powder is more preferably in the form of flakes.

The epoxy composition of this embodiment preferably has an epoxy equivalent of 1000 or more and a volume resistivity of 2 × 10-4 Ωcm or less. The epoxy composition of this embodiment has a large epoxy equivalent of 1000 or more, but has excellent conductivity (low volume resistivity) of 2 × 10-4 Ωcm or less.

In the epoxy composition of this embodiment, the relationship between the mass part of the onium salt and the volume resistivity in the epoxy compounds having different epoxy equivalents is shown in FIG. FIG. 2 shows the relationship between the epoxy equivalent and the volume resistivity when the onium salt is contained in 2 parts by mass with respect to the epoxy compound. As the epoxy compound, an epoxy compound having an epoxy equivalent of 165,186,194,250,263,470,1004,265,7318 was used. The epoxy compound and onium salt are the compound used in the examples described later and the corresponding onium salt.
The volume resistivity of these samples was measured under the curing conditions of 80 ° C. for 60 minutes in the same manner as in Example 33 described later.

As shown in FIGS. 1 and 2, an epoxy compound having an epoxy equivalent of 1000 or more exhibits excellent conductivity of 2 × 10-4 Ωcm or less, further 1 × 10-4 Ωcm or less, that is, on the order of 10-5 Ωcm. do. Volume resistivity on the order of 10-5 Ωcm is a level of conductivity that is difficult to achieve with conventional epoxy compositions.
As shown above, when the epoxy composition of this embodiment is blended with a conductive powder (silver powder), the relationship between the epoxy equivalent and the onium salt blending amount has been diligently examined. As a result, the epoxy equivalent and the onium salt blending amount have been determined. The relationship was clarified, and it was clearly found that each had an optimum compounding region.

Further, in the epoxy composition of the present embodiment, the relationship between the mass part of the onium salt and the tensile shear force in the epoxy compounds having different epoxy equivalents is shown in FIG. As the epoxy compound, an epoxy compound having an epoxy equivalent of 165,186,194,250,263,470,1004,265,7318 was used. The epoxy compound and the onium salt are the compound and the corresponding onium salt used in the examples described later.
The tensile shear force (die shear strength) of these samples was measured under the curing conditions of 80 ° C. × 60 minutes in the same manner as in Example 33 described later.

As shown in FIG. 3, among a plurality of types of epoxy compounds having different epoxy equivalents, the tensile shear force (adhesive force with the adherend) exhibits a high stress (adhesive force) of 5 MPa regardless of any of the epoxy compounds. I know I can do it. That is, by adjusting the content ratio of the onium salt contained in the epoxy composition, it can also be used as an adhesive having excellent adhesiveness.

It is preferable that the conductive adhesive further contains silica in an amount of 0.01 to 20 mass% when the whole is 100 mass%. Silica improves the dispersibility of the silver powder in the epoxy composition and prevents settling in the conductive adhesive. If the silica content is less than 0.01 mass%, the effect of the addition is not sufficiently exhibited. If it exceeds 20 mass%, the adhesive strength and conductivity tend to decrease. The silica content is more preferably 5 mass% or less, further preferably 2 mass% or less.
As the silica, silica used as a filler of a conventional conductive adhesive can be used, and it is more preferable that the silica is nanosilica having a particle size of nm, and further preferably hydrophobic nanosilica. As the silica, commercially available nanosilica made of amorphous material can be used.

(Reference example)
Next, prior to explaining the conductive epoxy composition of this embodiment, the epoxy composition containing no silver powder among the compositions will be described for reference.
The epoxy composition has a characteristic that when used as an adhesive, it exhibits strong adhesive strength in a relatively low temperature and short-time treatment. Adhesive strength can be defined by die shear tensile shear strength. The die shear tensile shear strength can be obtained by the method described later. The tensile shear strength after heat treatment at 70 to 80 ° C. for 60 minutes is preferably 5 MPa or more. Such epoxy compositions are more preferred because they lead to improved productivity, especially in industrial production lines. Those exhibiting a tensile shear strength of 10 MPa or more after 60 minutes of heat treatment at 70 to 80 ° C. are more preferable.
The epoxy composition of this embodiment is preferably used as an adhesive, and when a conductive material is added, it is preferably used as a conductive adhesive.

The epoxy composition preferably contains a reinforcing material. By containing the reinforcing material, the epoxy composition of the present embodiment can be obtained as a cured product containing the reinforcing material. This cured product contains a reinforcing material and has excellent strength.
The reinforcing material is not limited, and those used in conventional composite materials using an epoxy composition can be used. Examples of the reinforcing material include a dense or porous structure and a fibrous material. Further, the material thereof is not limited, and examples thereof include carbon, metal, inorganic material, and organic material. Further, the reinforcing material is preferably a structural material formed by arranging these fibers.
That is, the reinforcing material is an aggregate of one or more fibers selected from carbon fibers, metal fibers, inorganic fibers, and organic fibers, and / or a dense or porous structure made of an organic material or an inorganic material. Is preferable. The fiber accumulation is a state in which the fibers are oriented and arranged in a predetermined direction (arbitrary angle), or a state in which at least adjacent short fibers are entangled with each other. The reinforcing material is more preferably a strip-shaped body in which fibers are oriented and arranged in a predetermined direction, a woven fabric of the fibers, or a non-woven fabric of the fibers. In a dense or porous structure, the proportion of pores (porosity) is not limited. The porosity can be the same as that of the conventional porous structure. It is preferably a porous structure.

(Curing method)
The epoxy composition of this embodiment can be cured by heat treatment at a temperature of 60 ° C. or higher. By heat treatment in this temperature range, the reaction between the epoxy compound and the onium salt starts in the epoxy composition of the present embodiment, and the epoxy composition of the present embodiment is cured. Also, heating at this temperature allows for quick completion of curing.
The heat treatment temperature is not limited, and is a temperature higher than the reaction starting temperature of the onium salt contained in the epoxy composition. The temperature is preferably about the reaction start temperature to the reaction start temperature + 30 ° C. of the onium salt. More preferably, it is a temperature of about the reaction start temperature to the reaction start temperature + 10 ° C. of the onium salt.

The upper limit of the heat treatment temperature is not limited, and can be a temperature higher than the reaction start temperature of the onium salt contained in the epoxy composition. The temperature is preferably about the reaction start temperature to the reaction start temperature + 30 ° C. of the onium salt. In particular, when applied to films (film-like members) and heat-sensitive electronic component applications, a temperature of about reaction start temperature to reaction start temperature + 10 ° C. of the onium salt is preferable.
It is preferable to heat-treat at a temperature of 80 ° C. or lower. In an epoxy composition using an onium salt having a reaction starting temperature of 45 to 75 ° C., the curing reaction can proceed at a low temperature of 60 to 80 ° C.
In the epoxy composition, the curing temperature can be controlled by selecting the optimum compounding ratio of the epoxy equivalent and the onium salt. The curing temperature is a temperature within the range of the temperature at which the curing reaction starts to the temperature until the curing reaction is completed (the temperature at which the curing reaction is in progress). That is, when there is a change (temperature rise) in the temperature in the heat treatment, the curing temperature is one of the temperature at which the curing reaction starts, the temperature until the curing reaction is completed, and the temperature at which the curing reaction is in progress. It can be a temperature, preferably a temperature at which the curing reaction starts. As a result, the curing reaction can be performed under conditions that cannot be considered as the curing conditions of a normal epoxy resin. For example, heat treatment in a medium temperature range of about 150 ° C. enables the progress of the curing reaction at a second speed (that is, curing at a second speed).
The curing temperature of the epoxy composition of this embodiment is not limited. When shortening the curing time, it is preferable to set the curing temperature high.

This heat treatment preferably has a heating time of 5 seconds or more and 5 minutes or less. When the heating time is within this range, the epoxy composition is sufficiently cured. When the heating time is 5 seconds or more, the epoxy composition can be sufficiently cured. Since the curing reaction of the epoxy composition of this embodiment proceeds rapidly, the curing of the epoxy composition can be completed by heating for 5 minutes or less. That is, the epoxy composition can be sufficiently cured by heating for 5 minutes or less. The heating time is not limited as long as it is a heating time of 5 seconds or more, and is 10 seconds or more, 30 seconds or more, 60 seconds (1 minute) or more, 3 minutes or more, 5 minutes or more, 7 minutes or more, 10 minutes. Any heating time of 15 minutes or more, 20 minutes or more, 30 minutes or more, 60 minutes or more, and 120 minutes or more may be used.
The epoxy composition is sufficiently cured when the heating time is within the above range. Sufficient curing means that the die shear tensile shear strength is 5 MPa or more when used as an adhesive.

The atmosphere of the heat treatment is not limited. It can be appropriately selected from an atmosphere such as an atmospheric atmosphere, an oxidizing atmosphere containing oxygen, and an atmosphere of an inert gas such as argon gas. Atmospheric atmosphere is preferred. The pressure in the heat treatment atmosphere is also not limited. It can be appropriately selected from conditions such as atmospheric pressure, reduced pressure conditions, and pressurized conditions. Atmospheric pressure is preferred.

For the heat treatment, it is preferable to appropriately determine the heat treatment temperature and the heating time. When the heat treatment temperature is high, the heating time can be shortened. On the contrary, when the heat treatment temperature is lowered, the epoxy composition can be cured by lengthening the heating time.
For example, in the configuration of sample 5 described later, the cured product obtained under the conditions of 70 ° C. × 1 hr, 80 ° C. × 1 hr, 100 ° C. × 1 hr, 150 ° C. × 1 hr, and 200 ° C. × 1 hr has a high adhesive strength of 13 MPa to 28 MPa. Is shown. That is, a cured product showing high adhesive strength can be obtained.
Similarly, as shown in Table 8 below, although it is related to the amount of onium salt, it has a high adhesive force of about 20 to 30 MPa under heat treatment conditions of 155 ° C. × 60 seconds, 175 ° C. × 60 seconds, and 200 ° C. × 60 seconds. Is shown. Curing in seconds is possible, improving work efficiency. Further, even when an onium salt having a reaction start temperature of 136 ° C. is used, a high adhesive force of 15 to 45 MPa is exhibited at 275 ° C. × 30 seconds and 275 ° C. × 45 seconds.
As shown in Samples 241-245 in Table 9 below, the epoxy composition is stored at 40 ° C. × 4 weeks and then 25-35 MPa high at 150 ° C. × 1 hr, 250 ° C. × 90 seconds, 250 ° C. × 120 seconds. Shows adhesive strength.

(Preservation method)
In the method for storing the epoxy composition of the present embodiment, the epoxy composition of the present embodiment can be stored at a temperature of 0 ° C. or higher and lower than the reaction starting temperature of the onium salt. That is, the epoxy composition of this embodiment can be stored at a temperature equal to or higher than the freezing temperature of the epoxy composition and lower than the reaction starting temperature of the onium salt. The storage temperature is preferably a temperature lower than the reaction start temperature by about 10 to 20 ° C., more preferably room temperature (0 to 40 ° C.), and further preferably 5 to 30 ° C.
Of course, the epoxy composition of this embodiment can be stored at a temperature lower than 0 ° C. (freezing storage). In the conventional one-component epoxy composition using amine, the reaction proceeds without stopping (the reaction proceeds at a rate-determining rate even during frozen storage). However, in the epoxy composition of this embodiment, the reaction is stopped particularly in a semi-cured state. Therefore, long-term storage is possible at a temperature lower than 0 ° C.

Specifically, in the epoxy composition of this embodiment, the curing reaction is started by heating above the reaction starting temperature as described above. In other words, storage is possible by keeping the temperature below the reaction start temperature. That is, it can be stored at a low temperature.
The state (reaction stage) of the epoxy composition in the storage method of this embodiment is not limited. Whether it is an uncured state in which the epoxy composition and the onium salt are mixed, or a semi-cured state (generally also referred to as B stage), which is an intermediate stage of the reaction of the thermosetting resin. But it may be.

The epoxy composition in the storage method of this embodiment is the epoxy composition of this embodiment described above. That is, it contains silver powder (conductive powder), reinforcing material (carbon fiber, metal fiber, inorganic fiber, woven fabric or non-woven fabric of organic fiber, structure), and other additives (for example, viscosity modifier). Is also good. In particular, when the viscosity modifier is contained, the epoxy composition of the present embodiment can be stored in a state where the change (curing) in the viscosity of the epoxy composition is suppressed.
When the epoxy composition contains a woven fabric or a non-woven fabric of fibers as a reinforcing material, it is preferable that the mixture of the epoxy compound and the onium salt is impregnated in the woven fabric or the non-woven fabric.

The storage method of this embodiment can be applied to an epoxy composition containing an onium salt having a higher reaction starting temperature in addition to the above-mentioned epoxy composition. For example, it can be applied to an epoxy composition containing an onium salt having a reaction starting temperature of 100 ° C. or higher. Examples of such onium salts include SI-100 (reaction start temperature: about 100 ° C.) and SI-150 (reaction start temperature: about 150 ° C.) manufactured by Sanshin Chemical Industry Co., Ltd. can.
The method for preserving the epoxy composition of the present embodiment is a storage method applicable to the preservation of the epoxy composition of the present embodiment. The epoxy composition of this embodiment may be stored at a temperature equal to or lower than the reaction starting temperature of the onium salt and at a temperature of 0 ° C. or lower. That is, it can be stored frozen.
According to the storage method of this embodiment, even if the epoxy composition is useful for a composite material, as shown in Samples 251 to 256 in Table 10 described later, if an onium salt is selected, the epoxy resin is used as it is or is strengthened. After storing the material (for example, SiC, sintered aluminum, carbon fiber) in a semi-cured state (usually called B-stage resin) at room temperature for 1 year, it is 20 to 30 MPa at 150 ° C. x 60 minutes. Shows high adhesive strength.

Hereinafter, the present invention will be specifically described with reference to Examples.
The physical property values of the epoxy composition and its cured product were measured by the methods described below.

(A) Reaction start temperature of onium salt and bisphenol A type liquid epoxy resin First, the onium salt and its activity adjuster are dissolved in γ-butyl lactone (solvent), and the onium salt is 33 mass% and the activity adjuster is 0.33 mass. Make an onium salt solution contained in%. At this time, it is preferable to dissolve the onium salt first and then the storage stabilizer.

A 10 mg sample containing this onium salt solution and a bisphenol A type liquid epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: JER828) so as to have a mass ratio of 2: 100 is enclosed in a special aluminum pan.

This sample is set in a DSC device (manufactured by Seiko Instruments, Inc., trade name: DSC6200) and measured in a temperature range of 30 ° C. to 250 ° C. at a heating rate of 10 ° C./min. The reaction start temperature is a temperature at which the baseline of the DSC begins to shift to the heat generation side due to the reaction. Specifically, the baseline obtained by removing noise by processing is obtained, and the intersection of the tangents is set as the heat generation start temperature.

(B) Epoxy equivalent Measured by a method according to JIS K7236: 2001.
Specifically, in the case of a liquid epoxy resin, the state as it is, and in the case of a solid epoxy resin, a state in which the solid content is dissolved in 40 wt% is mixed in a 100 mL beaker at 6.0 × 10-4 to 9.0 × 10-4 mol. A sample corresponding to the epoxy group of No. 1 is collected and weighed (significant figure: 0.1 mg digit).
Add 10 mL of chloroform to the weighed epoxy solution and dissolve by stirring with a stirrer containing a stir bar.

Next, add 20 mL of acetic acid and 10 mL of tetraethylammonium bromide solution.
Immerse the electrode and titrate with 0.1 mol / L perchloric acid-acetic acid standard solution.
Perform a blank test by the same operation and leave it as a blank.
For titration, an automatic titration device (trade name: COM-1750), a glass electrode (trade name: GE-101B), and a comparison electrode (trade name: RE-201) (all manufactured by Hiranuma Sangyo Co., Ltd.) were used. The liquid inside the comparative electrode is measured using a saturated sodium perchlorate / acetic acid solution.

(C) Viscosity measurement of solution Using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., trade name: RE-80U), a dichotomized value of 3 ° cone 5 rpm at 25 ° C. is measured.

(D) Thermosetting treatment of epoxy composition A warm air oven with a temperature accuracy of ± 3 ° C. (manufactured by Isuzu Seisakusho Co., Ltd., trade name: AT-S13) is used for thermosetting. Insert a thermometer near the sample in the oven and inside the oven, and check the temperature indicated on the oven and the temperature at the three added points. As the processing temperature (thermosetting temperature), the temperature near the sample is adopted. When the sample is placed in the oven, the temperature near the sample drops after the sample temperature drops slightly due to the influence of the heat capacity of the adherend (adhesive) (when the heat capacity of the adherend is large, the amount of heat increases). When the temperature returns to -2 ° C. of the set temperature, the curing treatment is started (usually about 2 to 3 minutes), and then the curing treatment is performed for a predetermined time (30 minutes, 60 minutes, 180 minutes).
When the predetermined time is in seconds (10, 30, 60 seconds) (so-called fast curing per second), a heating device such as a hot plate is used instead of the oven.

(E) Adhesive strength (Die shear tensile shear strength)
An epoxy resin solution containing an onium salt is dropped onto a regular slide glass (manufactured by Matsunami Glass Industry Co., Ltd., trade name: S1112) as an adherend in a hemispherical shape of about 2 mm, and one side is 2 mm square x thickness. A 0.5 mm silicon chip placed on it and pressed with tweezers is subjected to the above heat curing reaction.

One day has passed after the curing reaction, and die shear tensile shear is measured at a tensile speed of 25 mm / min using a tensile compression tester (manufactured by Imada Seisakusho Co., Ltd., trade name: SH-2013M). The number of n is set to 5, and the average value thereof is adopted.

The judgment criteria were ⊚ (20 MPa or more), 〇 (5 MPa or more, less than 20 MPa), Δ (2 MPa or more and less than 5 MPa), × (less than 2 MPa), XX (uncured). All the adherends and jigs used are degreased with acetone.

(F) Volume resistance measurement Regular slide glass (manufactured by Matsunami Glass Industry Co., Ltd., trade name: S1112), polyimide film (manufactured by Toray DuPont Co., Ltd., trade name: Kapton), or PET with a thickness of 100 μm as the adherend. A sample is prepared by uniformly applying a conductive epoxy resin composition having a width of about 10 mm and a length of about 70 mm to a film (manufactured by Toray Industries, Inc., trade name: Lumirror S10) with a thickness of about 100 μm. The prepared sample is subjected to the above heat curing reaction.

The electric resistance value of the cured coating film is measured using a digital multimeter (manufactured by Takeda Riken Co., Ltd., trade name: TR6851) with an electrode distance of 50 mm.
(Calculation method of volume resistance) = Electrical resistance value (Ω) x cross-sectional area (film thickness x film width) / measurement distance).
A measuring device (manufactured by Ono Sokki Co., Ltd., trade name: ST-011) was used for film thickness measurement. Judgment criteria are ◎ (9 × 10-5Ωcm or less), 〇 (10-4Ωcm order), Δ (10-3Ωcm order), × (10-2Ωcm order or more).

(G) Color tone judgment Regular slide glass (manufactured by Matsunami Glass Industry Co., Ltd., trade name: S1112), polyimide film (manufactured by Toray DuPont Co., Ltd., trade name: Kapton), or PET film with a thickness of 100 μm (manufactured by Toray DuPont Co., Ltd., trade name: S1112) as an adherend. An epoxy resin solution containing an onium salt is dropped onto a hemispherical shape of about 5 mm on Toray Industries, Inc., trade name: Lumirror S10), and subjected to the above heat curing reaction.
A visual judgment is made on the cured coating film. The judgment criteria are 〇 (colorless and transparent), Δ (slightly colored transparent), and × (tan). Further, in the case of a conductive epoxy composition containing silver powder, a visual judgment is made on the cured coating film thereof. The judgment criteria are 〇 (no change), △ (slightly colored), and × (tan).

(H) Bending resistance test As an adherend, regular slide glass (manufactured by Matsunami Glass Industry Co., Ltd., trade name: S1112), polyimide film (manufactured by Toray DuPont Co., Ltd., trade name: Kapton), or PET with a thickness of 100 μm. A film (manufactured by Toray Industries, Inc., trade name: Lumirror S10) is cut into strips of about 30 x 100 mm, and an epoxy composition (conductive epoxy composition) having a width of about 10 mm and a length of about 50 mm with a thickness of about 50 μm. Is evenly applied to prepare a sample.

The curing reaction is carried out by the above method, and in the bending resistance test, the positions of the front and back surfaces of the coating film are shifted and the film is bent by 180 °, and cracks and cracks in the coating film are visually judged. The criteria for the bending resistance test are 〇 (no cracks), Δ (slight cracks or one crack), and × (both cracks or peeling).
In this evaluation as well, all the adherends and jigs used are degreased with acetone.

(I) Cross-cut test As an adherend, regular slide glass (manufactured by Matsunami Glass Industry Co., Ltd., product name: S1112), polyimide film (manufactured by Toray DuPont Co., Ltd., product name: Kapton), or a strip of approximately 30 x 100 mm. A 100 μm thick PET film (manufactured by Toray Co., Ltd., trade name: Lumirror S10) or a polyimide film (manufactured by Toray DuPont Co., Ltd., trade name: Kapton) with a width of about 13 mm with a thickness of 50 μm. An epoxy resin composition having a length of about 50 mm is uniformly applied to prepare a sample, which is cured by the above method. Since the PET film is a kind of poor adhesiveness, it was used as it is or after being subjected to corona treatment as a surface treatment and used for comparison.

The cured coating film is No. 1 conforming to JIS K5400. Using a 315 super cutter guide (manufactured by Taiyu Kikai Co., Ltd.), make 11 cuts to reach the substrate with a JIS K5400 compliant cutter at 1 mm intervals, then change the direction by 90 ° and pull 11 more in the same way, 100 stitches. Make a cut grid-like coating film. The cellophane adhesive tape is strongly pressure-bonded so as to cover the grid surface, and the cellophane adhesive tape is pulled apart at a stretch at an angle of 45 ° to determine the number of remaining coating films. The judgment criteria are 〇 (80 or more), Δ (less than 80 to 50 or more), and × (less than 50).

(J) Rubbing test Regular slide glass (manufactured by Matsunami Glass Ind. Co., Ltd., trade name: S1112), polyimide film (manufactured by Toray DuPont Co., Ltd., trade name: Kapton), or strip of approximately 30 x 100 mm as the adherend. An epoxy resin composition is applied to a 100 μm-thick PET film (manufactured by Toray Industries, Inc., trade name: Lumirror S10) having a thickness of about 50 μm, and then cured by the above method.

The cured coating film is dipped in toluene and rolled hard with absorbent cotton, and a load of 500 g is applied and rubbed 10 times back and forth to visually judge the change in the coating film. The judgment criteria are 〇 (insoluble or no change), Δ (partially dissolved), and × (50% or more dissolved).

(K) Storage stability test The prepared epoxy composition is placed in a screw cap bottle, sealed, and stored at a predetermined temperature for a predetermined period in a light-shielded state (a state in which ultraviolet rays are blocked). After a lapse of a predetermined period, the adhesive strength is measured by subjecting it to (E) adhesive strength (die shear tensile shear strength) test. Examples of the predetermined temperature include a freezing temperature (-10 ° C.), a refrigerating temperature (5 ° C.), a room temperature (25 ° C.), and an accelerated test temperature (40 ° C.).

[Example 1 and Comparative Example 1]
The epoxy composition of each sample of this example was prepared by the following method.
Weigh 10 g of an epoxy compound (liquid, manufactured by Mitsubishi Chemical Corporation, trade name: JER828) having an epoxy equivalent of 186 in a 20 mL screw cap bottle (manufactured by Nichiden Rika Glass Co., Ltd., trade name: SV-20).

Subsequently, an activity adjuster (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI auxiliary agent) was mixed and weighed with the onium salt shown in Table 1 at a mass ratio of 99: 1, and γ-butyl was used as a solvent. A lactone was added to prepare an onium salt solution containing an onium salt concentration of 33 mass% and an activity modifier of 0.33 mass%.

The prepared onium salt solution is added to the epoxy compound. The added onium salt has the ratio shown in Table 1 when the mass of the epoxy compound is 100 mass%.

As shown in Table 1, the epoxy composition of this example has a reaction starting temperature of 28 ° C. (Sample 1, trade name: SI-25) and 43 ° C. (Sample 2, trade name: SI-40). ), 48 ° C (Sample 3, trade name: SI-45), 50 ° C (Sample 4, trade name: SI-B2A), 63 ° C (Sample 5, trade name: SI-60), 71 ° C (Sample 6, Product name: SI-80), 78 ° C (Sample 7-8, PBPH), 83 ° C (Sample 9, product name: SI-B3A), 90 ° C (Sample 10, PBBQ), 108 ° C (Sample 11, product name) : SI-100), 136 ° C. (Sample 12, trade name: SI-150) (all commercially available products are manufactured by Sanshin Chemical Industry Co., Ltd.) were used. The PBPH of Samples 7 to 8 is N- (α-phenylbenzyl) -3-bromoquinolium hexafluoroantimonate. The PBBQ of Sample 10 is N- (α-phenylbenzyl) pyrazinenium hexafluoroantimonate. These were prepared by a known method.

As shown in Table 1, the epoxy composition of this example contains 3 mass% (samples 1 to 5, 7, 9 to 12) and 10 mass% (samples 1 to 5, 7, 9 to 12) when the onium salt has a mass of epoxy resin of 100 mass%. As shown in Samples 6 and 8), the blending amounts of the epoxy resin and the onium salt have been changed.

Here, the value of exp (−0.003X) (= Z) obtained from the epoxy equivalent 186 is 0.572. The compounding ratio (Ymass%) of the onium salt of each sample satisfies the relationship of 0.286 (= 0.5 × Z) ≦ Y ≦ 143.088 (= 250 × Z).

A stainless steel microspatula was inserted into the mixed solution, and the mixture was stirred on a touch mixer (manufactured by Yamato Kagaku Co., Ltd., trade name: MT-31) for 3 to 5 minutes to prepare a uniform solution.
As described above, the epoxy composition of this example was prepared.

The epoxy composition of this example is subjected to the measurement of the viscosity shown in (C) and the measurement of the die shear tensile shear strength shown in (E), and then the curing treatment shown in (D) under the predetermined conditions shown in Table 1. After that, the color tone determination shown in (G) was performed. The results are shown in Table 1.

As shown in Table 1, the epoxy compositions of Samples 3 to 6 in which the reaction starting temperature of the onium salt is within a predetermined range have a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength.

On the other hand, in Samples 1 and 2 in which the reaction start temperature of the onium salt was lower than the predetermined range (45 ° C.), the one-component epoxy composition was not established. Specifically, the reaction time of the curing reaction was too short, and the storage stability was deteriorated, so that the one-component epoxy composition could not be established. Further, the epoxy compositions of the samples 7 to 12 having a reaction starting temperature higher than that range (excessively high temperature) are not sufficiently cured at 70 to 80 ° C., and the die shear tensile shear strength is practically used as an adhesive. Especially, it is too small to be suitable.
As described above, it can be confirmed that the epoxy compositions of Samples 3 to 6 become a cured product having high strength by heating at 70 to 80 ° C.

[Example 2 and Comparative Example 2]
The epoxy composition of each sample of this example was prepared in the same manner as in Example 1 and Comparative Example 1 except that the mixing ratio of the onium salt was changed. The evaluation of this example was carried out in the same manner as in Example 1. Table 2 shows the measurement results measured in the same manner as in Example 1. The evaluation was carried out after the curing treatment was performed with the curing conditions shown in (D) as the conditions shown in Table 2.

In this example, the compounding ratio of the onium salt is different from that of the sample 5 of Example 1. Each sample was prepared using the onium salt whose compounding ratio is shown in Table 2. The ratio of the onium salt is as shown in Table 2 when the mass of the epoxy compound is 100 mass%.
For example, by adding 2.1 g of the prepared onium salt solution to the epoxy compound, the epoxy composition of the sample 28 is obtained. The onium salt added in the sample 28 corresponds to 7 mass% as shown in Table 2 when the mass of the epoxy compound is 100 mass%.

As shown in Table 2, the epoxy composition of this example contains 0.1 mass% (sample 21), 0.2 mass% (sample 22), when the onium salt has a mass of the epoxy resin of 100 mass%. 0.3 mass% (sample 23), 0.4 mass% (sample 24), 0.6 mass% (sample 25), 1 mass% (sample 26), 1.8 mass% (sample 27), 7 mass% (sample 28), It is contained in 15 mass% (sample 29), 60 mass% (sample 30), 100 mass% (sample 31), 140 mass% (sample 32), 160 mass% (sample 33), 180 mass% (sample 34).

Here, the value of exp (−0.003X) (= Z) obtained from the epoxy equivalent 186 is 0.572. The compounding ratio (Ymass%) of the onium salts of Samples 23 to 32 satisfies the relationship of 0.286 (= 0.5 × Z) ≦ Y ≦ 143.088 (= 250 × Z).
Further, the compounding ratio (Ymass%) of the onium salts of the samples 21 to 22 is less than 0.286. The compounding ratio (Ymass%) of the onium salts of the samples 33 to 34 is larger than 143.088.

As shown in Table 2, the epoxy compositions of the samples 23 to 32 in which the compounding ratio of the onium salt is within a predetermined range have a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength.

On the other hand, in the epoxy compositions of Samples 21 to 22 in which the mixing ratio of the onium salt is smaller than the predetermined range and Samples 33 to 34 in which the mixing ratio is large, the die shear tensile shear strength is so small that it is unsuitable for practical use as an adhesive.
Further, it can be confirmed that the epoxy compositions of the samples 23 to 32 become a cured product having high strength by heating at 70 to 80 ° C.

[Example 3 and Comparative Example 3]
Weigh 10 g of solid epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: JER1009) and 15 g of methyl ethyl ketone (MEK) with an epoxy equivalent of 2605 in a 50 mL screw cap bottle (manufactured by Nichiden Rika Glass Co., Ltd., trade name: SV-50). , The epoxy resin was dissolved to prepare an epoxy solution having an epoxy compound content of 40 mass%. If a part of the solvent evaporates during dissolution, the same amount of methyl ethyl ketone as the amount evaporated is added.

An onium salt (trade name: SI-60) having a reaction start temperature of 63 ° C. and an activity modifier (trade name: SI auxiliary agent) (both manufactured by Sanshin Chemical Industry Co., Ltd.) at a mass ratio of 99: 1. The mixture was weighed and weighed, and γ-butyl lactone was added as a solvent to prepare an onium salt solution containing an onium salt concentration of 33 mass% and an activity modifier of 0.33 mass%.

Add 0.30 g of the prepared onium salt solution to the epoxy solution. The added onium salt has the ratio shown in Table 3 when the mass of the epoxy compound is 100 mass%.

A stainless steel microspatula was inserted and stirred on a touch mixer (manufactured by Yamato Kagaku Co., Ltd., trade name: MT-31) for 3 to 5 minutes to prepare a uniform solution. If a part of the solvent evaporates even during stirring, the same amount of methyl ethyl ketone as the amount of evaporation is added.
As described above, the epoxy composition of this example was prepared. The epoxy composition of this example corresponds to sample 46 in Table 3.

As shown in Table 3, the epoxy composition of this example contains 0.01 mass% (sample 41), 0.02 mass% (sample 42), when the onium salt has a mass of the epoxy compound of 100 mass%. 0.1 mass% (sample 43), 0.3 mass% (sample 44), 0.6 mass% (sample 45), 1 mass% (sample 46), 10 mass% (sample 47), 20 mass% (sample 48), 40 mass% (Sample 49), 60 mass% (Sample 50), 100 mass% (Sample 51).
In the epoxy composition of this example, the mass ratio of the onium salt when the mass of the epoxy resin is 100 mass% is 0.01 and less than 0.02 for the sample 41, and 0.02 ≦ 1 for the samples 42 to 49. (= Y) It is within the range of ≦ 40, and it is 60 in the sample 50 and 100 in the sample 51, so that both are excessively larger than 40.
The evaluation of this example was carried out in the same manner as in Example 1. The measurement results are shown in Table 3.

As shown in Table 3, the epoxy compositions of the samples 42 to 49 in which the compounding ratio of the onium salt is within a predetermined range have a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength.

On the other hand, in the epoxy compositions of the sample 41 in which the mixing ratio of the onium salt is smaller than the predetermined range and the samples 50 to 51 in which the mixing ratio is large, the die shear tensile shear strength is so small that it is unsuitable for practical use as an adhesive.
Further, it can be confirmed that the epoxy compositions of the samples 42 to 49 become a cured product having high strength by heating at 70 to 80 ° C.

[Example 4 and Comparative Example 4]
The epoxy composition of each sample of this example was prepared in the same manner as in Example 1 except that different epoxy compounds were used and the compounding ratio of the onium salt and the epoxy compound was changed. The evaluation of this example was carried out in the same manner as in Example 1. Table 4 shows the measurement results measured in the same manner as in Example 1. The evaluation was carried out after the curing conditions shown in (D) were cured under the conditions shown in Table 4.
In this example, an epoxy compound having an epoxy equivalent of 165 (manufactured by Mitsubishi Chemical Corporation, trade name: JER806) was used as the epoxy compound. As the onium salt, the one having a reaction start temperature of 63 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI-60) was used as in the sample 5 of Example 1.

As shown in Table 4, the mixing ratio of the onium salt is 0.2 mass% (sample 61), 0.3 mass% (sample 62), 2 mass% (when the mass of the epoxy compound is 100 mass%). It is contained in Sample 63), 20 mass% (Sample 64), 50 mass% (Sample 65), 150 mass% (Sample 66), and 160 mass% (Sample 67).
In the epoxy composition of this example, the mass ratio (Ymass%) of the onium salt when the mass of the epoxy compound is 100 mass% is less than 0.304 (= 0.5 × Z) in the sample 61, and the sample 62. ~ 66 satisfies the relationship of 0.304 (= 0.5 × Z) ≦ Y ≦ 152.393 (= 250 × Z), and the sample 67 is larger than 152.393.

[Example 5 and Comparative Example 5]
The epoxy composition of each sample of this example was prepared in the same manner as in Example 4 except that different epoxy compounds were used and the compounding ratio of the onium salt and the epoxy compound was changed. The evaluation of this example was carried out in the same manner as in Example 4. Table 4 shows the measurement results measured in the same manner as in Example 4.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 186 (manufactured by Mitsubishi Chemical Corporation, trade name: JER828) was used. As the onium salt, a salt having a reaction start temperature of 63 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI-60) was used as in Example 4.

As shown in Table 4, the mixing ratio of the onium salt is 0.2 mass% (sample 71), 0.3 mass% (sample 72), 2 mass% (when the mass of the epoxy compound is 100 mass%). It is contained in Sample 73), 10 mass% (Sample 74), 50 mass% (Sample 75), 140 mass% (Sample 76), and 150 mass% (Sample 77).
In the epoxy composition of this example, the mass ratio (Ymass%) of the onium salt when the mass of the epoxy compound is 100 mass% is less than 0.286 (= 0.5 × Z) in the sample 71, and the sample 72. ~ 76 satisfies the relationship of 0.286 (= 0.5 × Z) ≦ Y ≦ 143.088 (= 250 × Z), and the sample 67 is larger than 143.088.

[Example 6 and Comparative Example 6]
The epoxy composition of this example was prepared in the same manner as in Example 4 except that different epoxy compounds were used and the compounding ratio of the onium salt and the epoxy compound was changed. The evaluation of this example was carried out in the same manner as in Example 4. Table 4 shows the measurement results measured in the same manner as in Example 4.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 194 (manufactured by Mitsubishi Chemical Corporation, trade name: YX8000) was used. As the onium salt, a salt having a reaction start temperature of 63 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI-60) was used as in Example 4.

As shown in Table 4, the mixing ratio of the onium salt is 0.2 mass% (sample 81), 0.3 mass% (sample 82), 2 mass% (when the mass of the epoxy compound is 100 mass%). It is contained in Sample 83), 6 mass% (Sample 84), 50 mass% (Sample 85), 140 mass% (Sample 86), and 150 mass% (Sample 87).
In the epoxy composition of this example, the mass ratio (Ymass%) of the onium salt when the mass of the epoxy compound is 100 mass% is less than 0.279 (= 0.5 × Z) in the sample 81, and the sample 82. ~ 86 satisfies the relationship of 0.279 (= 0.5 × Z) ≦ Y ≦ 139.695 (= 250 × Z), and the sample 87 is larger than 139.695.

[Example 7 and Comparative Example 7]
The epoxy composition of this example was prepared in the same manner as in Example 4 except that different epoxy compounds were used and the compounding ratio of the onium salt and the epoxy compound was changed. The evaluation of this example was carried out in the same manner as in Example 4. Table 4 shows the measurement results measured in the same manner as in Example 4.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 263 (manufactured by Mitsubishi Chemical Corporation, trade name: YX8034) was used. As the onium salt, a salt having a reaction start temperature of 63 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI-60) was used as in Example 4.

As shown in Table 4, the mixing ratio of the onium salt is 0.2 mass% (sample 91), 0.3 mass% (sample 92), 2 mass% (when the mass of the epoxy compound is 100 mass%). It is contained in Sample 93), 5 mass% (Sample 94), 50 mass% (Sample 95), 110 mass% (Sample 96), and 120 mass% (Sample 97).
In the epoxy composition of this example, the mass ratio (Ymass%) of the onium salt when the mass of the epoxy compound is 100 mass% is less than 0.227 (= 0.5 × Z) in the sample 91, and the sample 92. ~ 96 satisfies the relationship of 0.227 (= 0.5 × Z) ≦ Y ≦ 113.575 (= 250 × Z), and the sample 97 is larger than 113.575.

As shown in Table 4, the epoxy composition of each sample in which the epoxy equivalent and the compounding ratio of the onium salt are within a predetermined range has a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength.

On the other hand, in the epoxy composition of a sample in which the compounding ratio of the onium salt is smaller than a predetermined range and a sample in which the mixing ratio is large, the die shear tensile shear strength is so small that it is unsuitable for practical use as an adhesive.

Further, it can be confirmed that the epoxy composition of each sample having the epoxy equivalent and the compounding ratio of the onium salt within a predetermined range becomes a cured product having high strength by heating at 80 ° C.

[Example 8 and Comparative Example 8]
The epoxy composition of this example was prepared in the same manner as the sample 46 of Example 3 except that different epoxy compounds were used and the compounding ratio of the onium salt and the epoxy resin was changed. The evaluation of this example was carried out in the same manner as in Example 3. Table 5 shows the measurement results measured in the same manner as in Example 3. The evaluation was carried out after the curing conditions shown in (D) were cured under the conditions shown in Table 5.
In this example, each sample was prepared at the ratio shown in Table 5 for the compounding ratio of the onium salt.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 470 (manufactured by Mitsubishi Chemical Corporation, trade name: JER1001) was used. This epoxy compound was prepared as an epoxy solution having a content ratio of 50 mass%.

As shown in Table 5, the epoxy composition of this example contains 0.1 mass% (sample 101) and 0.2 mass% (sample 102) when the onium salt has a mass of the epoxy compound of 100 mass%. It is contained in 1 mass% (sample 103), 3 mass% (sample 104), 40 mass% (sample 105), 60 mass% (sample 106), and 70 mass% (sample 107).
In the epoxy composition of this example, the mass ratio (Ymass%) of the onium salt when the mass of the epoxy compound is 100 mass% is less than 0.122 (= 0.5 × Z) in the sample 101, and the sample 102. ~ 106 satisfies the relationship of 0.122 (= 0.5 × Z) ≦ Y ≦ 61.036 (= 250 × Z), and the sample 107 is larger than 61.038.

[Example 9 and Comparative Example 9]
The epoxy composition of this example was prepared in the same manner as in Example 8 except that different epoxy compounds were used and the compounding ratio of the onium salt and the epoxy compound was changed. The evaluation of this example was carried out in the same manner as in Example 8. Table 5 shows the measurement results measured in the same manner as in Example 8.
In this example, each sample was prepared at the ratio shown in Table 5 for the compounding ratio of the onium salt.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 1004 (manufactured by Mitsubishi Chemical Corporation, trade name: JER1004AF) was used. This epoxy compound was prepared as an epoxy solution having a content ratio of 45 mass%.

As shown in Table 5, the epoxy composition of this example contains 0.01 mass% (sample 111) and 0.02 mass% (sample 112) when the onium salt has a mass of the epoxy compound of 100 mass%. It is contained in 0.5 mass% (sample 113), 2 mass% (sample 114), 20 mass% (sample 115), 40 mass% (sample 116), and 50 mass% (sample 117).
In the epoxy composition of this example, the mass ratio (Ymass%) of the onium salt when the mass of the epoxy compound is 100 mass% is less than 0.02 for the sample 111, and 0.02 ≦ Y for the samples 112 to 116. The relationship of ≦ 40 is satisfied, and the sample 117 is larger than 40.

[Example 10 and Comparative Example 10]
The epoxy composition of this example was prepared in the same manner as in Example 8 except that different epoxy compounds were used and the compounding ratio of the onium salt and the epoxy compound was changed. The evaluation of this example was carried out in the same manner as in Example 8. Table 5 shows the measurement results measured in the same manner as in Example 8.
In this example, each sample was prepared at the ratio shown in Table 5 for the compounding ratio of the onium salt.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 2605 (manufactured by Mitsubishi Chemical Corporation, trade name: JER1009) was used. This epoxy compound was prepared as an epoxy solution having a content ratio of 40 mass%.

As shown in Table 5, the epoxy composition of this example contains 0.01 mass% (sample 121), 0.02 mass% (sample 122), when the onium salt has a mass of the epoxy compound of 100 mass%. It is contained in 0.5 mass% (sample 123), 1 mass% (sample 124), 20 mass% (sample 125), 40 mass% (sample 126), and 50 mass% (sample 127).
In the epoxy composition of this example, the mass ratio (Ymass%) of the onium salt when the mass of the epoxy compound is 100 mass% is smaller than 0.02 for the sample 121, and 0.02 ≦ Y ≦ for the samples 122 to 126. Satisfying the relationship of 40, sample 127 is greater than 40.

[Example 11 and Comparative Example 11]
The epoxy composition of this example was prepared in the same manner as in Example 8 except that different epoxy compounds were used and the compounding ratio of the onium salt and the epoxy compound was changed. The evaluation of this example was carried out in the same manner as in Example 8. Table 5 shows the measurement results measured in the same manner as in Example 8.
In this example, each sample was prepared at the ratio shown in Table 5 for the compounding ratio of the onium salt.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 7926 (manufactured by Mitsubishi Chemical Corporation, trade name: JER1256) was used. This epoxy compound was prepared as an epoxy solution having a content ratio of 40 mass%.

As shown in Table 5, the epoxy composition of this example contains 0.01 mass% (sample 131), 0.02 mass% (sample 132), when the onium salt has a mass of the epoxy compound of 100 mass%. It is contained in 0.5 mass% (sample 133), 2 mass% (sample 134), 20 mass% (sample 135), 40 mass% (sample 136), and 50 mass% (sample 137).
In the epoxy composition of this example, the mass ratio (Ymass%) of the onium salt when the mass of the epoxy compound is 100 mass% is less than 0.02 for the sample 131, and 0.02 ≦ Y for the samples 132 to 136. The relationship of ≦ 40 is satisfied, and the sample 137 is larger than 40.

As shown in Table 5, the epoxy composition of each sample in which the epoxy equivalent and the compounding ratio of the onium salt are within a predetermined range has a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength.
On the other hand, in the epoxy composition of a sample in which the compounding ratio of the onium salt is smaller than a predetermined range and a sample in which the mixing ratio is large, the die shear tensile shear strength is so small that it is unsuitable for practical use as an adhesive.
Further, it can be confirmed that the epoxy composition of each sample having the epoxy equivalent and the compounding ratio of the onium salt within a predetermined range becomes a cured product having high strength by heating at 80 ° C.

[Example 12]
The epoxy composition of this example was prepared in the same manner as in Example 1 except that different epoxy compounds were used and the mixing ratio of the auxiliary agent to the onium salt was changed. The evaluation of this example was carried out in the same manner as in Example 1. Table 6 shows the measurement results measured in the same manner as in Example 1. The evaluation was carried out after the curing conditions shown in (D) were cured under the conditions shown in Table 6.
In this example, each sample was prepared at the ratio shown in Table 6 for the compounding ratio of the onium salt.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 186 (manufactured by Mitsubishi Chemical Corporation, trade name: JER828) was used.

In the epoxy composition of this example, as shown in Table 6, the onium salt is an onium salt (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI-60) and an activity modifier (manufactured by Sanshin Chemical Industry Co., Ltd.). , Trade name: SI aid) in mass ratio, 100: 0 (sample 141), 99: 1 (sample 142), 97: 3 (sample 143), 95: 5 (sample 144), 93: 7 (sample 144). It was prepared using a mixture of samples 145 to 146) and 90:10 (samples 147 to 148). As a result, the reaction start temperature of the onium salt is 61 ° C (sample 141), 63 ° C (sample 142), 65 ° C (sample 143), 67 ° C (sample 144), 70 ° C (sample 145), 70 ° C (sample 146). ), 73 ° C (Sample 147), 73 ° C (Sample 148).

In each of the epoxy compositions of this example, the mass ratio of the onium salt (component containing no auxiliary agent) when the mass of the epoxy compound is 100 mass% is 0.286 (= 0.5 ×). Z) or more, and 143.088 (= 250 × Z) or less.

As shown in Table 6, the epoxy composition of each sample in which the epoxy equivalent and the compounding ratio of the onium salt are within a predetermined range has a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength. From this, it can be seen that a large die shear tensile shear strength can be obtained even when the onium salt is mixed with the auxiliary agent.

Further, it can be confirmed that the epoxy composition of each sample having the epoxy equivalent and the compounding ratio of the onium salt within a predetermined range becomes a cured product having high strength by heating at 80 ° C.

[Example 13]
The epoxy composition of this example was prepared in the same manner as in Example 12 (Sample 142) except that different epoxy compounds were used, the compounding ratio of the onium salt to the epoxy compound was changed, and the treatment conditions were further changed. The evaluation of this example was carried out in the same manner as in Example 12. Table 6 shows the measurement results measured in the same manner as in Example 12.
In this example, each sample (samples 151 to 157) was prepared at the ratio shown in Table 6 for the compounding ratio of the onium salt.
In this example, an epoxy compound having an epoxy equivalent of 165 (manufactured by Mitsubishi Chemical Corporation, trade name: JER806) was used as the epoxy compound.
As shown in Table 6, the epoxy composition of this example was evaluated with a treatment temperature of 80 to 65 ° C. and a treatment time of 15 to 120 minutes.

In each of the epoxy compositions of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is 0.305 (= 0.5 × Z) or more, and 152. It is 393 (= 250 × Z) or less.

As shown in Table 6, the epoxy composition of each sample in which the epoxy equivalent and the compounding ratio of the onium salt are within a predetermined range has a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength. From this, it can be seen that a large die shear tensile shear strength can be obtained even when the onium salt is mixed with the activity regulator.

On the other hand, the lower the treatment condition and the shorter the time, the smaller the die shear tensile shear strength. Then, it can be confirmed that the cured product has high strength by heating at 70 to 80 ° C.

[Example 14]
The epoxy composition of this example was prepared in the same manner as in Example 13 except that different epoxy compounds were used, different onium salts were used, and the treatment conditions were further changed. The evaluation of this example was carried out in the same manner as in Example 13. Table 6 shows the measurement results measured in the same manner as in Example 13.
In this example, each sample (samples 161 to 167) was prepared at the ratio shown in Table 6 for the compounding ratio of the onium salt.

In this example, as the onium salt, an onium salt having a reaction starting temperature of 54 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI-B2A) was used. As the epoxy compound, an epoxy compound having an epoxy equivalent of 186 (manufactured by Mitsubishi Chemical Corporation, trade name: JER828) was used.
As shown in Table 6, the epoxy composition of this example was evaluated with a treatment temperature of 80 to 65 ° C. and a treatment time of 15 to 120 minutes.

In each of the epoxy compositions of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is 0.286 (= 0.5 × Z) or more, and 143. It is 088 (= 250 × Z) or less.

As shown in Table 6, the epoxy composition of each sample in which the epoxy equivalent and the compounding ratio of the onium salt are within a predetermined range has a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength. From this, it can be seen that a large die shear tensile shear strength can be obtained even when the onium salt is mixed with the auxiliary agent.

On the other hand, the lower the treatment condition and the shorter the time, the smaller the die shear tensile shear strength. Then, it can be confirmed that the cured product has high strength by heating at 70 to 80 ° C.

[Example 15]
The epoxy composition of this example was prepared in the same manner as in Example 10 except that different onium salts were used and the compounding ratio of the onium salt and the treatment conditions were changed. The evaluation of this example was carried out in the same manner as in Example 14. Table 6 shows the measurement results measured in the same manner as in Example 14.
In this example, each sample (samples 171 to 175) was prepared at the ratio shown in Table 6 for the compounding ratio of the onium salt.

In this example, as the onium salt, an onium salt having a reaction starting temperature of 52 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI-45) was used. As the epoxy compound, an epoxy compound having an epoxy equivalent of 2605 (manufactured by Mitsubishi Chemical Corporation, trade name: JER1009) was used.
As shown in Table 6, the epoxy composition of this example was evaluated with a treatment temperature of 80 to 65 ° C. and a treatment time of 30 to 120 minutes.

In each of the epoxy compositions of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is 0.02 or more and 40 or less.

As shown in Table 6, the epoxy composition of each sample in which the epoxy equivalent and the compounding ratio of the onium salt are within a predetermined range has a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength. From this, it can be seen that a large die shear tensile shear strength can be obtained even when the onium salt is mixed with the auxiliary agent.

On the other hand, the lower the treatment condition and the shorter the time, the smaller the die shear tensile shear strength. Then, it can be confirmed that the cured product has high strength by heating at 70 to 80 ° C.

[Example 16]
The epoxy composition of this example was prepared in the same manner as in Example 12 except that different onium salts were used and the treatment conditions were further changed. The evaluation of this example was carried out in the same manner as in Example 12. Table 6 shows the measurement results measured in the same manner as in Example 12.
In this example, each sample (samples 181 to 182) was prepared at the ratio shown in Table 6 for the compounding ratio of the onium salt.

In this example, as the onium salt, an onium salt having a reaction starting temperature of 71 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI-80) was used. As the epoxy compound, an epoxy compound having an epoxy equivalent of 186 (manufactured by Mitsubishi Chemical Corporation, trade name: JER828) was used.

In each of the epoxy compositions of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is 0.286 (= 0.5 × Z) or more, and 143. It is 088 (= 250 × Z) or less.

As shown in Table 6, the epoxy composition of each sample in which the epoxy equivalent and the compounding ratio of the onium salt are within a predetermined range has a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength. From this, it can be seen that a large die shear tensile shear strength can be obtained even when the onium salt is mixed with the auxiliary agent.

On the other hand, the lower the treatment condition and the shorter the time, the smaller the die shear tensile shear strength. Then, it can be confirmed that the cured product has high strength by heating at 80 ° C.

[Example 17]
The epoxy composition of this example was prepared in the same manner as in Example 11 except that different epoxy compounds were mixed and used. The evaluation of this example was carried out in the same manner as in Example 11. Table 7 shows the measurement results measured in the same manner as in Example 11. The evaluation was carried out after the curing conditions shown in (D) were cured under the conditions shown in Table 7.
In this example, each sample (samples 191 to 192, samples 193 to 194) was prepared at the ratio shown in Table 7 for the compounding ratio of the onium salt.

In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 7926 (trade name: JER1256) and an epoxy compound having an epoxy equivalent of 186 (trade name: JER828) mixed at the same mass were used (both). , Made by Mitsubishi Chemical Corporation). The epoxy equivalent of the mixture of epoxy compounds of this example is 4095. This epoxy compound was prepared as an epoxy solution having a content ratio of 70 mass%.
In this example, the samples 191 to 192 and the samples 193 to 194 were prepared in the same manner except that the mixing ratio of the onium salt was changed.

In each of the epoxy compositions of this example, the mass ratio of the onium salt solution when the mass of the epoxy compound is 100 mass% is larger than 0.02 and less than 40.

[Example 18]
The epoxy composition of this example was prepared in the same manner as in Example 17 except that a different epoxy compound and an onium salt having a reaction starting temperature of 61 ° C. were used. In this example, the onium salt and the activity adjuster were prepared in a mass ratio of 97: 3, so that the reaction starting temperature in the mixed state of the onium salt was 65 ° C. The evaluation of this example was carried out in the same manner as in Example 17. Table 7 shows the measurement results measured in the same manner as in Example 17. In this example, the processing conditions in the evaluation are different.
In this example, as the epoxy compound, only an epoxy compound having an epoxy equivalent of 186 (manufactured by Mitsubishi Chemical Corporation, trade name: JER828) was used.

In the epoxy composition of this example, in each of the samples (samples 195 to 196), the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is 100 mass%, and the mass ratio of the epoxy compound is 100 mass%. The mass ratio of the onium salt is 0.286 (= 0.5 × Z) or more and 143.088 (= 250 × Z) or less.

[Example 19]
The epoxy composition of this example was prepared in the same manner as in Example 7. The evaluation of this example was carried out in the same manner as in Example 17. Table 7 shows the measurement results of each sample (samples 197 to 201) of this example.
In this example, each sample was prepared at the ratio shown in Table 7 for the compounding ratio of the onium salt.

In this example, as the onium salt, an onium salt having a reaction start temperature of 65 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI-60) and an activity modifier (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI) As an auxiliary agent), an epoxy compound having an epoxy equivalent of 263 (manufactured by Mitsubishi Chemical Industries, Ltd., trade name: YX8034) was used as the epoxy compound.

In each of the epoxy compositions of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is 0.227 (= 0.5 × Z) or more, and 113. It is 575 (= 250 × Z) or less.

[Example 20]
The epoxy composition of this example was prepared in the same manner as in Example 19 except that different epoxy compounds were mixed and used, and different onium salts were used. The evaluation of this example was carried out in the same manner as in Example 19. Table 7 shows the measurement results measured in the same manner as in Example 19.
In this example, each sample (samples 202 to 203) was prepared at the ratio shown in Table 7 for the compounding ratio of the onium salt.
In this example, as the onium salt, an onium salt and an activity modifier are prepared so as to have a mass ratio of 97: 3, and the reaction start temperature is 73 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI). -80) and an activity adjuster (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI auxiliary agent) were used.

In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 194 (trade name: YX8000) and an epoxy compound having an epoxy equivalent of 263 (trade name: YX8034) mixed at the same mass were used. (Both are manufactured by Mitsubishi Chemical Corporation) The epoxy equivalent of the epoxy compound of this example is 229.

In each of the epoxy compositions of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is 0.252 (= 0.5 × Z) or more, and 125. It is 771 (= 250 × Z) or less.

[Example 21]
The epoxy composition of this example was prepared in the same manner as in Example 20 except that different onium salts were used. The evaluation of this example was carried out in the same manner as in Example 20. Table 7 shows the measurement results measured in the same manner as in Example 20.
In this example, each sample (samples 204 to 205) was prepared at the ratio shown in Table 7 for the compounding ratio of the onium salt.
In this example, as the onium salt, an onium salt and an activity modifier are prepared so as to have a mass ratio of 97: 3, and the reaction start temperature is 65 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI). -60) and an activity adjuster (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI auxiliary agent) were used.

In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 194 (trade name: YX8000) and an epoxy compound having an epoxy equivalent of 263 (trade name: YX8034) mixed at the same mass were used. (Both are manufactured by Mitsubishi Chemical Corporation) The epoxy equivalent of the epoxy compound of this example is 229.

In each of the epoxy compositions of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is 0.252 (= 0.5 × Z) or more, and 125. It is 771 (= 250 × Z) or less.

[Example 22]
The epoxy composition of this example was prepared in the same manner as in Example 20 except that only one type of epoxy compound was used. The evaluation of this example was carried out in the same manner as in Example 20. Table 7 shows the measurement results measured in the same manner as in Example 20.
In this example, each sample (samples 206 to 207) was prepared at the ratio shown in Table 7 for the compounding ratio of the onium salt.
In this example, as the onium salt, an onium salt and an activity modifier are prepared so as to have a mass ratio of 97: 3, and the reaction start temperature is 73 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI). -80) and an activity adjuster (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI auxiliary agent) were used.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 263 (manufactured by Mitsubishi Chemical Corporation, trade name: YX8034) was used.

In each of the epoxy compositions of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is 0.227 (= 0.5 × Z) or more, and 113. It is 575 (= 250 × Z) or less.

[Example 23]
The epoxy composition of this example was prepared in the same manner as in Example 1 except that the onium salt and the compounding ratio were different. The evaluation of this example was carried out in the same manner as in Example 1. Table 7 shows the measurement results measured in the same manner as in Example 1.
In this example, the sample 208 was prepared at the ratio shown in Table 7 for the compounding ratio of the onium salt.
In this example, as the onium salt, an onium salt and an activity modifier are prepared so as to have a mass ratio of 97: 3, and the reaction start temperature is 73 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI). -80) and an activity adjuster (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI auxiliary agent) were used.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 186 (manufactured by Mitsubishi Chemical Corporation, trade name: JER828) was used.

In the epoxy composition of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is 0.286 (= 0.5 × Z) or more, and 143.088 (= 250 × Z). It is as follows.

[Comparative Example 12]
The epoxy composition of this example was prepared in the same manner as in Example 23 except that the compounding ratio of the onium salt was different. The evaluation of this example was carried out in the same manner as in Example 23. Table 7 shows the measurement results measured in the same manner as in Example 23.

In this example, as shown in Table 7 with the compounding ratio of the onium salt, the sample 211 was prepared at a ratio of 0.2 mass% when the mass of the epoxy compound was 100 mass%.
In this example, as the onium salt, an onium salt and an activity modifier are prepared so as to have a mass ratio of 97: 3, and the reaction start temperature is 71 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI). -80) and an activity adjuster (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI auxiliary agent) were used.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 186 (manufactured by Mitsubishi Chemical Corporation, trade name: JER828) was used.

In the epoxy composition of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is smaller than 0.286 (= 0.5 × Z).

[Comparative Example 13]
The epoxy composition of this example was prepared in the same manner as in Example 1 except that the epoxy compound, the onium salt and the compounding ratio were different. The evaluation of this example was carried out in the same manner as in Example 1. Table 7 shows the measurement results measured in the same manner as in Example 1.
In this example, each sample (samples 212 to 213) was prepared at the ratio shown in Table 7 for the compounding ratio of the onium salt.
In this example, as the onium salt, an onium salt and an activity modifier are prepared so as to have a mass ratio of 97: 3, and the reaction start temperature is 110 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI). -100) and an activity adjuster (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI auxiliary agent) were used.
In this example, an epoxy compound having an epoxy equivalent of 172 (manufactured by Mitsubishi Chemical Corporation, trade name: YL983U) was used as the epoxy compound.

In each of the epoxy compositions of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is 0.298 (= 0.5 × Z) or more.
[Comparative Example 14]

The epoxy composition of this example was prepared in the same manner as in Example 23 except that the onium salt was different. The evaluation of this example was carried out in the same manner as in Example 23. Table 7 shows the measurement results measured in the same manner as in Example 23.
In this example, as the onium salt, an onium salt and an activity modifier are prepared so as to have a mass ratio of 97: 3, and the reaction start temperature is 110 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI). -100) and an activity adjuster (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI auxiliary agent) were used.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 186 (manufactured by Mitsubishi Chemical Corporation, trade name: JER828) was used.

In the epoxy composition of this example, the mass ratio of the onium salt is 0.286 (= 0.5 × Z) when the mass of the epoxy compound is 100 mass% in each of the samples (samples 214 to 215). The above is 143.088 (= 250 × Z) or less.

[Comparative Example 15]
The epoxy composition of this example was prepared in the same manner as in Example 22 except that the epoxy compound, the onium salt and the compounding ratio were different. The evaluation of this example was carried out in the same manner as in Example 22. Table 7 shows the measurement results measured in the same manner as in Example 22.
In this example, each sample (samples 216 to 217) was prepared at the ratio shown in Table 7 for the compounding ratio of the onium salt.
In this example, as the onium salt, an onium salt and an activity modifier are prepared so as to have a mass ratio of 97: 3, and the reaction start temperature is 110 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI). -100) and an activity adjuster (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI auxiliary agent) were used.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 263 (manufactured by Mitsubishi Chemical Corporation, trade name: YX8034) was used.

In each of the epoxy compositions of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is 0.227 (= 0.5 × Z) or more.

[Comparative Example 16]
The epoxy composition of this example was prepared in the same manner as in Example 23 except that the epoxy compound and the onium salt were different. The evaluation of this example was carried out in the same manner as in Example 23. Table 7 shows the measurement results measured in the same manner as in Example 23.
In this example, each sample (samples 218 to 219) was prepared at the ratio shown in Table 7 for the compounding ratio of the onium salt.
In this example, as the onium salt, an onium salt and an activity modifier are prepared so as to have a mass ratio of 97: 3, and the reaction start temperature is 138 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI). -150) and an activity adjuster (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI auxiliary agent) were used.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 186 (manufactured by Mitsubishi Chemical Corporation, trade name: JER828) was used.

In each of the epoxy compositions of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is 0.286 (= 0.5 × Z) or more.

As shown in Table 7, the epoxy composition of each sample in which the epoxy equivalent and the compounding ratio of the onium salt are within a predetermined range has a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength. From this, it can be seen that a large die shear tensile shear strength can be obtained even when the onium salt is mixed with the activity regulator.

Further, the epoxy composition of each sample containing the onium salt having an epoxy equivalent and an onium salt compounding ratio within a predetermined range and having a reaction starting temperature of 45 ° C. to 75 ° C. as shown in Tables 1 to 7. Can be confirmed to be a cured product having high strength by heating at 80 ° C.

[Other evaluations]
The storage stability test shown in (K) above was carried out on the epoxy composition prepared in the same manner as in Sample 26 except that the sample 26 and the onium salt were changed.
In this evaluation, the reaction start temperature of the onium salt is 63 ° C (trade name: SI-60), 73 ° C (trade name: SI-80), 110 ° C (trade name: SI-100), 138 ° C (trade name:). Using SI-150), the storage stability of each sample prepared by appropriately blending an activity adjusting agent was evaluated. The predetermined time was one year.
In any of the samples, the cured product obtained by heating to a predetermined temperature (a temperature higher than the reaction starting temperature of the onium salt) obtained a high adhesive strength of 5 MPa or more.
As described above, it can be confirmed that the epoxy composition of each sample used in this evaluation is an epoxy composition that can be stored for a long period of time at 5 to 30 ° C. That is, it can be confirmed that the epoxy composition of each example is an epoxy composition that can be stored for a long time at room temperature.

[Example 24 and Comparative Example 17]
The epoxy composition of this example was prepared in the same manner as in Example 2 except that the mixing ratio of the onium salt was changed. The evaluation of this example was carried out in the same manner as in Example 2. Table 2 shows the measurement results measured in the same manner as in Example 2. The evaluation was carried out after the curing treatment was performed using the treatment conditions shown in (D) as the conditions shown in Table 8.
In this example, the onium salt further contains an activity modifier. That is, the onium salt is an onium salt having a reaction start temperature of 61 ° C. prepared so that the mass ratio of the onium salt and the activity modifier is 99: 1 (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI- 60) and an activity adjuster (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI auxiliary agent) were used.

As shown in Table 8, the epoxy composition of this example contains 0.1 mass% (samples 221, 222, 223) and 1 mass% (sample 224) when the onium salt has a mass of epoxy resin of 100 mass%. , 225,226), 20 mass% (samples 227, 228, 229), 150 mass% (samples 230, 231).

In the epoxy composition of this example, the mass ratio (Ymass%) of the onium salt when the mass of the epoxy compound is 100 mass% is less than 0.286 for the samples 221 to 223, and 0.286 for the samples 224 to 229. The relationship of ≦ Y ≦ 143.088 is satisfied, and the samples 230 and 231 are larger than 143.088.

As shown in Table 8, the epoxy composition of each sample of this example was cured at 155 ° C. × 60 seconds for samples 221,224,227,230, and for samples 222,225,228. A curing treatment of 175 ° C. × 60 seconds was performed, and a curing treatment of 200 ° C. × 60 seconds was applied to the samples 223, 226, 229, 231 respectively.

As shown in Table 8, the epoxy composition of each sample in which the epoxy equivalent and the compounding ratio of the onium salt are within a predetermined range has a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength. From this, it can be seen that the epoxy composition of this example can be cured in a short heating time of 60 seconds.

[Example 25]
The epoxy composition of this example was prepared in the same manner as in Example 24 except that different epoxy compounds and onium salts were used, the compounding ratio of the onium salt to the epoxy compound was changed, and the treatment conditions were further changed. The evaluation of this example was carried out in the same manner as in Example 24. Table 8 shows the measurement results measured in the same manner as in Example 24.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 194 (manufactured by Mitsubishi Chemical Corporation, trade name: YX8000) was used.
In this example, the onium salt is an onium salt having a reaction start temperature of 108 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI) prepared by preparing the onium salt and the activity modifier so as to have a mass ratio of 99: 1. -100) and an activity adjuster (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI auxiliary agent) were used.

As shown in Table 8, the epoxy composition of this example contains 0.5 mass% (sample 232, 233, 234) and 1 mass% (sample 235) of the onium salt when the mass of the epoxy resin is 100 mass%. , 236, 237).

In the epoxy composition of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% satisfies the relationship of 0.286 ≦ Y ≦ 143.088 in each sample.

As shown in Table 8, the epoxy composition of each sample of this example was cured at 150 ° C. for 60, 90, 120 seconds for samples 232 to 234, and 250 ° C. for samples 235 to 237. The curing treatment was performed for 10, 20 and 30 seconds, respectively.

As shown in Table 8, the epoxy composition of sample 232 has a die shear tensile shear strength of 3.2 MPa, and the epoxy compositions of each sample 233 to 237 have a large die shear tensile shear strength of 5 MPa or more. There is. That is, it can be seen that it has high adhesive strength. From this, it can be seen that the epoxy composition of this example can be cured even by heating at a medium temperature of 150 ° C.

[Example 26]
The epoxy composition of this example was prepared in the same manner as in Example 24 except that different onium salts were used, the compounding ratio of the onium salt to the epoxy compound was changed, and the treatment conditions were further changed. The evaluation of this example was carried out in the same manner as in Example 24. Table 8 shows the measurement results measured in the same manner as in Example 24.
In this example, the onium salt is an onium salt having a reaction start temperature of 138 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI) prepared by adjusting the mass ratio of the onium salt and the activity modifier to 99: 1. -150) and an activity adjuster (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI auxiliary agent) were used.

As shown in Table 8, the epoxy composition of this example contains the onium salt in an amount of 1 mass% (samples 238 to 240) when the mass of the epoxy resin is 100 mass%.

In the epoxy composition of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% satisfies the relationship of 0.286 ≦ Y ≦ 143.088 in each sample.

As shown in Table 8, the epoxy composition of each sample of this example was subjected to a curing treatment at 275 ° C. for 15, 30, 45 seconds, respectively.

As shown in Table 8, the epoxy composition of each sample has a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength. From this, it can be seen that the epoxy composition of this example can be cured by heating at medium and high temperatures of 275 ° C.

[Example 27]
The epoxy composition of this example was prepared in the same manner as in Example 2 except that different onium salts were used and the compounding ratio of the onium salt to the epoxy compound was changed. As an evaluation of this example, the storage stability test shown by (K) was performed. The measurement results are shown in Table 9.
In this example, the onium salt was prepared so that the mass ratio of the onium salt and the activity modifier was 97: 3. An onium salt having a reaction starting temperature of 138 ° C. (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI-150) and an activity modifier (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SI auxiliary agent) were used.

As shown in Table 9, the epoxy composition of each sample of this example contains 1.5 mass% (samples 241-244) of onium salt at 1 mass% (samples 241 to 244) when the mass of the epoxy resin is 100 mass%. It is contained in each sample 245).

In the epoxy composition of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% satisfies the relationship of 0.286 ≦ Y ≦ 143.088 in each sample.

As shown in Table 9, the epoxy composition of each sample of this example was measured for viscosity at 40 ° C. after 1 week, 2 weeks, 3 weeks, and 4 weeks. Further, the adhesive strength of each sample after 4 weeks was measured.

As shown in Table 9, the epoxy composition of each sample showed almost no change in viscosity when stored at 40 ° C. That is, it can be confirmed that the epoxy composition of this example hardly progresses to curing even if it is stored at 40 ° C. near room temperature for 4 weeks.
Furthermore, there is a common general knowledge that those whose viscosity doubles after being stored at 40 ° C. for one month can be stored at room temperature for one year. In view of this common general knowledge, it can be seen that the epoxy composition of this example can be stored at room temperature on a yearly basis because almost no change in viscosity is observed.
Further, according to the samples 241, and 245, it can be seen that the curing is possible at a medium temperature of 150 ° C. Further, according to the samples 242 to 244, it can be confirmed that the curing at a second speed is possible.
That is, the epoxy composition of this example can exhibit the above-mentioned excellent effects even after long-term storage on a yearly basis.

[Example 28]
The epoxy composition of this example was prepared in the same manner as in Example 27 except that different epoxy compounds were used, the compounding ratio of the onium salt to the epoxy compound was changed, and the treatment conditions were further changed. The evaluation of this example was carried out in the same manner as in Example 27. Table 9 shows the measurement results measured in the same manner as in Example 27.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 194 (manufactured by Mitsubishi Chemical Corporation, trade name: YX8000) was used.

As shown in Table 9, the epoxy composition of each sample of this example contains 0.8 mass% (sample 246) of onium salt at 0.4 mass% (sample 246) when the mass of the epoxy resin is 100 mass% (sample 246). Sample 247) contains 1.5 mass% (Sample 248), respectively.

In the epoxy composition of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% satisfies the relationship of 0.279 ≦ Y ≦ 139.695 for each sample.

As shown in Table 9, the epoxy composition of each sample increases in viscosity over time. However, it can be seen that the epoxy composition of each sample has a high die shear tensile shear strength of 5 MPa or more in the cured product. That is, it can be confirmed that the epoxy composition of this example has high strength even when stored at room temperature.

[Example 29]
The epoxy composition of this example was prepared in the same manner as in Example 28 except that the compounding ratio of the onium salt to the epoxy compound was changed and a storage stabilizer was further added. The evaluation of this example was carried out in the same manner as in Example 28. Table 9 shows the measurement results measured in the same manner as in Example 28.
In this example, diethylene glycol diethyl ether, which is used as a viscosity modifier in conventional epoxy compositions, was used as the storage stabilizer.

As shown in Table 9, the epoxy composition of each sample of this example contains the onium salt in an amount of 1.5 mass% (samples 249 to 250) when the mass of the epoxy resin is 100 mass%.
In the epoxy composition of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% satisfies the relationship of 0.279 ≦ Y ≦ 139.695 for each sample.

As shown in Table 9, the epoxy composition of each sample was stored at 40 ° C for 4 weeks at 40 ° C, which is used for the acceleration test of storage stability, although a slight increase in viscosity can be confirmed when stored at 40 ° C. It can be confirmed that the curing hardly progresses even if it goes.
Further, it can be seen that the epoxy composition of each sample has a high die shear tensile shear strength of 5 MPa or more. That is, it can be confirmed that the epoxy composition of this example has high strength even when stored at room temperature.

[Example 30]
The epoxy composition of this example was prepared in the same manner as in Example 27 except that the compounding ratio of the onium salt to the epoxy compound was changed.
As an evaluation of this example, it was treated under the conditions shown in Table 10 to be in a semi-cured state, and a storage stability test was performed. The measurement results are shown in Table 10.

As shown in Table 10, the epoxy composition of each sample of this example contains onium salt in an amount of 0.8 mass% (samples 251 to 253) when the mass of the epoxy resin is 100 mass%.

In the epoxy composition of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% satisfies the relationship of 0.286 ≦ Y ≦ 143.088 in each sample.

As shown in Table 10, it can be seen that the epoxy composition of each sample of this example has a high die shear tensile shear strength of 5 MPa or more for each sample even after storage at room temperature for one year. That is, it can be confirmed that the epoxy composition of this example has high strength even when stored at room temperature in a semi-cured state.
That is, the epoxy composition of this example can exhibit the above-mentioned excellent effects even after long-term storage in a semi-cured state on a yearly basis.

[Example 31]
The epoxy composition of this example was prepared in the same manner as in Example 30 except that it further contained a reinforcing material. As an evaluation of this example, it was treated under the conditions shown in Table 10 to be in a semi-cured state, and a storage stability test was performed. The measurement results are shown in Table 10.

As shown in Table 10, the epoxy composition of each sample of this example contains SiC (sample 254), sintered Al (sample 255), and CF plain weave (sample 256) as reinforcing materials, respectively. did. The reinforcing material is contained so as to be 89 mass% (sample 254), 70 mass% (sample 255), and 75 mass% (sample 256) when the mass of the epoxy composition (including the reinforcing material) is 100 mass%. do.
As SiC, SiC powder having an average particle size of 9.5 ± 8 μm (manufactured by Shinano Electric Smelting Co., Ltd., trade name: GP # 1200) was used.
As the sintered Al, short aluminum fibers having a fiber diameter of 100 μm (manufactured by Akao Aluminum Co., Ltd., prototype) were used.
For the CF plain weave, a carbon fiber woven fabric (manufactured by Toray Industries, Inc., trade name: C06151B) was used.

In the epoxy composition of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% satisfies the relationship of 0.286 ≦ Y ≦ 143.088 in each sample.

As shown in Table 10, it can be seen that the epoxy composition of each sample of this example has a high die shear tensile shear strength of 5 MPa or more for each sample even after storage at room temperature for one year. That is, it can be confirmed that the epoxy composition of this example has high strength even when stored at room temperature in a semi-cured state.
That is, the epoxy composition of this example can exhibit the above-mentioned excellent effects even after long-term storage in a semi-cured state on a yearly basis.

[Example 32]
The epoxy composition of this example was prepared in the same manner as in Example 30 except that both different epoxy compounds and different onium salts were used and the compounding ratio of the onium salt to the epoxy compound was changed. As an evaluation of this example, it was treated under the conditions shown in Table 10 to be in a semi-cured state, and a storage stability test was performed. The measurement results are shown in Table 10.

As shown in Table 10, the epoxy composition of this example has an onium salt reaction starting temperature of 110 ° C. (Sample 257, trade name: SI-100), 73 ° C. (Sample 258, trade name: SI-80). ), 63 ° C (Sample 259, trade name: SI-60), 110 ° C (Sample 260, trade name: SI-100) (all manufactured by Sanshin Chemical Industry Co., Ltd.) were used.

As shown in Table 10, the epoxy composition of each sample of this example was 0.5 mass% (samples 257 to 258, 260), 0. It is contained in 3 mass% (sample 259), respectively.

In the epoxy composition of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% satisfies the relationship of 0.286 ≦ Y ≦ 143.088 in the samples 257 to 259. Further, the sample 260 satisfies the relationship of 0.304 ≦ Y ≦ 152.393.

As shown in Table 10, the epoxy composition of each sample of this example has a high die shear tensile shear strength of 5 MPa or more even after storage for one year in a room temperature-refrigerated-frozen state for each sample. You can see that there is. Specifically, the samples 251 to 258 and 260 are kept at room temperature, and the sample 259 using an onium salt having a reaction start temperature of 63 ° C. has a high die shear of 5 MPa or more even after storage for 1 year from refrigeration to freezing. It can be seen that it has tensile shear strength. That is, it can be confirmed that the epoxy composition of this example has high strength even when stored in a semi-cured state at room temperature, refrigeration, or freezing. Of course, there is no problem even if it is stored frozen like a conventional one-component epoxy composition.
That is, the epoxy composition of this example can exhibit the above-mentioned excellent effects even after long-term storage in a semi-cured state on a yearly basis. That is, the epoxy composition of this example can stop the curing reaction by setting the temperature below the reaction starting temperature even in the semi-cured state. This is an advantage of the epoxy composition of this example, which is completely different from the conventional amine latent curing type one-component epoxy resin. In the conventional amine latent curing type one-component epoxy resin, once the curing reaction starts, the curing reaction cannot be stopped even if the temperature is returned to room temperature in a semi-cured state. For this reason, the amine latently curable one-component epoxy resin used for prepregs and the like has to be stored in a semi-cured state, usually by a storage method in which the reaction rate is slowed down under freezing at −30 ° C. or lower. Since the epoxy composition of this example can stop the curing reaction by keeping the temperature below the reaction starting temperature even in the semi-cured state, such freezing becomes unnecessary.

[Example 33 and Comparative Example 18]
The epoxy composition of this example was prepared by the following method. The epoxy composition of this example is a conductive epoxy composition. The following method is a specific method of sample 267 of this example. Other samples are produced using this method as appropriate.
A 50 mL screw cap bottle (manufactured by Nichiden Rika Glass Co., Ltd., trade name: SV-50), an onium salt with a reaction start temperature of 63 ° C. (brand name: SI-60), and an activity adjuster (brand name: SI auxiliary agent). ) (Both manufactured by Sanshin Chemical Industry Co., Ltd.) were mixed and weighed at a mass ratio of 99: 1, and γ-butyl lactone was added as a solvent, the concentration of the onium salt was 33 mass%, and the activity adjuster was 0. An onium salt solution contained at 33 mass% was prepared. Weigh 3.6 g of the prepared onium salt solution.

Then, 7.5 g of an epoxy compound (manufactured by Mitsubishi Chemical Corporation, trade name: YX8034) having an epoxy equivalent of 263 is weighed and mixed with the onium salt solution. The onium salt is 16 mass% when the mass of the epoxy compound is 100 mass%.

Next, two types of Ag powders having different particle shapes (trade names: AgC2351 and AgC234) (both manufactured by Fukuda Metal Foil Industry Co., Ltd.) are mixed at a mass ratio of 1: 1. 500 g of the Ag mixture was placed in a 1 L polybin (1 L polyethylene bottle), 250 ml of acetone was further added, and the mixture was shaken for 3 to 5 minutes.
52.5 g of the cleaned Ag mixed powder is added to the mixed solution.

Insert a stainless steel microspatula into a screw cap bottle that weighs these three types, and stir on a touch mixer (manufactured by Yamato Kagaku Co., Ltd., trade name: MT-31) for about 10 minutes to create a uniform solution with one-component conductivity. It was made into an epoxy composition.
As described above, the epoxy composition of sample 267 was prepared.

The epoxy composition of each sample (samples 261 to 273) of this example was prepared by the same method.
As shown in Table 11, the epoxy composition of this example contains 0.1 mass% (sample 261) and 0.3 mass% (sample 262) when the onium salt has a mass of the epoxy compound of 100 mass%. 0.5 mass% (sample 263), 1.0 mass% (sample 264), 2 mass% (sample 265), 4 mass% (sample 266), 16 mass% (sample 267), 20 mass% (sample 268), 40 mass% (sample) 269), 60 mass% (sample 270), 80 mass% (sample 271), 100 mass% (sample 272), 120 mass% (sample 273).
In the epoxy composition of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is less than 0.227 (= 0.5 × Z) in the sample 261 and 0 in the samples 262 to 272. It is 227 (= 0.5 × Z) or more and 113.575 (= 250 × Z) or less, and is larger than 113.575 (= 250 × Z) in the sample 273.
In the epoxy composition of this example, Ag powder is blended at 87.5 mass% when the mass of the entire epoxy composition excluding the onium salt that is thermally decomposed and the solvent as a viscosity adjusting agent is 100 mass%.
The evaluation of this example was carried out in the same manner as in Example 1. Table 8 shows the measurement results measured in the same manner as in Example 1.

The epoxy composition (conductive epoxy composition) of this example is measured for the viscosity shown in (C) above, the die shear tensile shear strength shown in (E), and the volume resistance value shown in (F), and then measured. After the curing treatment shown in (D) under the predetermined conditions shown in Table 11, the color tone determination shown in (G) was performed. The results are shown in Table 11.

As shown in Table 11, the epoxy composition of each sample of this example has a solution viscosity at 25 ° C. of 10 to 40 Pa · s, which is within a predetermined range.

As shown in Table 11, the epoxy composition of each sample in which the epoxy equivalent of this agent and the compounding ratio of the onium salt are within a predetermined range has a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength. From this, it can be seen that a large die shear tensile shear strength can be obtained even when the onium salt is mixed with the activity regulator.

Further, it can be confirmed that the epoxy composition of each sample becomes a cured product having high strength by heating at 80 ° C. and / or 150 ° C.
Further, it can be seen that the epoxy composition of each sample of this example has a small volume resistance value and has excellent conductivity.
As described above, the epoxy composition of each sample of this example has excellent properties as a conductive epoxy composition (conductive adhesive).

[Example 34 and Comparative Example 19]
The epoxy composition of this example was prepared in the same manner as in Example 33 except that the epoxy compound was changed. The evaluation of this example was carried out in the same manner as in Example 33. Table 13 shows the measurement results measured in the same manner as in Example 33. The epoxy composition (conductive epoxy composition) of this example is further subjected to the cross-cut test shown in (I), the bending resistance test shown in (H), and the rubbing test shown in (J). rice field.
In this example, an epoxy compound having an epoxy equivalent of 165 (manufactured by Mitsubishi Chemical Corporation, trade name: JER806) was used as the epoxy compound.
In this example, each sample (samples 281 to 289) was prepared at the ratio shown in Table 12 for the compounding ratio of the onium salt.

As shown in Table 12, the epoxy composition of this example contains 0.1 mass% (sample 281), 0.5 mass% (sample 282), when the onium salt has a mass of the epoxy compound of 100 mass%. Contains in 1 mass% (sample 283), 4 mass% (sample 284), 10 mass% (sample 285), 30 mass% (sample 286), 70 mass% (sample 287), 120 mass% (sample 288), 160 mass% (sample 289). do.
In the epoxy composition of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is less than 0.305 (= 0.5 × Z) for the sample 281 and 0 for the samples 282 to 288. It is .305 (= 0.5 × Z) or more and 152.393 (= 250 × Z) or less, and is larger than 152.393 (= 250 × Z) in the sample 289.
In the epoxy composition of this example, Ag powder is blended at 87.5 mass% when the mass excluding the onium salt and the solvent which are thermally decomposed from the entire epoxy composition is 100 mass%.

As shown in Table 12, the epoxy composition of each sample in which the epoxy equivalent and the compounding ratio of the onium salt of this example are within the predetermined range has a solution viscosity at 25 ° C. of 6 to 29 Pa · s, which is within the predetermined range. It has become.

As shown in Table 13, the epoxy composition of each sample of this example has a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength. From this, it can be seen that a large die shear tensile shear strength can be obtained even when the onium salt is mixed with the activity regulator.

Further, it can be confirmed that the epoxy composition of each sample becomes a cured product having high strength by heating at 80 ° C. and / or 150 ° C.
Further, it can be seen that the epoxy composition of each sample of this example has a small volume resistance value and has excellent conductivity.
As described above, the epoxy composition of each sample of this example has excellent properties as a conductive epoxy composition (conductive adhesive).

[Example 35 and Comparative Example 20]
The epoxy composition of this example was prepared in the same manner as in Example 33 except that the epoxy compound was changed. The evaluation of this example was carried out in the same manner as in Example 34. Table 15 shows the measurement results measured in the same manner as in Example 34.
As the poxy compound, an epoxy compound having an epoxy equivalent of 186 (manufactured by Mitsubishi Chemical Corporation, trade name: JER828) was used.

In this example, each sample (samples 291 to 299) was prepared at the ratio shown in Table 14 for the compounding ratio of the onium salt.
As shown in Table 14, the epoxy composition of this example contains 0.2 mass% (sample 291) and 0.5 mass% (sample 292) when the onium salt has a mass of the epoxy compound of 100 mass%. Contains in 1 mass% (sample 293), 4 mass% (sample 294), 10 mass% (sample 295), 30 mass% (sample 296), 70 mass% (sample 297), 120 mass% (sample 298), 150 mass% (sample 299). do.
In the epoxy composition of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is less than 0.286 (= 0.5 × Z) for the sample 291 and 0 for the samples 292 to 298. It is .286 (= 0.5 × Z) or more and 143.088 (= 250 × Z) or less, and is larger than 143.088 (= 250 × Z) in sample 299.
In the epoxy composition of this example, Ag powder is blended at 87.5 mass% when the mass excluding the onium salt and the solvent which are thermally decomposed from the entire epoxy composition is 100 mass%.

As shown in Table 14, the epoxy composition of each sample in which the epoxy equivalent and the compounding ratio of the onium salt of this example are within the predetermined range has a solution viscosity at 25 ° C. of 7 to 40 Pa · s, which is within the predetermined range. It has become.
As shown in Table 15, the epoxy composition of each sample of this example has a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength. From this, it can be seen that a large die shear tensile shear strength can be obtained even when the onium salt is mixed with the activity regulator.

Further, it can be confirmed that the epoxy composition of each sample becomes a cured product having high strength by heating at 80 ° C. and / or 150 ° C.
Further, it can be seen that the epoxy composition of each sample of this example has a small volume resistance value and has excellent conductivity.
As described above, the epoxy composition of each sample of this example has excellent properties as a conductive epoxy composition (conductive adhesive).

[Example 36 and Comparative Example 21]
The epoxy composition of this example was prepared in the same manner as in Example 33 except that the epoxy compound was changed. The evaluation of this example was carried out in the same manner as in Example 34. Table 17 shows the measurement results measured in the same manner as in Example 34.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 194 (manufactured by Mitsubishi Chemical Corporation, trade name: YX8000) was used.

In this example, each sample (samples 301 to 309) was prepared at the ratio shown in Table 16 for the compounding ratio of the onium salt.
As shown in Table 16, the epoxy composition of this example contains 0.2 mass% (sample 301), 0.3 mass% (sample 302), when the onium salt has a mass of the epoxy compound of 100 mass%. 4 mass% (sample 303), 10 mass %% (sample 304), 20 mass %% (sample 305), 40 mass% (sample 306), 70 mass% (sample 307), 120 mass% (sample 308), 150 mass% (sample 309). Contains in.

In the epoxy composition of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is less than 0.279 (= 0.5 × Z) in the sample 301, and 0 in the samples 302 to 308. It is .279 (= 0.5 × Z) or more and 139.695 (= 250 × Z) or less, and is larger than 139.695 (= 250 × Z) in the sample 309.
In the epoxy composition of this example, Ag powder is blended at 87.5 mass% when the mass excluding the onium salt and the solvent which are thermally decomposed from the entire epoxy composition is 100 mass%.

As shown in Table 16, the epoxy composition of each sample in which the epoxy equivalent and the compounding ratio of the onium salt of this example are within a predetermined range has a solution viscosity at 25 ° C. of 16 to 30 Pa · s, which is within a predetermined range. It has become.
As shown in Table 17, the epoxy composition of each sample of this example has a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength. From this, it can be seen that a large die shear tensile shear strength can be obtained even when the onium salt is mixed with the activity regulator.

Further, it can be confirmed that the epoxy composition of each sample becomes a cured product having high strength by heating at 80 ° C. and / or 150 ° C.
Further, it can be seen that the epoxy composition of each sample of this example has a small volume resistance value and has excellent conductivity.
As described above, the epoxy composition of each sample of this example has excellent properties as a conductive epoxy composition (conductive adhesive).

[Example 37 and Comparative Example 22]
The epoxy composition of this example was prepared in the same manner as in Example 33 except that the epoxy compound was changed. The evaluation of this example was carried out in the same manner as in Example 34. Table 19 shows the measurement results measured in the same manner as in Example 34.
In this example, an epoxy compound having an epoxy equivalent of 250 (manufactured by Mitsubishi Chemical Corporation, trade name: JER834) was used as the epoxy compound. This epoxy compound was prepared as an epoxy solution having a content ratio of 60 mass%.
In this example, each sample (samples 311 to 319) was prepared at the ratio shown in Table 18 for the compounding ratio of the onium salt.

As shown in Table 18, the epoxy composition of this example contains 0.2 mass% (sample 311) and 0.5 mass% (sample 312) when the onium salt has a mass of the epoxy compound of 100 mass%. Contains in 4 mass% (sample 313), 10 mass% (sample 314), 20 mass% (sample 315), 40 mass% (sample 316), 70 mass% (sample 317), 120 mass% (sample 318), 150 mass% (sample 319). do.
In the epoxy composition of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is less than 0.236 (= 0.5 × Z) in the sample 311 and 0 in the samples 312 to 317. It is .236 (= 0.5 × Z) or more and 118.091 (= 250 × Z) or less, and is larger than 118.091 (= 250 × Z) in the samples 318 to 319.
In the epoxy composition of this example, Ag powder is blended at 87.5 mass% when the mass excluding the onium salt and the solvent which are thermally decomposed from the entire epoxy composition is 100 mass%.

As shown in Table 18, the epoxy composition of each sample in which the epoxy equivalent and the compounding ratio of the onium salt of this example are within the predetermined range has a solution viscosity at 25 ° C. of 17 to 40 Pa · s, which is within the predetermined range. It has become.

As shown in Table 19, the epoxy composition of each sample of this example has a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength. From this, it can be seen that a large die shear tensile shear strength can be obtained even when the onium salt is mixed with the activity regulator.

Further, it can be confirmed that the epoxy composition of each sample becomes a cured product having high strength by heating at 80 ° C. and / or 150 ° C.
Further, it can be seen that the epoxy composition of each sample of this example has a small volume resistance value and has excellent conductivity.
As described above, the epoxy composition of each sample of this example has excellent properties as a conductive epoxy composition (conductive adhesive).

[Example 38 and Comparative Example 23]
The epoxy composition of this example was prepared in the same manner as in Example 33 except that the epoxy compound was changed. The evaluation of this example was carried out in the same manner as in Example 33. Table 20 shows the measurement results measured in the same manner as in Example 33.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 263 (manufactured by Mitsubishi Chemical Corporation, trade name: YX8034) was used.
In this example, each sample (samples 321 to 333) was prepared at the ratio shown in Table 20 for the compounding ratio of the onium salt.

As shown in Table 20, the epoxy composition of this example contains 0.1 mass% (sample 321) and 0.3 mass% (sample 322) when the onium salt has a mass of the epoxy compound of 100 mass%. 0.5 mass% (sample 323), 1 mass% (sample 324), 2 mass% (sample 325), 4 mass% (sample 326), 16 mass% (sample 327), 20 mass% (sample 328), 40 mass% (sample 329). , 60 mass% (sample 330), 80 mass% (sample 331), 100 mass% (sample 332), 120 mass% (sample 333).
In the epoxy composition of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is less than 0.227 (= 0.5 × Z) in the sample 321 and 0 in the samples 322 to 332. It is 227 (= 0.5 × Z) or more and 113.575 (= 250 × Z) or less, and is larger than 113.575 (= 250 × Z) in the sample 333.
In the epoxy composition of this example, Ag powder is blended at 87.5 mass% when the mass excluding the onium salt and the solvent which are thermally decomposed from the entire epoxy composition is 100 mass%.

As shown in Table 20, the epoxy composition of each sample in which the epoxy equivalent and the compounding ratio of the onium salt of this example are within the predetermined range has a solution viscosity at 25 ° C. of 10 to 40 Pa · s, which is within the predetermined range. It has become.

As shown in Table 20, the epoxy composition of each sample of this example has a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength. From this, it can be seen that a large die shear tensile shear strength can be obtained even when the onium salt is mixed with the activity regulator.

Further, it can be confirmed that the epoxy composition of each sample becomes a cured product having high strength by heating at 80 ° C. and / or 150 ° C.
Further, it can be seen that the epoxy composition of each sample of this example has a small volume resistance value and has excellent conductivity.
As described above, the epoxy composition of each sample of this example has excellent properties as a conductive epoxy composition (conductive adhesive).

[Example 39 and Comparative Example 24]
The epoxy composition of this example was prepared in the same manner as in Example 33 except that the epoxy compound was changed. The evaluation of this example was carried out in the same manner as in Example 33. Table 21 shows the measurement results measured in the same manner as in Example 33.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 470 (manufactured by Mitsubishi Chemical Corporation, trade name: JER1001) was used. This epoxy compound was prepared as an epoxy solution having a content ratio of 50 mass%.
In this example, each sample (samples 341 to 351) was prepared at the ratio shown in Table 21 for the compounding ratio of the onium salt.

As shown in Table 21, the epoxy composition of this example contains 0.1 mass% (sample 341) and 0.2 mass% (sample 342) when the onium salt has a mass of the epoxy compound of 100 mass%. 1 mass% (sample 343), 1.5 mass% (sample 344), 2 mass% (sample 345), 10 mass% (sample 346), 12 mass% (sample 347), 15 mass% (sample 348), 20 mass% (sample 349). , 50 mass% (sample 350), 70 mass% (sample 351).
In the epoxy composition of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is less than 0.122 (= 0.5 × Z) in the sample 341, and 0 in the samples 342 to 350. It is .122 (= 0.5 × Z) or more and 61.036 (= 250 × Z) or less, and is larger than 61.036 (= 250 × Z) in the sample 351.
In the epoxy composition of this example, Ag powder is blended at 87.5 mass% when the mass excluding the onium salt and the solvent which are thermally decomposed from the entire epoxy composition is 100 mass%.

As shown in Table 21, the epoxy composition of each sample in which the epoxy equivalent and the compounding ratio of the onium salt of this example are within the predetermined range has a solution viscosity at 25 ° C. of 5 to 20 Pa · s, which is within the predetermined range. It has become.

As shown in Table 21, the epoxy composition of each sample of this example has a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength. From this, it can be seen that a large die shear tensile shear strength can be obtained even when the onium salt is mixed with the activity regulator.

Further, it can be confirmed that the epoxy composition of each sample becomes a cured product having high strength by heating at 80 ° C. and / or 150 ° C.
Further, it can be seen that the epoxy composition of each sample of this example has a small volume resistance value and has excellent conductivity.
As described above, the epoxy composition of each sample of this example has excellent properties as a conductive epoxy composition (conductive adhesive).

[Example 40 and Comparative Example 25]
The epoxy composition of this example was prepared in the same manner as in Example 33 except that the epoxy compound was changed. The evaluation of this example was carried out in the same manner as in Example 33. Table 22 shows the measurement results measured in the same manner as in Example 33.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 1004 (manufactured by Mitsubishi Chemical Corporation, trade name: JER1004AF) was used. This epoxy compound was prepared as an epoxy solution having a content ratio of 50 mass%.
In this example, each sample (samples 361 to 371) was prepared at the ratio shown in Table 22 for the compounding ratio of the onium salt.

As shown in Table 22, the epoxy composition of this example contains 0.01 mass% (sample 361) and 0.03 mass% (sample 362) when the onium salt has a mass of the epoxy compound of 100 mass%. 0.1 mass% (sample 363), 1 mass% (sample 364), 4 mass% (sample 365), 10 mass% (sample 366), 12 mass% (sample 367), 15 mass% (sample 368), 20 mass% (sample 369). , 40 mass% (sample 370), 60 mass% (sample 371).
In the epoxy composition of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is less than 0.02 for the sample 361 and 0.02 or more and 40 or less for the samples 362 to 370. Sample 371 is greater than 40.
In the epoxy composition of this example, Ag powder is blended at 87.5 mass% when the mass excluding the onium salt and the solvent which are thermally decomposed from the entire epoxy composition is 100 mass%.

As shown in Table 22, the epoxy composition of each sample in which the epoxy equivalent and the compounding ratio of the onium salt of this example are within the predetermined range has a solution viscosity at 25 ° C. of 15 to 32 Pa · s, which is within the predetermined range. It has become.

As shown in Table 22, the epoxy composition of each sample of this example has a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength. From this, it can be seen that a large die shear tensile shear strength can be obtained even when the onium salt is mixed with the activity regulator.

Further, it can be confirmed that the epoxy composition of each sample becomes a cured product having high strength by heating at 80 ° C. and / or 150 ° C.
Further, it can be seen that the epoxy composition of each sample of this example has a small volume resistance value and has excellent conductivity.
As described above, the epoxy composition of each sample of this example has excellent properties as a conductive epoxy composition (conductive adhesive).

[Example 41 and Comparative Example 26]
The epoxy composition of this example was prepared in the same manner as in Example 33 except that the epoxy compound was changed. The evaluation of this example was carried out in the same manner as in Example 33. Table 23 shows the measurement results measured in the same manner as in Example 33.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 2605 (manufactured by Mitsubishi Chemical Corporation, trade name: JER1009) was used. This epoxy compound was prepared as an epoxy solution having a content ratio of 50 mass%.
In this example, each sample (samples 381 to 392) was prepared at the ratio shown in Table 23 for the compounding ratio of the onium salt.

As shown in Table 23, the epoxy composition of this example contains 0.01 mass% (sample 381) and 0.03 mass% (sample 382) when the onium salt has a mass of the epoxy compound of 100 mass%. 0.1 mass% (sample 383), 0.4 mass% (sample 384), 1 mass% (sample 385), 4 mass% (sample 386), 10 mass% (sample 387), 12 mass% (sample 388), 15 mass% (sample) 389), 20 mass% (sample 390), 40 mass% (sample 391), 60 mass% (sample 392).
In the epoxy composition of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is less than 0.02 for the sample 381 and 0.02 or more and 40 or less for the samples 382 to 391. Sample 392 is greater than 40.
In the epoxy composition of this example, Ag powder is blended at 87.5 mass% when the mass excluding the onium salt and the solvent which are thermally decomposed from the entire epoxy composition is 100 mass%.

As shown in Table 23, the epoxy composition of each sample in which the epoxy equivalent and the compounding ratio of the onium salt of this example are within the predetermined range has a solution viscosity at 25 ° C. of 12 to 22 Pa · s, which is within the predetermined range. It has become.
As shown in Table 23, the epoxy composition of each sample of this example has a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength. From this, it can be seen that a large die shear tensile shear strength can be obtained even when the onium salt is mixed with the activity regulator.

Further, it can be confirmed that the epoxy composition of each sample becomes a cured product having high strength by heating at 80 ° C. and / or 150 ° C.
Further, it can be seen that the epoxy composition of each sample of this example has a small volume resistance value and has excellent conductivity.
As described above, the epoxy composition of each sample of this example has excellent properties as a conductive epoxy composition (conductive adhesive).

[Example 42 and Comparative Example 27]
The epoxy composition of this example was prepared in the same manner as in Example 33 except that the epoxy compound was changed. The evaluation of this example was carried out in the same manner as in Example 33. Table 24 shows the measurement results measured in the same manner as in Example 33.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 7318 (manufactured by Mitsubishi Chemical Corporation, trade name: JER1256M40) was used. This epoxy compound was prepared as an epoxy solution having a content ratio of 40 mass%.
In this example, each sample (samples 401 to 412) was prepared at the ratio shown in Table 24 for the compounding ratio of the onium salt.

As shown in Table 24, the epoxy composition of this example contains 0.01 mass% (sample 401) and 0.03 mass% (sample 402) when the onium salt has a mass of the epoxy compound of 100 mass%. 0.1 mass% (sample 403), 0.4 mass% (sample 404), 1 mass% (sample 405), 4 mass% (sample 406), 10 mass% (sample 407), 12 mass% (sample 408), 15 mass% (sample) 409), 20 mass% (sample 410), 40 mass% (sample 411), 60 mass% (sample 412).
In the epoxy composition of this example, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is less than 0.02 for the sample 401, and 0.02 or more and 40 or less for the samples 402 to 411. In sample 412, it is larger than 40.
In the epoxy composition of this example, Ag powder is blended at 87.5 mass% when the mass excluding the onium salt and the solvent which are thermally decomposed from the entire epoxy composition is 100 mass%.

As shown in Table 24, the epoxy composition of each sample in which the epoxy equivalent and the compounding ratio of the onium salt of this example are within the predetermined range has a solution viscosity at 25 ° C. of 15 to 22 Pa · s, which is within the predetermined range. It has become.

As shown in Table 24, the epoxy composition of each sample of this example has a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength. From this, it can be seen that a large die shear tensile shear strength can be obtained even when the onium salt is mixed with the activity regulator.

Further, it can be confirmed that the epoxy composition of each sample becomes a cured product having high strength by heating at 80 ° C. and / or 150 ° C.
Further, it can be seen that the epoxy composition of each sample of this example has a small volume resistance value and has excellent conductivity.
As described above, the epoxy composition of each sample of this example has excellent properties as a conductive epoxy composition (conductive adhesive).

[Example 43]
The epoxy composition of this example was prepared in the same manner as in Example 33 except that the composition of the epoxy compound, the onium salt and the solvent was changed. The evaluation of this example was carried out in the same manner as in Example 33. The epoxy composition of this example has the configurations shown in Table 25.
In this example, as the epoxy compound, an epoxy compound having an epoxy equivalent of 7318 (manufactured by Mitsubishi Chemical Corporation, trade name: JER1256M40) was used. This epoxy compound was prepared as an epoxy solution having a content ratio of 35 mass%.

In the epoxy composition of this example, in each of the samples 421 to 422, the mass ratio of the onium salt when the mass of the epoxy compound is 100 mass% is larger than 0.02 and less than 40.
The epoxy composition of this example was evaluated in the same manner as in Example 34 except that the heating conditions were different. The evaluation results are shown in Table 26.
The sample 421 and the sample 422 are heat-treated to be held at predetermined temperatures of 100 ° C., 125 ° C., 150 ° C., 175 ° C., and 200 ° C. for 30 minutes.

The sample 422 is a heat treatment in which the heating at 100 ° C. in Table 26 is held at 100 ° C. for 30 minutes. Heating at 125 ° C. is a heat treatment in which the product is held at 100 ° C. for 30 minutes and then at 125 ° C. for 30 minutes. The heating at 150 ° C. is a heat treatment in which the heating at 150 ° C. is held for 30 minutes after the heating at 125 ° C. The heating at 175 ° C. is a heat treatment that is held at 175 ° C. for 30 minutes after the heating at 150 ° C. The heating at 200 ° C. is a heat treatment that is held at 200 ° C. for 30 minutes after the heating at 175 ° C.

As shown in Table 25, the epoxy composition of each sample in which the epoxy equivalent and the compounding ratio of the onium salt of this example are within a predetermined range has a solution viscosity at 25 ° C. of 25 Pa · s, which is within a predetermined range. ing.

As shown in Table 26, the epoxy composition of each sample of this example has a large die shear tensile shear strength of 5 MPa or more. That is, it can be seen that it has high adhesive strength. From this, it can be seen that a large die shear tensile shear strength can be obtained even when the onium salt is mixed with the activity regulator.

Further, it can be confirmed that the epoxy composition of each sample becomes a cured product having high strength even when heated at 100 ° C. or higher.
Further, it can be seen that the epoxy composition of each sample of this example has a small volume resistance value and has excellent conductivity.
As described above, the epoxy composition of each sample of this example has excellent properties as a conductive epoxy composition (conductive adhesive).

[Example 44 and Comparative Example 28]
In a 30 mL screw cap bottle (manufactured by Nichiden Rika Glass Co., Ltd., trade name: SV-30), add an onium salt (brand name: SI-100) to an onium salt (brand name: SI-100) so that the reaction start temperature becomes 108 ° C. SI aid) (both manufactured by Sanshin Chemical Industry Co., Ltd.) were mixed and weighed at a mass ratio of 99: 1, and γ-butyl lactone was added as a solvent to adjust the onium salt concentration to 33 mass% and the activity adjuster. Prepared an onium salt solution containing 0.33 mass%. Weigh 0.24 g of the prepared onium salt solution.

Then, 5.40 g of an epoxy compound (manufactured by Mitsubishi Chemical Corporation, trade name: YX8000) having an epoxy equivalent of 194 is weighed and added to the onium salt solution.
The onium salt corresponds to 1.5 mass% when the total mass of the epoxy compounds is 100 mass%.

Then, 37.80 g of the purified Ag mixed powder prepared in Example 33 is added to the mixed solution with stirring.
Subsequently, 0.02 g of fine silica (manufactured by Nippon Aerosil Co., Ltd., trade name: R972) is weighed and added to the mixed solution. The fine silica (nanosilica) corresponds to 0.2 mass% when the entire epoxy composition is 100 mass%.
Further, 0.40 g of diethylene glycol diethyl ether is added as a viscosity modifier.

Insert a stainless steel microspatula into a screw cap bottle containing these five substances, and stir on a touch mixer (manufactured by Yamato Kagaku Co., Ltd., trade name: MT-31) for 3 to 5 minutes to create a uniform liquid. A mold conductive epoxy composition was used.
As described above, the conductive epoxy composition of the sample 432 of this example was prepared.
Similarly, each sample of this example was prepared by changing the compounding ratio so as to have the composition shown in Table 27.

As shown in Table 27, the epoxy composition of each sample of this example has a silica compounding ratio of 0 mass% (sample 431) and 0.2 mass% when the total mass of the epoxy composition is 100 mass%. (Sample 432), 2 mass% (Sample 433), 5 mass% (Sample 434), 10 mass% (Sample 435), 15 mass% (Sample 436), 20 mass% (Sample 437).
Further, as shown in Table 27, the epoxy composition of each sample of this example contains 0 mass% (samples 431 to 433) and 2 mass of the viscosity modifier when the total mass of the epoxy composition is 100 mass%. % (Sample 434), 10 mass% (Sample 435), 14 mass% (Sample 436), 18 mass% (Sample 437).
The epoxy composition of each sample of this example contains the mass ratio of the onium salt in the range of 0.279 or more and 139.695 or less when the mass of the epoxy compound is 100 mass%.

The one-component conductive epoxy composition of this example was applied under predetermined conditions, cured under predetermined conditions (150 ° C. × 60 minutes), and then subjected to physical property measurement (measurement of tensile shear strength and volume resistance). ..
As shown in Table 27, the tensile shear strength of this example was as high as 5 MPa or more in the samples 431 to 436. As the silica content ratio increases, the tensile shear strength tends to decrease. This is due to the relative decrease in the compounding ratio of the epoxy component.

Further, the volume resistance value of this example is a small resistance value of 10-4 Ωcm level in all the samples. That is, the cured product of the epoxy composition of this example exhibits excellent conductivity.
Furthermore, in the test results of the cross-cut test, the samples 431 to 436 show excellent test results.
As described above, it can be confirmed that the epoxy composition of this example can maintain its characteristics even if it contains fine silica or a viscosity modifier.

[Other comparisons]
Similarly, an epoxy composition having an epoxy equivalent of 186 (manufactured by Mitsubishi Chemical Corporation, trade name: JER828) is prepared by blending fine silica (manufactured by Nippon Aerosil Co., Ltd., trade name: R972) with less than 20 mass%. Was used for physical property measurement (measurement of tensile shear strength). The tensile shear strength was as high as 20 MPa to 22 MPa.

Prepared by blending an epoxy composition having an epoxy equivalent of 2605 (manufactured by Mitsubishi Chemical Corporation, trade name: JER1009) with fine silica particles (manufactured by Nippon Aerosil Co., Ltd., trade name: R972) having a mass% of less than 20 mass%, and measuring physical properties in the same manner. It was used for (measurement of tensile shear strength). The tensile shear strength was as high as 20 MPa to 22 MPa.
As described above, it can be confirmed that the epoxy composition can maintain its properties even if it contains fine silica, regardless of the epoxy compound.

From the above evaluation results, it was confirmed that the epoxy composition of each sample contained in each example is an epoxy composition that can be cured at a low temperature, which was difficult with the conventional one-component epoxy composition. can. The epoxy composition of each example has both characteristics of a high hardness and high strength epoxy resin that the conventional epoxy composition is good at, and a super-flexible epoxy resin that is supple like a film that the epoxy composition is not good at. It becomes a cured product (epoxy resin) equipped with. From this, the epoxy composition of each example can be used for various electric and electronic materials sensitive to heat, various films, etc., and the productivity is improved by low temperature and short time curing in industrial line production. , It demonstrates the effect of cost reduction and workability improvement by energy saving.

Further, the epoxy composition (conductive epoxy resin) containing the conductive particles is a conductive adhesive having high conductivity by containing the conductive particles.

In addition, the epoxy composition of each example is prepared at a low temperature (60 ° C. or higher, 80 ° C. or lower), which is difficult with the conventional one-component epoxy composition, by selecting the optimum compounding ratio of the epoxy equivalent and the onium salt. It is possible to heat-treat and obtain a cured resin having a tough epoxy composition. Furthermore, by selecting the optimum blending ratio of epoxy equivalent and onium salt, selecting the blending ratio of onium salt and activity modifier, and selecting onium salts with different reaction start temperatures, a conventional low-temperature type one-liquid solution can be selected. The epoxy composition of the mold latent curing agent enables storage at room temperature, which has been difficult. In addition, the reaction start temperature can be significantly lowered as compared with the epoxy composition of the medium / high temperature type one-component latent curing agent, and curing starts easily and at a low heating temperature.

Further, in the relationship between the onium salt and the epoxy equivalent, the epoxy composition having a large epoxy equivalent has excellent test results in the bending resistance test. In particular, even if the cured product is bent, it can be bent (curved, deformed) without cracking. That is, the epoxy composition of each example can be obtained as a cured product having excellent flexibility.
In addition, the epoxy compositions of Example 33 and subsequent examples containing silver powder are conductive compositions (conductive adhesives) having excellent conductivity (low volume resistivity). In particular, an excellent conductivity (low volume resistivity unthinkable in the past) on the order of 10-5 Ωcm, which is difficult to realize with a conventional epoxy composition, can be obtained. When pattern printing of an electric circuit is performed using this epoxy composition, the width and thickness of the printing can be shortened, so that cost reduction and high integration can be achieved. Further, according to the pattern printing of this electric circuit, it is possible to reduce the generation of heat, so that it is possible to prevent thermal runaway due to heat storage or the like.
In particular, according to the epoxy compositions of Example 33 and later containing silver powder, it has been found that a more excellent effect can be exhibited by setting a specific relationship between the epoxy equivalent and the compounding amount of the onium salt within the optimum compounding region.

Claims (1)

A composition comprising only an epoxy compound composed of a single component as a resin component, the epoxy compound, an onium salt, and silver powder.
The onium salt has a reaction start temperature of 45 ° C. or higher when heated together with a bisphenol A type liquid epoxy resin.
The compounding ratio of the onium salt is in the range of 10 to 70 mass% with respect to 100 mass% of the epoxy compound.
The die shear tensile shear strength of the cured product obtained by curing is 5 MPa or more, and the cured coating film obtained by applying it to the film is visually in a bending resistance test in which the position is shifted between the front and back surfaces of the film and the film is bent 180 °. A conductive epoxy composition characterized by not causing cracks.

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